WO2005095115A1 - 中空円筒状印刷基材 - Google Patents
中空円筒状印刷基材 Download PDFInfo
- Publication number
- WO2005095115A1 WO2005095115A1 PCT/JP2005/005751 JP2005005751W WO2005095115A1 WO 2005095115 A1 WO2005095115 A1 WO 2005095115A1 JP 2005005751 W JP2005005751 W JP 2005005751W WO 2005095115 A1 WO2005095115 A1 WO 2005095115A1
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- WIPO (PCT)
- Prior art keywords
- layer
- photosensitive resin
- hollow cylindrical
- core material
- resin layer
- Prior art date
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a general shape other than plane
- B32B1/08—Tubular products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/02—Engraving; Heads therefor
- B41C1/04—Engraving; Heads therefor using heads controlled by an electric information signal
- B41C1/05—Heat-generating engraving heads, e.g. laser beam, electron beam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N1/00—Printing plates or foils; Materials therefor
- B41N1/16—Curved printing plates, especially cylinders
- B41N1/22—Curved printing plates, especially cylinders made of other substances
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/18—Coating curved surfaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/05—5 or more layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/734—Dimensional stability
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2597/00—Tubular articles, e.g. hoses, pipes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L2201/00—Special arrangements for pipe couplings
- F16L2201/60—Identification or marking
Definitions
- the present invention relates to the formation of a relief image for flexographic printing plate or gravure printing by laser engraving, the formation of a surface processing pattern such as anilox roll and embossing, the formation of a relief image for printing tiles, and the formation of an electronic circuit.
- a surface processing pattern such as anilox roll and embossing
- the formation of a relief image for printing tiles and the formation of an electronic circuit.
- Patterning of functional materials such as conductor, semiconductor and insulator pattern printing, anti-reflective coatings of optical components, color filters, (near) infrared cut filters, etc., as well as liquid crystal displays or organic electorescence displays.
- the present invention relates to a cylindrical printing original plate suitable for forming an alignment film, an underlayer, a light emitting layer, an electron transporting layer, a coating film pattern of a sealing material layer and the like in the production of a display element, and a method for producing the same.
- the method of pasting a plate onto a rigid or flexible cylindrical support which is not the method of pasting a sheet-like plate while accurately aligning it on a plate cylinder, is used.
- a hollow cylindrical core material serving as a core of a cylindrical printing base material a glass fiber cloth impregnated with a thermosetting resin is wound around the surface of a cylindrical support, and is thermally cured while applying pressure.
- the method of forming a core-like material is already known as described in FRP molding in Non-patent Document 1 (Practical Plastics Molding Processing Encyclopedia, Industrial Conference, Encyclopedia Publishing Center).
- Such a hollow cylindrical core material can be obtained as a glass fiber reinforced plastic sleeve (hollow cylindrical core material) from a plurality of sleeve manufacturers.
- this method uses a thermosetting resin, there is a problem that it takes a lot of time to cure.
- a sheet-shaped printing substrate is attached to the surface of the fiber-reinforced plastic sleeve. For this reason, it is necessary to ensure the smoothness of the sleeve surface, and in the manufacturing process of the fiber-reinforced plastic sleeve, after the thermosetting process, the sleeve surface is polished to ensure surface accuracy. . Polishing this surface also took a lot of time, and there was also a problem that the reinforcing glass fibers could be scattered. In addition, the grinding wheel has been rapidly consumed for polishing the glass fiber.
- Patent Document 1 Japanese Patent No. 33917964 discloses that a sleeve (hollow cylindrical core material) for supporting a flexible printing plate is formed using a polyester film and a thermoplastic adhesive.
- a thermoplastic adhesive is used to fix the polyester film, there is a major problem that the polyester film is deformed by heat.
- Patent Document 2 Japanese Patent Application Laid-Open No. 7-506780 discloses a resin molded into a sheet on a flexible support on a cylindrical core material reinforced with synthetic resin, which is not photosensitive resin. There is a description of a laser-engravable printing substrate on which a photosensitive resin layer is laminated. However, in order to laminate the sheet-shaped photosensitive resin layer, it is premised that the cylindrical core material used has good surface accuracy V.
- Patent Document 3 Japanese Unexamined Patent Publication No. 5-505352 describes that a fibrous material is impregnated with a photosensitive resin to obtain a structure having an arbitrary shape such as a pipe by photocuring. However, there is no description of using this structure as a printing substrate. Further, there is no description about the use of a specific photopolymerization initiator, and the photosensitive resin described in Patent Document 3 is used in place of a synthetic resin used in the production of fiber-reinforced plastic conventionally used. When a fiber impregnated with a natural resin is used, there is a major problem that the surface of the resulting photocured product becomes sticky and sticky even when irradiated with light in the atmosphere where oxygen is present. Was.
- a hollow cylindrical core material for printing obtained by photo-curing a photosensitive resin composition has been unknown. Therefore, a hollow cylindrical printing substrate in which a resin layer capable of forming a pattern or a resin layer having a pattern formed on the surface of the hollow cylindrical core material is not known. Furthermore, there is no known method of using a fiber-reinforced plastic layer without polishing.
- Non-patent document 1 Industrial Research Council "Practical plastic molding and processing encyclopedia” (Encyclopedia Publishing Center)
- Patent document 1 Japanese patent 3391794
- Patent Document 2 Japanese Patent Publication No. Hei 7-506780
- Patent Document 3 Japanese Patent Publication No. 5-505352
- An object of the present invention is to provide a hollow cylindrical printing base material having good plate thickness accuracy and dimensional accuracy, easily and in a short time.
- a cured photosensitive resin layer having a thickness of 0.05 mm or more and 50 mm or less.
- a cured resin layer (1) comprising a fibrous, cloth-like or film-like reinforcing material.
- the present invention optionally comprises at least a hollow cylindrical core material (A) of the hollow cylindrical printing base material including the perimeter adjusting layer (F), the cushion layer (E), or the rigid body layer (G).
- the photosensitive The technical idea of the present invention is to form the resin composition by photo-curing. By using a photosensitive resin, it is possible to form a structure including the hollow cylindrical core material (A) in a very short time. Further, since printing can be performed simply by installing a hollow cylindrical printing plate having an uneven pattern on the surface of the hollow cylindrical printing substrate of the present invention in a printing press, the printing plate on a plate cylinder, which has been conventionally performed, is used. The alignment step and the printing plate fixing step can be omitted, and the steps can be greatly simplified.
- the present invention is as follows.
- the hollow cylindrical core material (A) comprising a reinforcing material in the form of a resin, a cloth or a film, and having a Shore D hardness of 30 to 100 degrees of the cured photosensitive resin layer (1); as well as
- a cylindrical printing substrate comprising:
- the patternable resin layer (B) is a photosensitive resin composition layer capable of forming a pattern by photoengraving technology or a photosensitive resin cured layer (3) capable of laser engraving.
- a cushion layer (E) is further laminated between the hollow cylindrical core material (A) and the resin layer (B) on which the pattern can be formed or the resin layer (C) with the pattern formed on the surface.
- the thickness of the cushion layer (E) is not less than 0.05 mm and not more than 50 mm.
- the hollow cylindrical printing substrate according to any one of 3.
- the hollow cylindrical printing substrate according to the above item 4 wherein the thickness of the substrate is 0.1 mm or more and 100 mm or less.
- a rigid body layer (G) is further provided between the resin layer (B) capable of forming a pattern or the resin layer (C) having a pattern formed on its surface and the cushion layer (E). 4.
- the photosensitive resin cured material constituting the hollow cylindrical core material (A) is formed by photo-curing a liquid photosensitive resin composition at 20 ° C./1. 7.
- Resin layer (B) which also has strength has at least one kind of bond selected from the group consisting of carbonate bond, urethane bond and ester bond force 2.
- the hollow cylindrical printing substrate according to the above item 2 comprising a compound and an inorganic porous material.
- the cured photosensitive resin constituting the hollow cylindrical core material (A) contains a photopolymerization initiator or a decomposition product of the photopolymerization initiator, and the photopolymerization initiator starts hydrogen abstraction type photopolymerization.
- a hollow cylindrical core material for forming a hollow cylindrical printing substrate comprising a cured photosensitive resin layer (1) having a thickness of 0.05 mm or more and 50 mm or less, wherein the photosensitive resin is The above-mentioned hollow, wherein the cured product layer (1) contains a fibrous, cloth-like or film-like reinforcing material, and the Shore D hardness of the photosensitive resin cured product layer (1) is 30 to 100 degrees. Cylindrical core material.
- the photosensitive resin is irradiated with a light beam containing light having a wavelength of 200 nm or more and 450 nm or less in the atmosphere.
- a step of photo-curing the composition layer to form a cured photosensitive resin layer (1), a resin layer (B) or a resin layer capable of forming a pattern on the hollow cylindrical core material (A) formed by the above steps A method for producing a hollow cylindrical printing substrate, comprising a step of laminating a resin layer (C) having a pattern formed on a surface.
- a sheet obtained by adding a liquid photosensitive resin composition or a semi-cured liquid photosensitive resin composition to a fibrous, cloth-like or film-like reinforcing material is wound around the surface of a cylindrical support. And irradiating the formed photosensitive resin composition layer with a light beam containing light having a wavelength of 200 nm or more and 450 nm or less in the atmosphere, and photo-curing the photosensitive resin composition layer to cure the photosensitive resin composition layer ( Step 1), a step of laminating a resin layer (B) capable of forming a pattern on the hollow cylindrical core material (A) formed in the above step or a resin layer (C) having a pattern formed on the surface.
- a method for producing a hollow cylindrical printing substrate comprising:
- the method of laminating the resin layer (B) includes a step of applying the photosensitive resin composition, a step of applying the photosensitive resin composition and then photo-curing, or a step of forming the photosensitive layer formed into a sheet.
- the method further includes the step of forming at least one resin layer (D) on the cylindrical support, When the resin film is wound on the cylindrical support in the step of forming the resin film, the both ends of the resin film are not overlapped (the seam generated at the joint portion between the both ends is 2 mm or less). Or a step of covering with a seamless resin tube formed in a cylindrical shape, or a step of applying a liquid photosensitive resin composition on a cylindrical support and curing it by light irradiation. The method described in 12. or 13. above.
- the method includes a step of laminating a perimeter adjusting layer (F) on the hollow cylindrical core material (A). 12. The method according to any one of 12. above, wherein the step of laminating (F) includes a step of applying a liquid photosensitive resin on the hollow cylindrical core material (A) and photo-curing by light irradiation. the method of.
- the hollow cylindrical core material (A) or Includes a step of laminating a cushion layer (E) on the perimeter adjusting layer (F), and the method of laminating the cushion layer (E) is based on the hollow cylindrical core material (A) or the perimeter adjusting layer (F). 17.
- the method according to the above 16 including a step of applying a liquid photosensitive resin thereon and photocuring it by light irradiation, or a step of attaching a cushion tape via an adhesive layer or an adhesive layer.
- the step of laminating the rigid body layer (G) on the cushion layer (E) includes the step of laminating the rigid body layer (G).
- the hollow cylindrical printing substrate of the present invention has good plate thickness accuracy and dimensional accuracy, and can be formed easily and in a short time.
- the hollow cylindrical core material (A) of the present invention has a thickness of 0.05 to 50 mm, preferably 0.1 to 20 mm, and more preferably 0.2 to 10 mm. It is preferably formed from 1). Further, the cured photosensitive resin layer (1) preferably has a fibrous, cloth-like or film-like reinforcing material.
- the thickness of the cylindrical core material of the present invention is 0.05 mm or more and 50 mm or less, shape stability can be ensured, the weight is not extremely heavy, and it is easy to carry.
- the term fibrous refers to a thread-like material, in which fine fibers are bundled or broken. Including things.
- the term “fabric” refers to a woven fabric in which fibers are knitted or a nonwoven fabric in which short fibers are irregularly joined.
- the cloth-like reinforcing material used in the present invention may be a woven cloth or a non-woven cloth.
- specific examples of the organic fibers include aramide fibers, polyimide fibers, polyester fibers, and acrylic fibers.
- a nonwoven fabric formed with the strength of cellulose nanofibers produced by Nocteria may be used.
- Specific examples of the inorganic fibers include glass fibers and carbon fibers.
- the fibrous reinforcing material made of the above-mentioned organic fiber or inorganic fiber can be used by being wound around the surface of the cylindrical support.
- the film-like reinforcing material used in the present invention preferably has a thickness of 1 ⁇ m or more and 100 ⁇ m or less. A more preferred range is from 5 m to 80 m, and an even more preferred range is from 10 m to 50 ⁇ m. If the thickness of the film-like reinforcing material is 1 ⁇ m or more and 100 ⁇ m or less, the handling of the film-like reinforcing material is easy and the reinforcing effect of the photosensitive resin cured material layer (1) is sufficiently obtained. be able to.
- the film-like reinforcing agent is not particularly limited, but is selected from a group of polyester, polyimide, polyamide, polyamideimide, polysulfone, polyether ether ketone, polyphenylene ether, polyphenylene ether, and polyolefin. It is preferable that at least one kind of material is formed, and two or more kinds of laminates may be used.
- the linear thermal expansion coefficient of the film-like reinforcing material is preferably from -10 ppmZ ° C to 150 ppmZ ° C, and more preferably from -10 ppmZ ° C to 100 ppmZ ° C.
- the coefficient of linear thermal expansion of the film-like reinforcing material is preferably measured using a thermomechanical measurement method (TMA) in a temperature range of 20 ° C to 80 ° C.
- the film-like reinforcing material and the photosensitive resin cured product forming the photosensitive resin cured product (1) are alternately laminated. It is preferable to have a laminated structure.
- the thickness of the cured photosensitive resin laminated on the film-like reinforcing material is preferably 1 ⁇ m or more and 100 ⁇ m or less. A more preferred range is from 5 ⁇ m to 80 ⁇ m, and a still more preferred range is from 10 m to 50 m. If the thickness of the cured photosensitive resin is within the above range, sufficient adhesion or tackiness to the film-like reinforcing material is ensured. And the dimensional stability of the cured photosensitive resin layer (1) can be ensured.
- the adhesiveness or tackiness between the film-like reinforcing material and the cured photosensitive resin is preferably 50 NZm or more, more preferably 200 NZm or more, and even more preferably 500 NZm or more.
- adheresiveness refers to a property capable of peeling, and is used separately from adhesiveness in which an interface is broken when peeled.
- the light transmittance of the film-like reinforcing material used in the present invention is preferably from 10% to 100%, more preferably from 30% to 100%, and more preferably from 10% to 100% in the range of wavelength 370 nm to 350 nm.
- the preferred range is 50% or more and 100% or less.
- the surface of the reinforcing material used in the present invention may be surface-modified with a compound having a polymerizable unsaturated group.
- a silane coupling agent having a functional group such as an acrylic group, a methacryl group, a mercapto group, or a vinyl group, a titanium coupling agent, or the like can be used to chemically react with a functional group such as a hydroxyl group exposed on the surface of the reinforcing agent. .
- an active functional group such as a hydroxyl group can be formed on the surface by surface treatment of irradiation with plasma, vacuum ultraviolet rays, or the like, and the silane coupling agent or the titanium coupling agent can be reacted.
- the Shore D hardness of the cured photosensitive resin layer (1) of the present invention is 30 to 100 degrees, preferably 40 to 100 degrees, and more preferably 50 to 100 degrees. When the Shore D hardness is 30 degrees or more and 100 degrees or less, it is easy to maintain a cylindrical shape and dimensional stability can be secured.
- the photosensitive resin composition (6) has, as components, a resin (a) having a number average molecular weight of 1,000 to 300,000 and a polymerizable unsaturated group in the molecule having a number average molecular weight of less than 1000.
- organic compound (b) In order to obtain the cured photosensitive resin layer (1) having the above hardness range, two or more, more preferably three or more polymerizable polymers are present in the molecule of the resin (a) and the organic compound (b). It is desirable that the compound structure containing a saturated group contains 10% by weight or more, more preferably 20% by weight or more of the total amount of the resin (a) and Z or the organic compound (b).
- a compound having a rigid skeleton site such as an aromatic hydrocarbon group and Z or an alicyclic hydrocarbon group in the molecule of the resin (a) and Z or the organic compound (b) may be used.
- the content of the resin (a) and Z or the organic compound (b) is preferably at least 10 wt%, more preferably at least 20 wt%.
- the monomer unit having a rigid portion is contained in an amount of 1% or more, more preferably 5% or more, further preferably 10% or more of the monomer unit constituting the resin (a).
- the maximum difference of the unevenness existing on the surface is preferably 30 m or less, more preferably 20 m or less. Below, more preferably 10 m or less. If the maximum value of the height difference is 30 m or less, a sheet-shaped printing plate, printing plate, blanket, etc. can be directly attached. Further, the surface of the hollow cylindrical core material (A) may have irregularities on the surface which does not need to be smoothed by polishing. In this case, since the polishing step is not performed, the manufacturing time of the hollow cylindrical core material (A) can be greatly reduced, and the powder of the inorganic reinforcing material such as glass fiber does not scatter.
- the height difference between the irregularities is preferably 20 m or more and 500 m or less.
- the height difference is within the above range, when the liquid photosensitive resin is applied on the hollow cylindrical core material (A) and a layer to be laminated thereon is formed, entrapment of air bubbles and the like can be prevented.
- the height difference of the unevenness existing on the surface of the cylindrical core material (A) of the present invention is measured using a contact displacement sensor (trade name “AT3-010” manufactured by KEYENCE CORPORATION), and the contact displacement sensor is fixed. Then, the circumference of one place is measured by rotating the cylindrical core material (A) fixed to the cylindrical support such as an air cylinder once.
- the rotation speed of the cylindrical core material (A) is preferably set to a speed at which the response of the contact-type sensor can follow, and is preferably 1 rotation or less per second.
- the height difference is measured with one point arbitrarily selected on the surface of the cylindrical support as a reference point.
- the maximum value of the height difference with respect to the three reference points at the measurement points is defined as the maximum value of the height difference of the unevenness in the present invention.
- the height difference of the entire surface of the cylindrical support is 10 / zm or less, more preferably 5 / zm or less with respect to this reference position. Desirably. Therefore, it is desirable that the production accuracy of the air cylinder and the device for fixing and rotating the air cylinder is also less than 10 ⁇ m, preferably less than 5 ⁇ m.
- the cured photosensitive resin layer (1) constituting the hollow cylindrical core material (A) and the layer (4) constituting the resin layer (D) are each heated at 20 ° C.
- the photosensitive resin compositions (6) and (7) in a liquid state are preferably formed by photo-curing in the air.
- the viscosity of the liquid photosensitive resin composition at 20 ° C is lOPa's or more and 50 kPa's or less, more preferably 50? &'5 or more and 201 ⁇ 1 ⁇ 2'5 or less, further preferably lOOPa's or less. It is not more than lOkPa's.
- the liquid resin can be easily applied in a cylindrical shape, and within the above viscosity range, it can be easily formed without causing liquid dripping due to gravity.
- the method for forming the cured photosensitive resin layer (1) constituting the hollow cylindrical core material (A) of the present invention comprises the steps of: forming the photosensitive resin composition (6) on a cylindrical support; Coating, irradiating a light beam containing light having a wavelength of 200 nm or more and 450 nm or less, and a step of adjusting the thickness of the obtained cured photosensitive resin layer.
- the method for applying the photosensitive resin composition (6) on the cylindrical support is not particularly limited, but includes spray coating, blade coating, gravure coating, reverse roller coating, and kistati coating. And a commonly used coating method such as a high-pressure knife coating method. Rotating the cylindrical support around the axis during application of the photosensitive resin composition (6) is effective for uniform application.
- the light source used for photo-curing the formed photosensitive resin composition layer (1) is preferably a light source that emits light including light having a wavelength of 200 nm or more and 450 nm or less! / ⁇ .
- a light source that emits light including light having a wavelength of 200 nm or more and 450 nm or less! / ⁇ .
- metalno, ride lamp, high pressure mercury lamp, ultra high pressure mercury lamp, carbon arc lamp, chemical lamp, germicidal lamp and the like can be mentioned.
- the light irradiation can be performed simultaneously with the application of the photosensitive resin composition (6), or the light irradiation may be performed after the application.
- the thickness of the cured photosensitive resin layer (1) obtained by light irradiation can be adjusted by cutting with a turning tool such as a turning tool or cutting with a rotating polishing wheel.
- a step of winding a fibrous material, a cloth-like material or a film-like material around the surface of the cylindrical support may be further included.
- the method of winding the fibrous material, the cloth-like material or the film-like material is not particularly limited.
- a method of spirally winding the formed material is preferable because it has a large effect of maintaining the strength of the hollow cylindrical core material (A).
- the photosensitive resin composition (6) or the semi-cured photosensitive resin composition (6) is applied to the surface of or inside a fibrous or cloth-like material wound on a cylindrical support, or to the surface of a film-like material. It is also possible to use one containing an object!
- the semi-cured product of the photosensitive resin composition (6) refers to the photosensitive resin composition (6) that is completely cured and hardened before the stage where physical properties such as hardness no longer change. It refers to the photo-cured state of the object, and can be easily obtained by setting the amount of light to be applied to be small.
- the standard of the amount of light that can form a semi-hardened product is 80% or less, more preferably 50% or less, even more preferably 30% or less of the minimum light amount at which physical properties such as hardness do not change.
- the photosensitive resin composition (6) When the photosensitive resin composition (6) is applied to the surface of a fibrous, cloth-like, or film-like material and wound on a cylindrical support, apply the photosensitive resin composition (6).
- the method for carrying out the method is not particularly limited, and a known method can be used. For uniform application, a doctor blade method, a roll coating method, and a spray coating method are preferable. Further, the inside of the fibrous material or cloth (the space between the fibers) may be impregnated with the photosensitive resin composition (6) or filled by impregnation. The fiber or cloth containing the semi-cured photosensitive resin composition (6) can be photocured while being wound on a cylindrical support. This method is effective for securing light transmittance when fibrous or cloth-like materials are laminated.
- the cured photosensitive resin layer (1) constituting the hollow cylindrical core material (A) of the present invention is a compound having a rigid skeleton site such as an aromatic hydrocarbon group and Z or an alicyclic hydrocarbon group. It is preferable to have
- the aromatic hydrocarbon group is one of the skeletons of an aromatic compound such as a phenyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a pyrenyl group. Refers to a functional group having an atomic group excluding a hydrogen atom.
- An alicyclic hydrocarbon group is a functional group having the remaining atomic group of a carbocyclic compound having a structure in which carbon atoms are bonded in a ring, except for one hydrogen atom of a compound that does not belong to an aromatic compound.
- a cyclohexyl group, a bicyclooctyl group, a cyclopentagel group, a cyclooctyl group and the like can be mentioned.
- the Shore D hardness of the cured resin layer (1) can be increased, which is effective in maintaining rigidity and ensuring dimensional stability.
- the photosensitive resin composition (6) for forming the cured photosensitive resin layer (1) of the present invention comprises a resin (a) having a number average molecular weight of 1,000 or more and 300,000 or less, and a number average molecular weight of 1,000. It is preferable to contain an organic compound (b) having a polymerizable unsaturated group in a molecule thereof and a photopolymerization initiator. Further, the photopolymerization initiator contains a hydrogen abstraction type photopolymerization initiator and a collapse type photopolymerization initiator, or a site acting as a hydrogen abstraction type photopolymerization initiator in the same molecule and a collapse type photopolymerization initiator. A compound having a site that acts as an initiator is particularly preferable because a photosensitive resin composition that is photocured by a radical polymerization reaction can be photocured in the atmosphere.
- the resin (a) a known polymer compound which is not particularly limited can be used.
- compounds having a rigid molecular structure such as an aromatic hydrocarbon compound and Z or an alicyclic hydrocarbon compound in the molecule are preferable.
- a rubber-based polymer compound having high rubber elasticity such as synthetic rubber, thermoplastic elastomer, etc., a thermoplastic resin having a high elastic modulus, a solid resin at 20 ° C, or an intramolecular resin.
- Preferred examples of the polymer include liquid polyurethane at 20 ° C., such as unsaturated polyurethane having a polymerizable unsaturated group, unsaturated polyester, and liquid polybutadiene.
- Preferred rubber-based polymer compounds include natural rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, polybutadiene rubber, polyisoprene rubber, ethylene propylene rubber, and a polymer of a monobutyl-substituted aromatic hydrocarbon monomer and a conjugated gen monomer. ,.
- the monovinyl-substituted aromatic hydrocarbon monomer styrene, a-methylstyrene, p-methylstyrene, p-methoxystyrene and the like are used, and as the conjugated diene monomer, butadiene and isoprene are used.
- thermoplastic elastomer examples include styrene butagen block copolymer and styrene isoprene block copolymer.
- thermoplastic resin having a high elastic modulus examples include polycarbonate, polysulfone, polyethersulfone, polyamide, polyamic acid, polyester, and polyphenylene ether. In the case of a solid resin at 20 ° C., those which can be dissolved in a solvent are particularly preferred.
- the preferred range of the number average molecular weight of the resin (a) is 1000 or more and 300,000 or less, more preferably 50 or less. It is from 00 to 100,000, and more preferably from 7000 to 50,000.
- the number average molecular weight in the present invention is measured by gel permeation chromatography (GPC method), and a value obtained by converting polystyrene having a known molecular weight into a standard is used.
- the polymerizable unsaturated group is preferably a functional group involved in a radical polymerization reaction, an addition polymerization reaction, or a ring-opening addition polymerization reaction.
- examples of the polymerizable unsaturated group that undergoes a radical polymerization reaction include a butyl group, an acetylene group, a methacryl group, and an acryl group.
- examples of the polymerizable unsaturated group that undergoes the addition polymerization reaction include a cinnamoyl group, a thiol group, and an azide group.
- epoxy group, oxetane group, cyclic ester group, dioxysilane group, spiro orthocarbonate group, spiro ortho ester group, bicyclo ortho ester group, cyclosiloxane group, cyclic Examples include an iminoether group.
- the resin (a) is an aryl group, a linear or branched alkyl group substituted with at least one aryl group in the molecule, an alkyl group , An alkoxycarbon group, a hydroxyl group, and a formyl group force having at least one type of organic group selected, or a carbonate bond or an ester bond, and the organic group or the bond is directly bonded. It is preferable to have at least 2% of hydrogen atoms ( ⁇ -position hydrogen) bonded to the carbon atoms with respect to all hydrogen atoms in the molecule.
- a photo-curable photosensitive resin composition is provided.
- Preferred examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthryl group, a pyrenyl group, and a phenanthryl group. Further, a linear or branched alkyl group substituted with an aryl group, such as a methylstyryl group or a styryl group, is preferred.
- the content of ⁇ -position hydrogen can be analyzed by nuclear magnetic resonance spectroscopy (NMR) focusing on hydrogen atoms.
- NMR nuclear magnetic resonance spectroscopy
- the content of the resin (a) component is preferably in the range of 10 to 90 wt%, more preferably, based on the total weight of the nonvolatile components. Is from 20 to 80% by weight, more preferably from 30 to 70% by weight.
- the organic compound (b) having a polymerizable unsaturated group contained in the photosensitive resin composition (6) is a compound that undergoes a radical polymerization reaction, an addition polymerization reaction, and a ring-opening addition polymerization reaction, and known compounds may also be used. It can be used and is not particularly limited.
- radical-reactive compounds unsaturated-tolyls such as ethylene, propylene, styrene, dibutylbenzene and other olefins, acetylenes, (meth) acrylic acid and derivatives thereof, haloolefins and acrylonitrile, and (meth) Acrylamide and its derivatives, unsaturated dicarboxylic acids such as maleic anhydride, maleic acid, fumaric acid and its derivatives, vinyl acetate, N-bulpyrrolidone, N-vinylcarbazole, etc. (Meth) acrylic acid and its derivatives are preferred examples.
- the derivative examples include an aliphatic compound having a cycloalkyl group, a bicycloalkyl group, a cycloalkenyl group, a bicycloalkenyl group, a benzyl group, a fuel group, a phenoxy group, a naphthalene skeleton, an anthracene skeleton, Aromatic compounds having a biphenyl skeleton, a phenanthrene skeleton, a fluorene skeleton, etc., compounds having an alkyl group, a halogenated alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, an aminoalkyl group, a glycidyl group, etc., alkylene glycol, poly Examples thereof include ester compounds with polyhydric alcohols such as oxyalkylene glycol and polyalkylene glycol / trimethylolpropane, and compounds having a polysiloxane structure such as polydimethyls
- Examples of the polymerizable unsaturated group having addition polymerization reactivity include a compound having a cinnamoyl group, a thiol group, and an azide group.
- a polymerizable unsaturated group having ring-opening addition reactivity epoxy group, oxetane group, cyclic ester group, dioxysilane group, spiro orthocarbonate group, spiro ortho ester group, bicyclo ortho ester group, cyclosiloxane group, cyclic imino ether Compounds having a group or the like can be given.
- Particularly useful compounds having an epoxy group As compounds having an epoxy group, compounds obtained by reacting epichlorohydrin with various polyols such as diols and triols, and peracids reacting with ethylene bonds in the molecule And epoxy conjugates obtained by the above method.
- Epoxy compounds such as glycidyl ether, polytetramethylene glycol diglycidyl ether, poly (propylene glycol adipate) diol diglycidyl ether, poly (ethylene glycol adipate) diol diglycidyl ether, poly (force prolataton) diol diglycidyl ether, epoxy-modified silicone Oils can be mentioned.
- an alicyclic group is used as the resin (a) or the organic compound (b). It is preferable to contain at least one or more hydrocarbon compounds or aromatic hydrocarbon compounds, and these alicyclic hydrocarbon compounds or aromatic hydrocarbon compounds can be used as the entirety of the resin (a) or the organic compound (b).
- the content is preferably 20% by weight or more, more preferably 50% by weight or more.
- the derivative of the aromatic hydrocarbon compound may be an aromatic hydrocarbon compound having an element such as nitrogen or sulfur.
- the ratio of the resin (a) and the organic compound (b) in the photosensitive resin composition (6) is preferably 5 to 200 parts by weight based on 100 parts by weight of the resin (a).
- Magusu 20-: L00 parts by weight is more preferable.
- a known photopolymerization initiator can be used as the photopolymerization initiator (c) contained in the photosensitive resin composition (6).
- known radical polymerization initiators such as aromatic ketones and benzoyl ethers can be used.
- a combination of a hydrogen abstraction type photopolymerization initiator such as benzophenone and a collapse type photopolymerization initiator such as 2,2-dimethoxyphenylacetophenone is particularly preferable. Furthermore, even when a compound having a site acting as a hydrogen abstraction type polymerization initiator and a site acting as a decay type photopolymerization initiator in the same molecule is used, the effect of photohardening in the atmosphere can be seen. a-Aminoacetophenones can be mentioned.
- each R independently represents a hydrogen atom or an alkyl group of 1 to LO carbon atoms.
- X represents an alkylene group having 1 to 10 carbon atoms.
- photoinitiated thione polymerization initiators such as aromatic diazonium salts, aromatic odonium salts, aromatic sulfo-pam salts that absorb light to generate acids, or generate bases by absorbing light And a photopolymerization initiator.
- the addition amount of the photopolymerization initiator is preferably in the range of 0.01 to 10 wt% of the total amount of the resin (a) and the organic compound (b).
- a resin layer (D) can be provided as an optional layer.
- the resin layer (D) is provided on the inner surface of a hollow cylindrical core material (A) (reference numeral 2) composed of a photosensitive resin cured material layer (1) as shown by reference numeral 1 in FIG. It has a composition different from that of the photosensitive resin composition (6) that forms the photosensitive resin cured material layer (1), and has a thickness of 0.01 mm or more and 1 mm or less, more preferably 0.05 mm or more and 0.5 mm or less. .
- the resin layer (D) is used for the purpose of reducing unevenness on the inner surface of the photosensitive resin cured layer (1) containing a reinforcing material. Use fiber as reinforcement It is effective when you are.
- the material constituting the resin layer (D) may be a resin film or a resin tube formed into a cylindrical shape. When wrapping a resin film around a cylindrical support, it is preferable that the resin film be wrapped so that both ends do not overlap and the seam generated at the joint between the both ends is 2 mm or less. . Further, the cured photosensitive resin layer (4) having a different composition from the cured photosensitive resin layer (1) containing a reinforcing material may be used. In particular, the resin layer (D), which is a joint, is preferred. When the thickness of the resin layer (D) is not less than 0.5 Olmm and not more than 0.5 mm, it is sufficient to reduce unevenness on the inner surface of the cured photosensitive resin layer (1) having a reinforcing material.
- fine particles may be contained as a reinforcing material for the purpose of reducing friction on the inner surface of the resin layer (D).
- the average particle diameter of the fine particles to be contained is preferably from 0.01 ⁇ m to 100 ⁇ m, more preferably from 0.05 ⁇ m to 20 ⁇ m, and still more preferably from 0.1 ⁇ m to 10 ⁇ m. m or less.
- the shape of the fine particles is preferably spherical.
- spherical fine particles having a sphericity in the range of 0.5 to 1 are contained in 70% or more of the total number of particles.
- the sphericity of the present invention is defined as the radius R1 of the largest circle completely falling within the projected shape of the fine particles and the smallest circle completely including the projected shape when the fine particles are observed with a scanning electron microscope. Defined as the ratio to the radius R2, ie R1ZR2.
- the number of spherical microparticles is observed with a scanning electron microscope and measured at a magnification at which at least about 100 particles enter the microscope field of view. It is preferable to use image recognition software for the measurement.
- the spherical fine particles referred to in the present invention include those having a smooth surface without projections or the like on the surface which does not need to be perfectly spherical. Examples of the material of the fine particles include hard ceramics such as silicon nitride, boron nitride and silicon carbide; hard metals such as titanium and chromium; and organic substances having a fluorine atom or a silicon atom such as polytetrafluoroethylene and polydimethylsiloxane.
- a perimeter adjusting layer (F) can be provided as an optional layer.
- the circumferential length adjusting layer (F) can be provided on the hollow cylindrical core material (A) according to the circumferential length of the printing plate to be used.
- the circumference of the printing plate varies widely depending on the printed material to be produced. Conventionally, adjust the circumference
- a method was generally used in which a hard rubber was wound on a cylindrical core material, a vulcanization crosslinking, surface polishing, and a crosslinking stabilization process were performed, and a layer was formed over a considerable time.
- the circumference adjusting layer (F) has a function of adjusting the circumference of the printing plate and also a function of smoothing irregularities on the surface of the hollow cylindrical core material (A).
- the unevenness of the surface is extremely large.
- the process of polishing the surface of the hollow cylindrical core material requires additional work to increase the smoothness, and if it takes time, there is a demerit that the production cost is greatly increased without the need for force.
- the hollow cylindrical core material (A) has a very good conformability to irregularities on the surface. There is no need to polish the surface of the core material (A). Of course, a polishing treatment may be performed to finish the surface.
- the material of the circumference adjusting layer (F) of the present invention is not particularly limited, but is preferably a cured product of the photosensitive resin composition (9).
- the cured product preferably has a Shore D hardness of 5 to 100 degrees, more preferably 20 to 100 degrees, and still more preferably 30 to 100 degrees. If the Shore D hardness is 5 degrees or more and 100 degrees or less, dimensional stability in the thickness direction during printing can be sufficiently ensured.
- the photosensitive resin composition (9) constituting the circumference adjusting layer (F) may be a solid photosensitive resin composition at 20 ° C., but may be a liquid photosensitive resin composition. Liquid photosensitive resin compositions are particularly preferred from the viewpoint that the thickness of the circumference adjusting layer (F) can be arbitrarily changed. A solvent may be contained in the liquid photosensitive resin composition. However, a solvent removing step is required, and therefore, a solventless liquid photosensitive resin composition is more preferable. When a liquid photosensitive resin composition is used, a seamless layer having a uniform thickness can be formed.
- the liquid photosensitive resin composition preferably has a viscosity at 20 ° C.
- the method of forming the circumference adjusting layer (F) includes a step of applying the photosensitive resin composition (9) on the hollow cylindrical core material (A), and a step of irradiating light to cure the resin. It is preferable to include a step of adjusting the thickness of the obtained cured photosensitive resin layer.
- the method of applying the photosensitive resin composition (9) on the hollow cylindrical core material (A) is not particularly limited, but includes spray coating, blade coating, gravure coating, reverse roller coating, and the like. Commonly used coating methods such as a kistastic coating method and a high-pressure air knife coating method can be used. When the photosensitive resin composition (9) is applied and applied, rotating the hollow cylindrical core material (A) around the axis is effective for uniform application.
- the light source used for photocuring the formed photosensitive resin layer is preferably a light source that generates a light beam including light having a wavelength of 200 nm or more and 450 nm or less.
- a light source that generates a light beam including light having a wavelength of 200 nm or more and 450 nm or less.
- metal halide lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, chemical lamps, germicidal lamps, and the like can be given.
- the light irradiation can be performed simultaneously with the application of the photosensitive resin composition, or the light irradiation may be performed after the application.
- the thickness of the cured photosensitive resin layer obtained by light irradiation can be adjusted by cutting with a cutting tool such as a turning tool, cutting with a rotating polishing wheel, or polishing with a polishing cloth. Can be implemented in combination.
- processing can be performed while fixing the long axis of the hollow cylindrical core material (A) and rotating in the
- the surface of the hollow cylindrical core material (A) can be treated to improve the adhesiveness with the circumference adjusting layer (F).
- the method include a method of forming a thin adhesive layer on the surface of the hollow cylindrical core material (A), a method of forming a primer layer for improving adhesion, and a method of performing physical and chemical treatment.
- the physical treatment include a method of irradiating high energy rays such as plasma, light in a vacuum ultraviolet region, an electron beam, an ion beam, and the like, and a method of exposing to an atmosphere of high energy rays.
- an excimer UV wavelength: 172 nm
- the adhesion improving primer layer is specifically a silane coupling agent or a titanium coupling. Forming a thin layer with an agent, a silicone-based adhesion aid, or the like.
- the circumferential length adjusting layer (F) can be easily formed on the hollow cylindrical core material (A) without a seam containing bubbles.
- the hollow cylindrical printing substrate can be lightened.
- the cells contained in the layer may be open cells, but closed cells are more preferable in terms of mechanical strength.
- the open cells can be formed by a method of mixing a gas such as air into the photosensitive resin composition (9), a method of mixing a compound which generates nitrogen by heat or light, or the like.
- closed cells can be formed using hollow fine particles. Examples thereof include inorganic hollow fine particles such as hollow glass fine particles and hollow silica fine particles, and organic fine particles in the form of microcapsules.
- microcapsules having a thermal expansion property whose volume expands when heated it is preferable to use microcapsules having a thermal expansion property whose volume expands when heated.
- This type of thermally expandable microcapsule contains a volatile organic liquid inside, and when mixed with the photosensitive resin composition (9), ensures light transmittance that does not hinder photocurability. can do. Therefore, by performing the curing of the photosensitive resin composition (9) by light irradiation in combination with the thermal expansion of the thermally expandable microcapsules by heating, light curing of a thick film becomes possible.
- the photosensitive resin composition is mixed with hollow microparticles, it generally becomes cloudy because there is a large difference in the refractive index between the air layer inside and the photosensitive resin composition. Even if such a cloudy resin is applied, a thick-film photocured product can be obtained by repeatedly applying the photocured process while applying the film in a thin film state.
- the thickness of the perimeter adjusting layer (F) formed by thermal expansion is preferably 1.1 to 100 times, more preferably 1.1 to 100 times the thickness of the thermally expanded microcapsules before expansion. The range is 50 times. 1. If it is 1 time or more, it is possible to secure the lightweight adjustment of the circumference adjustment layer (F), and if it is 100 times or less, it is possible to obtain the mechanical strength of the circumference adjustment layer (F). .
- the thickness of the circumference adjusting layer (F) is preferably observed by using a scanning electron microscope or an optical microscope while exposing the cross section.
- the average diameter of the bubbles having the partition walls present in the circumference adjusting layer (F) is preferably from 0.5 m to 500 m. If it is 0.5 m or more, the circumference adjustment layer (F) is reduced in weight If it is 500 m or less, mechanical properties can be ensured even in the circumference adjusting layer (F) having a thickness of several mm.
- the size of the bubbles in the perimeter adjusting layer (F) is preferably observed using an optical microscope or a laser confocal microscope.
- the average value of the partition wall thickness is preferably 0.05 m or more and 10 m or less.
- the thickness of the partition wall can be evaluated by cutting the perimeter adjusting layer (F) and observing the cross section using a high-resolution scanning electron microscope.
- the heat-expandable microcapsules are fine particles containing a thermoplastic elastomer as a partition and containing a volatile organic liquid therein, preferably at 60 to 250 ° C, more preferably at 100 to 200 ° C.
- a thermoplastic elastomer examples include polychloride bilidene, polyacrylonitrile, polymethyl methacrylate, and the like.
- the volatile organic liquid examples include hydrocarbons such as butane, isobutane, butene, isobutene, pentane, isopentane, neopentane, hexane, and heptene.
- the partition walls may be coated with inorganic fine particles.
- the inorganic fine particles include silica, calcium carbonate, and titanium oxide.
- a preferred density range of the circumference adjustment layer (F) is, 0. lgZcm 3 or 0. 9gZcm 3 below, good Ri preferably 0. 3gZcm 3 or 0. 7gZcm 3 below. If it is 0.9 lgZcm 3 or more, the mechanical strength of the circumference adjustment layer (F) can be secured. If it is 0.9 gZcm 3 or less, the circumference adjustment layer (F) can have a light weight. Can be.
- the photosensitive resin composition (9) contains heat-expandable microcapsules, it is difficult to thermally expand the microcapsules if the photosensitive resin composition is completely light-cured. Therefore, the amount of energy of light to be irradiated is adjusted so that the photosensitive resin composition is in a semi-cured state, and thereafter, a heat treatment is performed to expand the heat-expandable microcapsules. Preferably, the photosensitive resin composition is completely cured. Alternatively, when the content of the heat-expandable microcapsules is large, the photosensitive resin composition is thinly applied on the hollow cylindrical core material (A), and the microcapsules are thermally expanded. Irradiate By repeatedly performing the operation of completing the photo-curing, the circumference adjustment layer (F) having a predetermined thickness can be formed. Also, microcapsules that have already been thermally expanded may be added to the photosensitive resin composition!
- the hollow cylindrical core material Rotating the hollow cylindrical core (A) between A) and the plate or roll-shaped object (h) placed at a certain distance while heating the photosensitive resin layer (g) For this reason, it is preferable that the photosensitive resin layer (g) is passed through the object (h) while being in contact with the object (h), as a method for forming a circumferential length adjusting layer (F) having a uniform thickness.
- Examples of the heating method include a method of blowing hot air, a method of irradiating infrared rays, and a method of heating a plate-shaped or roll-shaped object (h) using a heater, and a combination of these methods. Can also be used. Examples of a method for rapidly stopping foaming by heating include a method of blowing and cooling cold air, and a method of contacting with a cooling roll or a cooling plate.
- the photosensitive resin composition (9) for forming the perimeter adjusting layer (F) of the present invention comprises at least one kind of binder (i) and at least one kind of polymerizable unsaturated group. It is preferable that the organic compound G) has at least one or more photopolymerization initiators (k).
- a seamless layer having a uniform film thickness can be formed in which the liquid state at 20 ° C. is preferable from the viewpoint of moldability.
- the thickness to be formed is very thin, it is desirable to keep the viscosity low. As a method of lowering the viscosity, a method of adding a solvent is convenient.
- a known polymer compound can be used as the noinder (i). Specifically, a rubber-based polymer compound with rubber elasticity such as synthetic rubber or thermoplastic elastomer, a solid resin at 20 ° C such as a thermoplastic resin with a high elastic modulus, or polymerizable in the molecule.
- a rubber-based polymer compound with rubber elasticity such as synthetic rubber or thermoplastic elastomer
- a solid resin at 20 ° C such as a thermoplastic resin with a high elastic modulus
- Preferred examples of the high molecular compound include resins and the like which are liquid at 20 ° C., such as unsaturated polyurethane having an unsaturated group, unsaturated polyester, and liquid polybutadiene.
- Preferred rubber-based polymer compounds are natural rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, polybutadiene rubber, polyisoprene rubber, ethylene propylene rubber, and a polymer of a monobutyl-substituted aromatic hydrocarbon and a conjugated gen monomer.
- the monobule replacement Styrene, a-methylstyrene, p-methylstyrene, p-methoxystyrene, etc. are used as aromatic hydrocarbon monomers, butadiene, isoprene, etc. are used as conjugated diene monomers.
- thermoplastic elastomers include: Examples include styrene butagen block copolymer and styrene isoprene block copolymer.
- thermoplastic resin having a high elastic modulus include polycarbonate, polysulfone, polyether sulfone, polyether ether ketone, polyamide, polyamic acid, polyester, and polyphenylene ether. In the case of a solid resin at 20 ° C., those which can be dissolved in a solvent are particularly preferred.
- the preferred range of the number average molecular weight of the binder (i) is from 1,000 to 300,000, more preferably from 5,000 to 100,000, and still more preferably from 7000 to 50,000.
- the number average molecular weight of the present invention is a value measured by gel permeation chromatography (GPC) and converted based on polystyrene having a known molecular weight.
- the binder (i) is a linear or branched alkyl machine substituted with an aryl group, at least one aryl group in the molecule, an alkyl group, an alkoxy group. It has at least one organic group selected from the group consisting of a carbonyl group, a hydroxyl group, and a formyl group, or has a carbonate bond or an ester bond, and the organic group or the bond is directly bonded! It is preferable to have at least 2% of hydrogen atoms ( ⁇ -position hydrogen) bonded to carbon atoms relative to all hydrogen atoms in the molecule.
- a compound having the specific functional group and having a hydrogen atom bonded to a carbon atom to which the organic group is directly bonded allows the compound to be exposed to the air.
- Preferred examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthryl group, a pyrenyl group, and a phenanthryl group.
- a linear or branched alkyl group substituted with an aryl group, such as a methylstyryl group or a styryl group is preferred.
- the content of ⁇ -position hydrogen can be analyzed by nuclear magnetic resonance spectroscopy H-NMR method focusing on hydrogen atoms.
- the content of the binder (i) is preferably in the range of 10 to 90 wt%, more preferably 20 to 80 wt%, and more preferably 20 to 80 wt%. Preferably it is 30 to 69 wt%.
- the organic compound (j) having a polymerizable unsaturated group contained in the photosensitive resin composition (9) is a compound that undergoes a radical polymerization reaction, an addition polymerization reaction, and a ring-opening addition polymerization reaction. Compounds can also be used and are not particularly limited.
- radical reactive compounds ethylene, propylene, styrene, dibutylbenzene, etc., olefins, acetylenes, (meth) acrylic acid and derivatives thereof, haloolefins, acrylonitrile and other unsaturated-tolyls, (meth) acrylamide and the like
- unsaturated dicarboxylic acids such as maleic anhydride, maleic acid, fumaric acid, and derivatives thereof, vinyl acetates, N-butylpyrrolidone, N-vinylcarbazole, etc.
- acrylic acid and its derivatives are preferred examples.
- the derivative examples include an aliphatic compound having a cycloalkyl group, a bicycloalkyl group, a cycloalkenyl group, a bicycloalkenyl group, a benzyl group, a fuel group, a phenoxy group, a naphthalene skeleton, an anthracene skeleton, Aromatic compounds having a biphenyl skeleton, a phenanthrene skeleton, a fluorene skeleton, etc., compounds having an alkyl group, a halogenated alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, an aminoalkyl group, a glycidyl group, etc., alkylene glycol, poly Examples thereof include ester compounds with polyhydric alcohols such as oxyalkylene glycol and polyalkylene glycol / trimethylolpropane, and compounds having a polysiloxane structure such as polydimethyls
- Examples of the polymerizable unsaturated group having addition polymerization reactivity include a compound having a cinnamoyl group, a thiol group, and an azide group.
- a polymerizable unsaturated group having ring-opening addition reactivity epoxy group, oxetane group, cyclic ester group, dioxysilane group, spiro orthocarbonate group, spiro ortho ester group, bicyclo ortho ester group, cyclosiloxane group, cyclic imino ether Compounds having a group or the like can be given.
- Particularly useful compounds having an epoxy group As compounds having an epoxy group, compounds obtained by reacting epichlorohydrin with various polyols such as diols and triols, and peracids reacting with ethylene bonds in the molecule And epoxy conjugates obtained by the above method.
- Epoxy compounds such as glycidyl ether, polytetramethylene glycol diglycidyl ether, poly (propylene glycol adipate) diol diglycidyl ether, poly (ethylene glycol adipate) diol diglycidyl ether, poly (force prolataton) diol diglycidyl ether, epoxy-modified silicone Oil (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "HF-105”) can be mentioned.
- the organic compound (j) has at least one kind of an alicyclic or aromatic derivative.
- the content of (j) is preferably at least 20 wt%, more preferably at least 50 wt%.
- the aromatic derivative may be an aromatic compound having an element such as nitrogen or sulfur.
- the ratio of the binder (i) and the organic compound (j) in the photosensitive resin composition (9) is usually 5 to 200 parts by weight of the organic compound (j) based on 100 parts by weight of the binder (i).
- the preferred range is 20 to 100 parts by weight.
- a known photopolymerization initiator can be used as the photopolymerization initiator (k) contained in the photosensitive resin composition (9).
- known radical polymerization initiators such as aromatic ketones and benzoyl ethers can be used.
- benzophenone, Michler's ketone, benzoin methyl ether, benzoin E chill ether, benzoin isopropyl ether, a Mechiroru base emission zone in ether, a Metokishi base Nzoinmechi ether, 2, 2-dimethoxy Hue - the force in such Ruasetofuenon be used Can also be used in combination.
- a combination of a hydrogen abstraction type photopolymerization initiator such as phenone and a collapse type photopolymerization initiator such as 2,2-dimethoxyphenylacetophenone is particularly preferred. Furthermore, even when a compound having a site acting as a hydrogen abstraction-type polymerization initiator and a site acting as a collapse-type photopolymerization initiator in the same molecule is used, the effect of photocuring in the atmosphere can be seen.
- a photoinitiated thione polymerization initiator such as an aromatic diazonium salt, an aromatic odonium salt, or an aromatic sulfodium salt that absorbs light to generate an acid, or a polymerization initiator that generates a base by absorbing light. I can do it.
- the addition amount of the polymerization initiator is preferably in the range of 0.01 to 10 wt% of the total amount of the binder (i) and the organic compound (j)!
- a circumference adjusting layer (F) (reference numeral 3), a resin layer (B) (reference numeral 6) capable of forming a pattern on the surface, or a resin having a pattern formed on the surface. It may be a laminate in which a cushion layer (E) (reference numeral 4) having cushioning properties is formed between the layers (C) (reference numeral 6). If there is no circumference adjusting layer (F), the hollow cylindrical core material (A) (reference numeral 2) and a resin layer (B) or a resin layer on which a pattern can be formed are formed. The laminate may have a cushion layer (E) having cushioning properties between (C).
- the cushion layer (E) formed on the circumferential length adjusting layer (F) or the hollow cylindrical core material (A) is obtained by forming a cushion tape with an adhesive layer on the circumferential length adjusting layer (F) or the hollow cylindrical shape.
- the photosensitive resin composition layer can be formed on the adjustment layer (F) or the hollow cylindrical core material (A), and cured by photo-curing to form a rubber-elastic cushion layer. .
- a simple method of forming a seamless cushion layer is a method of photo-curing a photosensitive resin composition. Of course, as described in the section of the perimeter adjusting layer (F), open cells and closed cells can be contained.
- the hardness of the cushion layer (E) of the present invention is preferably from 10 to 70 degrees in Shore A hardness, more preferably from 10 to 60 degrees, still more preferably from 10 to 50 degrees. If the cushion layer (E) contains air bubbles and it is difficult to measure with a Shore A hardness meter, ASKER —C hardness can be used as the hardness of the cushion layer (E).
- the preferred range of ASKER-C hardness is 20 to 70 degrees, more preferably 20 to 60 degrees.
- the hardness of the cushion layer (E) is preferably lower than the hardness of the resin layer (B) capable of forming a pattern on the surface or the resin layer (C) having a pattern formed on the surface.
- a resin layer (B) or a pattern capable of forming a pattern is formed on the hollow cylindrical core material (A), the circumference adjusting layer (F), or the cushion layer (E).
- the fat layer (C) can be laminated.
- the method of forming a noturn is a method using photoengraving technology through an exposure and development process, and a laser engraving method in which a concave portion is formed by irradiating a laser beam and removing the resin in the portion irradiated with the laser beam. Can be used.
- the laser engraving method is a method that can form a pattern on a resin layer based on image data using a computer, since a pattern can be formed without undergoing a developing step, and is preferable.
- the resin layer (B) or resin layer (C) has a hardness of 20 to 75 degrees in the area of Shore A hardness, paper, film, and building material surface irregularity pattern in normal printing plate applications.
- Shore A hardness a hardness of 20 to 75 degrees in the area of Shore A hardness, paper, film, and building material surface irregularity pattern in normal printing plate applications.
- relatively hard materials are required, with a Shore D hardness range of 30-80 degrees.
- the laser-engravable photosensitive resin cured material layer (3) contains an inorganic porous material (f) to form a laser. Liquid scum generated in one engraving process can be absorbed and removed.
- the photosensitive resin composition (10) before photocuring is a resin (d) having a number average molecular weight of 1,000 to 200,000 and an organic compound having a number average molecular weight of less than 1000 and having a polymerizable unsaturated group in the molecule. (e) and an inorganic porous material (f).
- the type of resin (d) may be an elastomer or a non-elastomer, and may be a solid polymer or a liquid polymer at 20 ° C. .
- a thermoplastic resin When a thermoplastic resin is used, it is desirably contained in an amount of 30% by weight or more, preferably 50% by weight or more, more preferably 70% by weight or more of the total weight of the polymer. If the content of the thermoplastic resin is S30 wt% or more, the resin is sufficiently fluidized by laser beam irradiation, and is absorbed by the inorganic porous material described later.
- Solvent-soluble resin is dissolved in solvent and applied It is preferable to use them.
- the photosensitive resin composition to be formed is also liquid, and thus can be molded at a low temperature.
- the number average molecular weight of the resin (d) used in the present invention is preferably in the range of 1,000 to 200,000. A more preferable range is 5000 to 100,000. When the number average molecular weight is in the range of 1,000 to 200,000, the mechanical strength of the printing original plate can be ensured, and the resin can be sufficiently melted or decomposed during laser engraving.
- the number average molecular weight of the present invention is measured by gel permeation chromatography (GPC) and evaluated with respect to a standard polystyrene having a known molecular weight.
- the scum liquified by laser beam irradiation can be absorbed and removed using the inorganic porous material.
- the photosensitive resin cured product (10) to be used a resin that easily liquefies and is easily decomposed is preferable.
- easily decomposable resins include styrene, ⁇ -methylstyrene, ⁇ -methoxystyrene, acrylic esters, methacrylic esters, ester compounds, ether compounds, nitro compounds as monomer units which are easily decomposed in a molecular chain.
- polyethers such as polyethylene glycol, polypropylene glycol, polytetraethylene dalicol, aliphatic polycarbonates, aliphatic cellulose, polymethyl methacrylate, polystyrene, nitrocellulose, polyoxyethylene, polynorbornene, polycyclohexene hydrogenated
- a polymer having a molecular structure such as a substance or a dendrimer having many branched structures is a typical example of a substance which is easily decomposed.
- a polymer containing a large number of oxygen atoms in the molecular chain is preferable from the viewpoint of decomposability.
- a compound having a carbonate group, a sulfamate group, and a methacryl group in the polymer main chain is preferable because of its high thermal decomposability.
- polyesters and polyurethanes synthesized from (poly) carbonate diol and (poly) carbonate dicarboxylic acid as raw materials, and polyamides synthesized from (poly) carbonate diamine as raw materials are examples of polymers having good thermal decomposability. It can be mentioned as.
- These polymer main chains and side chains may contain a polymerizable unsaturated group.
- the terminal has a reactive functional group such as a hydroxyl group, an amino group or a carboxyl group, it is easy to introduce a polymerizable unsaturated group at the terminal of the main chain.
- thermoplastic elastomer used in the present invention is not particularly limited, SBS (polystyrene polybutadiene polystyrene), SIS (polystyrene polyisoprene polystyrene), and SEBS (polystyrene polyethylene Z polybutylene, which are styrene-based thermoplastic elastomers, may be used.
- SBS polystyrene polybutadiene polystyrene
- SIS polystyrene polyisoprene polystyrene
- SEBS polystyrene polyethylene Z polybutylene, which are styrene-based thermoplastic elastomers
- Polyolefin or other thermoplastic elastomers, urethane-based thermoplastic elastomers, ester-based thermoplastic elastomers, amide-based thermoplastic elastomers, silicone-based thermoplastic elastomers, and the like.
- thermoplastic elastomer is fluidized by heating, it can be mixed with the inorganic porous material used in the present invention.
- Thermoplastic elastomer is a material that flows when heated, can be molded in the same manner as ordinary thermoplastics, and exhibits rubber elasticity at room temperature.
- the molecular structure is composed of soft segments such as polyether or rubber molecules, and hard segments that prevent plastic deformation at around room temperature, similar to vulcanized rubber.
- the hard segments include a frozen phase, a crystalline phase, hydrogen bonds, There are various types such as ionic crosslinking.
- thermoplastic elastomer can be selected depending on the use of the printing plate. For example, urethane-based, ester-based, amide-based, and fluorine-based thermoplastic elastomers are preferred in fields where solvent resistance is required. A fluorinated thermoplastic elastomer is preferred. Further, the hardness can be greatly changed depending on the type of the thermoplastic elastomer.
- Non-elastomeric thermoplastic resin is not particularly limited. Polyester resin, unsaturated polyester resin, polyamide resin, polyamideimide resin, polyurethane resin, unsaturated polyurethane resin, polysulfone Resin, polyethersulfone resin, polyimide resin, polycarbonate resin, wholly aromatic polyester resin, etc. You can do it.
- the softening temperature of the thermoplastic resin is preferably from 50 ° C to 300 ° C. A more preferable range is 80 ° C or more and 250 ° C or less, more preferably 100 ° C or more and 200 ° C or less. If the softening temperature is 50 ° C or higher, it can be handled as a solid at room temperature, and can be handled without deforming a sheet or a cylinder. When the softening temperature is 300 ° C or less, when processing into a cylindrical shape, it is not necessary to heat the thermoplastic resin to an extremely high temperature. .
- the measurement of the softening temperature of the present invention uses a dynamic viscoelasticity measuring device, and when the room temperature force temperature is increased, the first temperature at which the viscosity changes greatly (the slope of the viscosity curve changes).
- the resin (d) may be a solvent-soluble resin. Specific examples include polysulfone resin, polyethersulfone resin, epoxy resin, alkyd resin, polyolefin resin, polyester resin and the like.
- the resin (d) generally does not have a highly reactive polymerizable unsaturated group, but even if it has a highly reactive and polymerizable unsaturated group at the terminal or side chain of the molecular chain, I don't care.
- a polymer having high reactivity and having a polymerizable unsaturated group is used, a printing master having extremely high mechanical strength can be produced.
- polyurethane-based or polyester-based thermoplastic elastomers it is possible to relatively easily introduce highly reactive polymerizable unsaturated groups into the molecule.
- introduction includes the case where a polymerizable unsaturated group is directly attached to the terminal of the polymer main chain, the terminal of the polymer side chain, the polymer main chain or the side chain.
- a polymerizable unsaturated group is directly introduced into the molecular terminal may be used.
- reactive groups such as hydroxyl, amino, epoxy, carboxyl, anhydride, ketone, hydrazine, isocyanate, isothiosinate, cyclic carbonate, and ester groups
- a method of reacting the group reacting with the terminal bonding group with an organic compound having a polymerizable unsaturated group to introduce a polymerizable unsaturated group into the terminal etc.
- the method of (1) is preferred.
- the organic compound (e) is a compound having an unsaturated bond involved in a radical polymerization reaction or an addition polymerization reaction, and has a number average molecular weight of less than 1000 in consideration of the ease of dilution with the resin (d). It is preferable that.
- Preferred examples of the functional group having an unsaturated bond involved in the radical polymerization reaction include a vinyl group, an acetylene group, an acryl group, a methacryl group, and an aryl group.
- Examples of the functional group having an unsaturated bond involved in the addition polymerization reaction include a cinnamoyl group, a thiol group, an azide group, an epoxy group that undergoes a ring-opening addition reaction, an oxetane group, a cyclic ester group, a dioxysilane group, and a spiro orthocarbonate group. And a spiroorthoester group, a bicycloorthoester group, a cyclosiloxane group, a cyclic iminoether group and the like.
- organic compound (e) examples include olefins such as ethylene, propylene, styrene, and dibutylbenzene, acetylenes, (meth) acrylic acid and its derivatives, halolefins, and unsaturated-tolyl such as acrylonitrile.
- olefins such as ethylene, propylene, styrene, and dibutylbenzene
- acetylenes examples include (meth) acrylic acid and its derivatives, halolefins, and unsaturated-tolyl such as acrylonitrile.
- (Meth) acrylamide and its derivatives aryl compounds such as aryl alcohol and aryl isocyanate, unsaturated dicarboxylic acids such as maleic anhydride, maleic acid and fumaric acid and derivatives thereof, vinyl acetates, N-vinyl (Meth) acrylic acid and its derivatives are preferred in terms of their abundance, cost, and decomposability upon irradiation with a laser beam, and examples thereof are U, and examples thereof include pyrrolidone and N-butyl rubazole.
- the derivative examples include an aliphatic compound having a cycloalkyl group, a bicycloalkyl group, a cycloalkenyl group, a bicycloalkenyl group, a benzyl group, a phenyl group, a phenoxy group, or a naphthalene skeleton, an anthracene skeleton, biphenyl Aromatic compounds having skeleton, phenanthrene skeleton, fluorene skeleton, etc., compounds having alkyl group, halogenated alkyl group, alkoxyalkyl group, hydroxyalkyl group, aminoalkyl group, glycidyl group, etc., alkylene glycol, polyoxyalkylene Examples thereof include ester compounds with polyhydric alcohols such as glycol, polyalkylene glycol, and trimethylolpropane, and compounds having a polysiloxane structure such as polydimethylsiloxane and polydimethylsilox
- Examples of the compound having an epoxy group that undergoes a ring-opening addition reaction include compounds obtained by reacting epichlorohydrin with various polyols such as diol and triol; Epoxy conjugates obtained by reacting a peracid with an ethylene bond of the above.
- ethylene glycol diglycidyl ether diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene daryl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol resid glycidinoleate, glycerin diglycidinoleate, glycerin triglycidyl ether, trimethylolpropane triglycidylate Bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol Diglycidyl ether, polytetramethylene glycol diglycidyl ether, poly (propylene glycol adipate
- one or more of these organic compounds (e) having a polymerizable unsaturated bond can be selected according to the purpose.
- organic compound (e) used to suppress swelling in organic solvents such as alcohols and esters, which are solvents for printing ink
- organic solvents such as alcohols and esters, which are solvents for printing ink
- the organic compound (e) preferably has at least one alicyclic or aromatic derivative.
- the aromatic derivative may be an aromatic compound having an element such as nitrogen or sulfur.
- a methacrylic monomer described in JP-A-7-239548 may be used, or a known photosensitive resin for printing may be used. It can be selected using technical knowledge and the like.
- the inorganic porous material (f) refers to a non-porous material having fine pores or fine voids in particles. Machine particles. It is an additive for absorbing and removing viscous liquid residue generated in large quantities in laser engraving, and also has an effect of preventing tack on the plate surface. In addition to not being melted even by laser irradiation, when photocuring using ultraviolet light or visible light, the addition of black fine particles significantly reduces the light transmittance inside the photosensitive resin composition, Black fine particles such as carbon black, activated carbon, and graphite are not suitable as the inorganic porous material (f) of the present invention, although they are not particularly excluded as a material because they cause deterioration in physical properties.
- the pore volume of the inorganic porous material (f) is preferably from 0.1 mlZg to 10 mlZg, more preferably from 0.2 mlZg to 5 mlZg.
- the pore volume is 0.1 lmZg or more, the absorption amount of the viscous liquid scum is sufficient, and when the pore volume is 10 OmZg or less, the mechanical strength of the particles can be secured.
- the nitrogen adsorption method is used for measuring the pore volume.
- the pore volume of the present invention is determined from the adsorption isotherm of nitrogen at -196 ° C.
- the average pore diameter of the inorganic porous material (f) has a very large effect on the absorption amount of liquid scum generated during laser engraving.
- the preferred range of the average pore diameter is 1 nm or more and 100 nm or less, more preferably 2 nm or more and 200 nm or less, and further preferably 2 nm or more and 50 nm or less.
- the average pore diameter is 1 nm or more, the absorbability of liquid scum generated during laser engraving can be ensured.
- the average pore diameter is 100 nm or less, the specific surface area of the particles is large and the liquid scum absorption amount can be sufficiently ensured.
- the average pore diameter in the present invention is a value measured using a nitrogen adsorption method. Those having an average pore diameter of 2 to 50 nm are particularly called mesopores, and the ability of porous particles having mesopores to absorb liquid residue is extremely high.
- the pore size distribution of the present invention also requires the nitrogen isotherm at 196 ° C.
- the present invention preferably employs a resin having a relatively low molecular weight so as to be easily cut by laser irradiation. Therefore, when a molecule is cut, a large amount of low molecular monomers and oligomers are generated.
- U a new concept
- U the number average particle diameter of the inorganic porous material
- the inorganic porous material (f) preferably has a number average particle size of 0.1 to: LOO / zm.
- the porosity is the ratio of the specific surface area P to the surface area S per unit weight calculated from the average particle diameter D (unit: zm) and the density d (unit: gZcm 3 ) of the substance constituting the particles, ie, PZS Defined by
- the surface area per particle is ⁇ ⁇ 2 ⁇ 10 _12 (unit: m 2 ), and the weight of one particle is ( ⁇ ⁇ 3 (! ⁇ 6) X 10 _ 12 (unit: g).
- the specific surface area P is a value measured by adsorbing nitrogen molecules on the surface.
- the porosity of the inorganic porous material (f) is preferably 20 or more, more preferably 50 or more, and even more preferably 100 or more. If the porosity is 20 or more, it is effective in removing and removing liquid residues. Since the specific surface area P increases as the particle diameter decreases, the specific surface area alone is not appropriate as an index indicating the properties of the porous body. Therefore, taking into account the particle size, porosity was adopted as a dimensionless index. For example, carbon black, which is widely used as a reinforcing material for rubber and the like, has a very large specific surface area of 150 m 2 / g to 20 m 2 / g and a very small force average particle size, usually 10 nm to 100 nm.
- the porosity of the porous silica used in the present invention is a high value well over 500.
- the inorganic porous material (f) used in the present invention preferably has a specific specific surface area and a specific oil absorption in order to obtain even better adsorptivity.
- the range of the specific surface area of the inorganic porous material (f) is preferably from 10 m 2 Zg to 1500 m 2 Zg. A more preferred range is 100 m 2 Zg or more and 800 m 2 Zg or less.
- the specific surface area of the present invention is determined from the adsorption isotherm of nitrogen at ⁇ 196 ° C. based on the BET equation.
- an oil absorption amount As an index for evaluating the amount of adsorbed liquid residue, there is an oil absorption amount. This is defined as the amount of oil absorbed by 100 g of the inorganic porous material.
- the preferred range of the oil absorption of the inorganic porous material (f) used in the present invention is from lOmlZlOOg to 2000mlZl00g, more preferably from 50ml / lOOg to lOOOmlZlOOg, more preferably ⁇ 200mlZl00g to 800mlZl00g.
- the oil absorption is lOmlZlOOg or more, it is effective in removing liquid scum generated during laser engraving, and when the oil absorption is 2000mlZl00g or less, the mechanical strength of the inorganic porous material (f) can be sufficiently ensured.
- the measurement of the oil absorption is preferably performed according to JIS-K5101.
- the inorganic porous body (f) needs to maintain its porosity without being deformed or melted by laser light irradiation particularly in the infrared wavelength region.
- the loss on ignition when treated at 950 ° C for 2 hours is preferably 15 wt% or less, more preferably 10% or less.
- the particle shape of the inorganic porous material (f) is not particularly limited, and spherical particles, flat particles, needle-like particles, amorphous particles, or particles having projections on the surface can be used. Among them, spherical particles are particularly preferable from the viewpoint of abrasion resistance of the printing plate. In addition, it is also possible to use spherical particles having a uniform pore diameter, such as hollow particles or silica sponge, in which the inside of the particles becomes hollow.
- porous silica, mesoporous silica, silica-zircoa porous gel, mesoporous molecular sieve, porous alumina, porous glass and the like can be mentioned.
- organic pigments such as pigments and dyes that absorb light having a wavelength of laser light can be incorporated into these pores or voids.
- Sphericity is defined as an index for defining spherical particles.
- the sphericity used in the present invention is defined as the ratio (D / ⁇ ) of the maximum value D of a circle completely entering a projected figure when a particle is projected and the minimum value D of a circle completely entering a projected figure. I do. For a true sphere, the sphericity is 1.0
- the sphericity of the preferred spherical particles used in the present invention is 0.5 or more and 1.0 or less, more preferably 0.7 or more and 1.0 or less. If it is 0.5 or more, the abrasion resistance of the printing plate is good.
- the sphericity 1.0 is the upper limit of the sphericity.
- the spherical particles preferably have a particle force of 70% or more, more preferably 90% or more, and a sphericity of 0.5 or more.
- a method for measuring sphericity a method for measuring based on a photograph taken using a scanning electron microscope can be used. At this time, it is preferable to take a photograph at a magnification at which at least 100 or more particles enter the monitor screen. Also, the above D and D are measured based on the photograph,
- the surface of the inorganic porous material (f) is coated with a silane coupling agent, a titanium coupling agent, or another organic compound and subjected to a surface modification treatment to make the surface more hydrophilic or hydrophobic. It is possible to use particles that have been prepared.
- one or more of these inorganic porous bodies (f) can be selected.
- the generation of liquid scum during laser engraving can be suppressed, and the relief can be achieved. Improvements such as tack prevention of the printing plate are effectively performed.
- the ratio of the resin (d), the organic compound (e), and the inorganic porous material (f) in the photosensitive resin composition (10) of the present invention is usually based on 100 parts by weight of the resin (d).
- the organic compound is preferably in the range of 5 to 200 parts by weight, more preferably in the range of 20 to 100 parts by weight.
- the inorganic porous material (f) is from 1 to: LOO parts by weight is preferred 2 to 50 parts by weight is more preferred The range is more preferred Is from 2 to 20 parts by weight.
- the proportion of the organic compound (e) is in the above range, the hardness of the resulting printing plate or the like and the tensile strength and elongation are easily balanced, and the shrinkage during crosslinking and curing is small, and the thickness accuracy is secured. Can be.
- the amount of the inorganic porous material (f) is in the above range, the effect of preventing tackiness of the plate surface and the effect of suppressing the generation of engraved liquid scum during laser engraving are sufficiently exhibited. Can secure the mechanical strength, and can also maintain transparency. In particular, when used as a flexographic plate, the hardness can be prevented from becoming too high.
- a photosensitive resin composition is cured using light, particularly ultraviolet light, to produce a laser engraving printing original plate, the light transmittance affects the curing reaction. Therefore, it is effective to use an inorganic porous material whose refractive index is close to that of the photosensitive resin composition.
- the photosensitive resin composition (10) is cross-linked by light irradiation to exhibit physical properties as a printing plate or the like.
- a polymerization initiator can be added.
- the polymerization initiator can be selected from commonly used ones. For example, radical polymerization, cationic polymerization, and tertiary polymerization exemplified in “Polymer Data 'Handbook, One Basic Edition”, edited by The Society of Polymer Science, Japan, 1986 (published by Baifukan). An initiator for dion polymerization can be used.
- Cross-linking by photopolymerization using a photopolymerization initiator is useful as a method for producing a printing plate with high productivity while maintaining the storage stability of the resin composition of the present invention.
- Suitable initiators can be used in this case.
- benzoin alkyl ethers such as benzoin and benzoinethyl ether, 2-hydroxy-2-methylpropiophenone, 4'isopropyl-2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-2-phenylacetophenone, and diethyl Acetophenones such as xyacetophenone; 1-hydroxycyclohexylphenol ketone, 2 methyl 1 [4 (methylthio) phenyl] 2 morpholinopropane 1-one, methyl phenylglyoxylate, benzophenone, benzyl Aromatic diazonium salts, aromatic rhododium salts, and aromatic sulfo- ⁇ salts that absorb light from photo-radical polymerization initiators such as diacetyl, diacetyl sulfide, eosine, thionine, and anthraquinone to generate an acid.
- Thione polymerization initiator such as salt Such that the weight initiator, and the like.
- the amount of the polymerization initiator to be added depends on the sum of the resin (d) and the organic compound (e). 0.01 to weighing: L0 wt% range is preferred.
- a polymerization inhibitor, an ultraviolet absorber, a dye, a pigment, a lubricant, a surfactant, a plasticizer, a fragrance, and the like may be added to the photosensitive resin composition (10) according to the application and purpose.
- an existing resin molding method can be used as a method for molding the photosensitive resin composition (10) into a cylindrical shape.
- a casting method, a method in which resin is extruded from a nozzle and a die using a machine such as a pump or an extruder, the thickness is adjusted by a blade, and the thickness is adjusted by calendering with a roll, and the like can be exemplified.
- the molding while heating with calo as long as the performance of the resin is not deteriorated. Further, a rolling process, a grinding process, and the like may be performed as necessary. Further, after the photosensitive resin composition (10) is applied in a cylindrical shape, light is irradiated to cure and solidify the photosensitive resin composition (10).
- the printing plate can also be formed using the cylindrical printing plate precursor molding 'engraving apparatus incorporated. When such a device is used, a conventional rubber sleeve, which can engrave a laser immediately after forming a cylindrical printing plate precursor and form a printing plate, requiring several weeks for molding. In short, it is possible to realize short-time processing that cannot be considered.
- the photosensitive resin composition (10) in the step of producing the hollow cylindrical printing original plate, the hollow cylindrical printing original plate can be produced in an extremely short time.
- the adhesiveness between the circumference adjusting layer (F) and the cured photosensitive resin layer (3) capable of laser engraving can also be improved.
- the physical treatment method include a sand blast method, a wet blast method for injecting a liquid containing fine particles, a corona discharge treatment method, a plasma treatment method, and an ultraviolet or vacuum ultraviolet irradiation method.
- the chemical treatment method there are a strong acid / strong alkali treatment method, an oxidizing agent treatment method, a coupling agent treatment method and the like.
- the molded photosensitive resin composition (10) is cross-linked by irradiation with light or an electron beam to form a laser-engravable printing original plate.
- crosslinking can be performed by light or electron beam irradiation while molding.
- the method of cross-linking using light is preferable because it has advantages such as simple apparatus and high thickness accuracy.
- High pressure mercury as the light source used for curing Lamps, ultra-high pressure mercury lamps, ultraviolet fluorescent lamps, carbon arc lamps, xenon lamps, etc., and curing can be performed by other known methods. Further, light from a plurality of types of light sources may be irradiated.
- the surface When the photosensitive resin composition is cured with light, the surface may be covered with a transparent cover film and irradiated with light in a state where oxygen is blocked.
- the cover film can also be used to protect the surface of the printing plate. However, it is used after laser engraving.
- the atmosphere in which the photosensitive resin composition layer is irradiated with light is preferably a gas atmosphere, particularly an air atmosphere. This is because it is not necessary to attach a cover film covering mechanism for blocking oxygen, an oxygen deficiency preventing mechanism when using an inert gas, and the like to the apparatus.
- the thickness of the laser-engravable photosensitive resin cured material layer (3) may be arbitrarily set according to the intended use, but when used as a printing plate, it is generally 0.1 l. It is in the range of ⁇ 7mm. In some cases, a plurality of materials having different compositions may be stacked.
- a portion irradiated with the light beam is photo-cured by using a mask exposure method or a high energy single-line scanning exposure method to form a latent image, It may be a photosensitive resin layer from which uncured portions are removed in a subsequent development step.
- a method is used in which a thin layer containing a black pigment such as carbon black called a black layer is formed on the surface of the photosensitive resin layer, and a pattern is formed using a near-infrared laser, and the pattern is used as an exposure mask. You can also.
- a developing solution in which the uncured resin is dissolved or dispersed can be used, and a heat developing method in which the uncured resin is melted by heat and absorbed by a nonwoven fabric without using a developing solution can also be used.
- the mask exposure method is a method in which a photosensitive resin is irradiated with a light beam including light in a wavelength region of 200 nm to 450 nm through a negative film having a light-shielding pattern.
- the high-energy one-line scanning exposure method is a method in which a beam energy beam such as an ultraviolet laser beam or an electron beam is scanned using an optical system such as a galvanometer mirror or an electron lens to irradiate the photosensitive resin. It is.
- the resin layer (C) having a pattern formed on the surface is provided with a hollow cylindrical core material (A), a circumference adjusting layer (F), or a cushion layer (E) via an adhesive layer or an adhesive layer. Alternatively, it may be stuck on the rigid body layer (G).
- a cushion layer (E) (reference numeral 4 in the figure) Functional resin layer (B) or patterned resin layer (C) (symbol 6 in the figure) and a rigid body layer (G) with a thickness of at least Olmm to at most 0.5 mm (in the figure) , 5) may be present.
- the preferred range of the linear thermal expansion coefficient of the rigid body layer (G) is 10 ppmZ ° C or more and 150 1117 when measured in the temperature range of 20 ° C to 80 ° C using the thermomechanical measurement method (TMA method). Below, more preferably OppmZ ° C or more and 100 ppmZ ° C or less.
- a hollow cylindrical printing substrate can be produced by a method of sequentially laminating and laminating a plurality of photosensitive resin composition layers, and a plurality of photosensitive resin compositions can be produced. After laminating the material layers, photo-curing can be performed at once to produce a hollow cylindrical printing substrate.
- the resin layer (C) on which is formed is preferably formed by photocrosslinking and curing a photosensitive resin composition.
- the polymerizable unsaturated group present in the photosensitive resin composition reacts to form a three-dimensional cross-linked structure, which is commonly used for ester, ketone, aromatic, ether, alcohol, and halogen. Insoluble in solvent. This reaction takes place between the polymerizable unsaturated groups and consumes the polymerizable unsaturated groups.
- the photopolymerization initiator When crosslinking and curing using a photopolymerization initiator, the photopolymerization initiator is decomposed by light.Therefore, the crosslinked cured product is extracted with a solvent and separated by GC-MS (mass separation is performed by gas chromatography. Analysis method), LC MS method (method of mass spectrometry of liquid separated by liquid chromatography), GPC-MS method (method of separation and mass spectrometry by gel permeation chromatography), LC NMR method (liquid chromatography) The unreacted photopolymerization initiator and decomposition products can be identified by analyzing using a method for analyzing the product separated by the above using a nuclear magnetic resonance spectrum).
- Pyrolysis GC-MS method is a method in which a sample is thermally decomposed, the generated gas components are separated by gas chromatography, and then mass spectrometry is performed.
- the crosslinked cured product decomposition products derived from the photopolymerization initiator and unreacted photopolymerization initiator together with the unreacted polymerizable unsaturated group or the site obtained by the reaction of the polymerizable unsaturated group are included. If detected, it can be concluded that the photosensitive resin composition was obtained by photocrosslinking and curing.
- the amount of the inorganic porous material fine particles present in the cross-linked cured product can be determined by heating the cross-linked cured product in the air, burning off the organic component, and measuring the weight of the residue. it can.
- the presence of the inorganic porous material fine particles in the residue was confirmed by morphological observation with a field emission type high resolution scanning electron microscope, particle size distribution with a laser scattering type particle size distribution measuring device, and nitrogen adsorption method. The measurement power of pore volume, pore diameter distribution, and specific surface area can be identified.
- a relief image is created on an original by operating a laser device using a combi- ter, using the formed image as digital data.
- Laser As the laser used for engraving, any laser may be used as long as it contains a wavelength at which the original plate has absorption. However, in order to perform engraving at a high speed, a laser with a high output is desirable. Lasers having an oscillation wavelength in the infrared or near-infrared region, such as lasers, YAG lasers, semiconductor lasers, and fiber lasers, are one of the preferred lasers.
- Ultraviolet lasers having an oscillation wavelength in the ultraviolet region such as excimer lasers, YAG lasers converted to the third or fourth harmonic, copper vapor lasers, and the like, are subjected to an abrasion process for breaking bonds of organic molecules. It is possible and suitable for fine processing.
- a laser having a very high peak output such as a femtosecond laser can also be used.
- the laser beam may be continuous irradiation or pulse irradiation.
- resin absorbs around 10 m of a carbon dioxide laser, so it is not necessary to add a component that helps to absorb laser light.
- YAG lasers, semiconductor lasers, and fiber lasers have oscillation wavelengths around 1 ⁇ m, but few organic substances have light absorption in this wavelength range.
- dyes and pigments which are components that help absorb this.
- dyes include poly (substituted) phthalocyanine conjugates and metal-containing phthalocyanine conjugates; cyanine compounds; squarylium dyes; chalcogenopyrroloarylidene dyes; Metal thiolate dyes; bis (chalcogenopyri) polymethine dyes; oxyindolizine dyes; bis (aminoaryl) polymethine dyes; merocyanine dyes; and quinoid dyes.
- pigments include dark inorganic pigments such as carbon black, graphitic copper chromite, oxidized chromium, cobalt chrom aluminate, iron oxide, and metal powders such as iron, aluminum, copper, and zinc. And those doped with Si, Mg, P, Co, Ni, Y, and the like. These dyes and pigments may be used alone, may be used in combination of two or more, and may be combined in any form such as a multilayer structure. However, when curing the photosensitive resin composition using ultraviolet light or visible light, in order to cure the inside of the printing plate precursor, the addition amount of dyes and pigments that absorb in the used light region should be kept low. preferable.
- Laser engraving is performed under an oxygen-containing gas, generally in the presence of air or in an air stream, but can also be performed under carbon dioxide gas or nitrogen gas.
- powdery or liquid substances that are slightly generated on the relief printing plate surface can be washed by an appropriate method, for example, by washing with water containing a solvent or a surfactant, or by irradiating a water-based detergent with a high-pressure spray. Alternatively, it may be removed using a method of irradiating high-pressure steam.
- a wavelength of 200 ⁇ ! Post-exposure with ⁇ 450 nm light can also be performed.
- Post-exposure may be performed in the atmosphere, in an inert gas atmosphere, in water, or in an offset environment. It is particularly effective when the photosensitive resin composition used contains a hydrogen abstraction type photopolymerization initiator.
- the surface of the printing plate may be treated with a treatment liquid containing a hydrogen abstraction type photopolymerization initiator and exposed. Further, the exposure may be performed in a state where the printing plate is immersed in a processing solution containing a hydrogen abstraction type photopolymerization initiator.
- the original plate of the present invention can be used for stamping stamps, design rolls for embossing, and insulators, resistors, and conductor paste used for making electronic components, in addition to relief images for printing plates. It can be applied and used in various applications such as relief images for Jung, relief images for moldings of ceramic products, relief images for displays such as advertisements and display boards, and prototypes for various molded products.
- Laser engraving was performed using a carbon dioxide laser engraving machine (trade name "ZED-mini-1000", manufactured by ZED, UK), and engraving was performed using halftone dots, line drawings with 500 m wide convex lines, and 500 m wide A pattern including a white line was created and implemented. If the engraving depth is set to a large value, the area of the top of the fine halftone dot pattern cannot be secured, and the shape will collapse and become unclear, so the engraving depth is set to 0.55 mm.
- the shape of the halftone dot area with an area ratio of about 10% at 801 pi (Lines per inch) was observed with an electron microscope at a magnification of 200 to 500 times.
- the halftone dot is conical or pseudo-conical (a divergent shape in which the vicinity of the apex of the cone is cut by a plane parallel to the bottom of the cone), it is good as a printing plate.
- the weight of the porous or non-porous material for measurement was recorded.
- the sample for measurement is placed in a high-temperature electric furnace (FG31; manufactured by Yamato Scientific Co., Ltd. in Japan), and placed in an air atmosphere at 950 ° C. Time processed.
- the change in weight after the treatment was defined as a loss on ignition.
- the average particle diameter of the porous body and the non-porous body was measured using a laser diffraction type particle size distribution analyzer (trademark, SALD-2000J type; manufactured by Shimadzu Corporation, Japan).
- SALD-2000J type manufactured by Shimadzu Corporation, Japan.
- the specification of the instrument states in the force catalog that it is possible to measure a particle size range from 0.03 ⁇ m force to 500 ⁇ m.
- ultrasonic waves were irradiated for about 2 minutes to disperse the particles and prepare a measurement solution.
- the viscosity of the photosensitive resin composition was measured at 20 ° C. using a B-type viscometer (trademark, type B8H; manufactured by Tokyo Keiki, Japan).
- the number average molecular weight of the resin (a) was determined by gel permeation chromatography (GPC) using a polystyrene having a known molecular weight. The measurement was carried out using a high-speed GPC apparatus (HLC 8020 manufactured by Tosoh Corporation, Japan) and a column packed with polystyrene (trademark: TSKgel GMHXL; manufactured by Tosoh Corporation, Japan) with tetrahydrofuran (THF). The column temperature was set at 40 ° C. As a sample to be injected into the GPC device,
- the injection volume was 10 ⁇ l.
- an ultraviolet absorption detector was used for resin (a), and light of 254 nm was used as monitor light.
- the average number of polymerizable unsaturated groups present in the molecule of the synthesized resin (a) can be determined by nuclear magnetic resonance spectroscopy (NMR method) after removing unreacted low molecular components by liquid chromatography. ) was used to determine the molecular structure.
- the Shore D hardness of the perimeter adjusting layer (F) was measured using Tek-lock's trademark “GS-720G TypeDj.” The value immediately after the start of the measurement was adopted as the Shore D hardness, which was formed on a cylindrical support. The Shore D hardness of the cylindrical core material (A) was measured with the cylindrical support attached. The weight used for the measurement was 8 kg.
- thermomechanical measurement method (10) Measurement of linear thermal expansion coefficient
- the linear thermal expansion coefficient of the film-like reinforcing material was measured using a thermomechanical measurement method (TMA).
- TMA thermomechanical measurement method
- the measurement temperature range was from room temperature to 80 ° C using a thermomechanical measuring device (trademark “TMA-50” manufactured by Shimadzu Corporation).
- Resins (dl), (d2) and (d3) were produced as Resin (d) in Production Examples 1 to 3 below.
- the mixture was further reacted for about 3 hours to produce a resin (d3) having a number-average molecular weight of about 3000, which is a terminally acryl group (an average of about 2 polymerizable unsaturated groups per molecule).
- the resin was syrupy at 20 ° C, flowed when an external force was applied, and did not recover its original shape even when the external force was removed.
- a PET film with a thickness of 125 m is wound around the surface of an air cylinder with a thickness of 213.384 mm, which is thinly coated with polydimethylsiloxane as a release agent. . Aligned to 5mm or less and temporarily fastened. A glass cloth tape having a width of 25 mm and a thickness of 0.13 mm coated with an adhesive was spirally wound around the PET film to cover the surface of the PET film to obtain a cylindrical laminated body.
- the lamp illuminance on the surface of the photosensitive resin composition layer was measured using a UV meter (trade name “UV-M02” manufactured by Oak Manufacturing Co., Ltd.). Filter (Oak Seisakusho Co., Ltd., trademark "UV- 35- APR filter one") lamp illumination was measured using a can, lOOmW / cm 2, using a filter (Oak Seisakusho Co., Ltd., trademark "UV- 25 Filter”) The lamp illuminance measured was 14 mW / cm 2 Met. After that, cutting was performed using a carbide tool so that the thickness became 1.5 mm, and the surface was further roughened using a cutting gantry, and then a film with fine munitions attached to the surface was used.
- the Shore D hardness of the obtained hollow cylindrical core material ( ⁇ ) was 55 degrees.
- the height difference of the surface measured using a contact-type displacement sensor (trade name “ ⁇ 3-010” manufactured by KEYENCE CORPORATION) was within 20 / zm.
- the time required to produce the hollow cylindrical core material (ex) was within 30 minutes.
- a liquid photosensitive resin composition (XII) was prepared by adding 1 part by weight of benzophenone to 99 parts by weight of a liquid photosensitive resin composition (trade name “APR-G-42” manufactured by Asahi Kasei Chemicals Corporation). did.
- Liquid photosensitive resin composition (trade name "APR-G-42", manufactured by Asahi Kasei Chemicals Corporation) contains unsaturated polyurethane resin, an organic compound having several kinds of polymerizable unsaturated groups, and a photopolymerization initiator. Resin.
- the photosensitive resin composition (XII) used in Example 1 is impregnated in a nylon mesh sheet (150 mesh) having a thickness of 110 m and an opening of about 60 m, in which nylon fibers are knitted vertically and horizontally. After the photosensitive resin composition was removed with a blade, light of a chemical lamp (center wavelength: 370 ⁇ m) was irradiated at 50 miZcm 2 in the air to form a cured photosensitive resin in a semi-cured state. The surface remained sticky. When the surface tack was measured, it was larger than 200 NZm.
- a nylon mesh sheet containing a photosensitive resin cured product in a semi-cured state was spirally wound twice on a PET film coated on an air cylinder having an outer diameter of 213.384 mm. Further, a photosensitive resin composition ( ⁇ ) was applied on this nylon mesh sheet using a doctor blade to form a photosensitive resin composition layer. Light from a metal halide lamp was irradiated to obtain a photosensitive resin cured product. A hollow cylindrical core material
- a photosensitive resin composition (XIII) was prepared by mixing 5 parts by weight of silicon nitride spherical fine particles having an average particle diameter of 5 ⁇ m with 100 parts by weight of the photosensitive resin composition (XII). As a result of observation using a scanning electron microscope, 90% or more of the spherical particles of silicon nitride have a sphericity of 0.8 or more. Particles.
- the photosensitive resin composition (XIII) is applied to a 213.384 mm air cylinder subjected to a mold release treatment using a doctor blade, and is irradiated with light from a metal halide lamp to be light-cured and cured. D) was formed.
- the photosensitive resin composition (XII) was impregnated into a nylon mesh sheet, and irradiated with a chemical lamp at 50 mjZcm 2 in the air to obtain a cured photosensitive resin in a semi-cured state.
- the surface was sticky.
- the resulting semi-cured photosensitive resin cured product was pressed onto the resin layer (D) by pressing with a roller, and after being wound with a force S, the light of a metal nitride lamp was irradiated at 4000 mi / cm 2 , A cured photosensitive resin layer constituting a hollow cylindrical core material in which a nylon mesh sheet was wound three times was formed.
- the Shore D hardness of the hollow cylindrical core material ( ⁇ ) comprising the obtained cured photosensitive resin layer was as high as over 60 degrees.
- the thickness of the circumference adjustment layer was determined by calculating backward from the thickness of the material used.
- the thickness of the photosensitive resin cured layer that can be engraved with a laser is 1.14 mm
- the thickness of the cushion tape with adhesive layers on both sides is 0.55 mm (the thickness of the adhesive layer is 25 zm)
- the set value of the thickness of the circumference adjustment layer will be 1.526 mm.
- a photosensitive resin composition (XIV) was prepared for producing a circumference adjusting layer (a).
- the liquid photosensitive resin composition (XIV) was placed on a hollow cylindrical core material having an inner diameter of 213.384 mm and a width of 300 mm obtained as described above, and the thickness was measured using a doctor blade. about 1. was applied with a 1mm, then, Metaruno ⁇ halide lamp (eye 'graphics Co., Ltd., trademark "M0 56 -L21J) 4000mjZcm 2 (UV meter (Oak Seisakusho Co., Ltd.
- UV —M02 a light under a nitrogen atmosphere
- a filter a value obtained by integrating the illuminance measured with a filter (trade name“ UV-35—APR filter ”manufactured by Oak Manufacturing Co., Ltd.)) over time to obtain a cured photosensitive resin layer.
- the lamp illuminance on the surface of the photosensitive resin composition layer was measured using a UV meter (manufactured by Oak Manufacturing Co., Ltd., trade name “UV-M02”).
- a liquid photosensitive resin composition (trade name “APR-G-42” manufactured by Asahi Kasei Chemicals Co., Ltd.) is added to a thermally expandable capsule (trade name “Matsumoto Microsphere F—trade name, manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.”).
- a thermally expandable capsule (trade name “Matsumoto Microsphere F—trade name, manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.”).
- the obtained photosensitive resin composition (XV) is applied onto a hollow cylindrical core material attached to an air cylinder while rotating the air cylinder in the circumferential direction using a doctor blade, and a seamless photosensitive composition is applied.
- a resin composition layer was obtained.
- the thickness of the obtained photosensitive resin composition layer was 50 m.
- the light of a chemical lamp was applied to the obtained photosensitive resin composition layer with a lOOmjZcm 2 (UV meter (manufactured by Oak Manufacturing Co., Ltd., trade name “UV-MO 2”) and a filter (Oak Prototype Co., Ltd., trade name “UV-35 -APR filter ”) is irradiated with energy amount) were totalized was used to obtain a cured product in a semi-cured state (until hardness reaches arrives at a constant value, it is necessary at least 200MjZcm 2 energy) Then, the semi-cured resin layer was heated using an infrared lamp while rotating, and heated to 150 ° C.
- the heat-expandable microcapsules were expanded to have a circumferential length of about 200 m.
- a metal halide lamp was irradiated with light of 2000 mj / cm 2 (UV meter (manufactured by Oak Works, trademark “UV-M02”) and a filter (manufactured by Oak Works, trade name “UV-35—APR filter”). ) Irradiation) Thereafter, cutting and shaping were performed using a carbide tool so that the thickness of the circumference adjusting layer was 1.026 mm, and a circumference adjusting layer ( ⁇ ) was obtained. The time required to produce the adjustment layer ( ⁇ ) was within 20 minutes.
- the circumference adjusting layer having closed cells obtained by thermal expansion was devitrified, and it was confirmed that the thermally expandable microcapsule capsule was expanded. Observation of the bubble diameter near the surface using an optical microscope showed that in the obtained circumference adjustment layer, more than 70% of the bubbles were in the range of 30 to 60 m, and the average value was 48 ⁇ m.
- the Shore D hardness of the circumference adjusting layers (a) and ( ⁇ ) were 55 degrees and 58 degrees.
- a 0.55 mm thick cushion tape (manufactured by 3M, trademark "1820") having a double-sided adhesive layer is carefully placed on the circumference adjustment layer obtained as described above so that no air bubbles enter. By pasting, a cushion layer (a) was formed.
- a liquid photosensitive resin composition (XVI) was prepared by adding 1 part by weight of benzophenone to 99 parts by weight of a liquid photosensitive resin composition (trade name “APR-F320” manufactured by Asahi Kasei Chemicals Corporation).
- the obtained liquid photosensitive resin composition (XVI) is applied on the circumference adjusting layer using a doctor blade, and is light-cured by irradiating light from a metal halide lamp, and further has a thickness of 0.55 mm.
- a planetary vacuum defoaming kneader trade name "Mazerustar DD-300" manufactured by Kurashiki Boseki Co., Ltd.
- the obtained photosensitive resin composition was used for producing a resin layer (B) capable of laser engraving.
- the circumference adjusting layer (O) was laminated on the hollow cylindrical core material (O) produced as described above, and the cushion layer (oc) was further laminated thereon.
- a 100- ⁇ m-thick PET film (rigid body layer (G)) was attached on the cushion layer (a) with an adhesive layer on one side so that the adhesive layer was exposed on the front side.
- the photosensitive resin composition for forming the laser engravable resin layer (B) prepared as described above was placed in a circumferential direction by an air cylinder as a cylindrical support.
- a hollow cylindrical printing plate precursor capable of laser engraving was prepared.
- the total processing time required to produce the hollow cylindrical printing plate precursor was within 70 minutes.
- An irregular pattern was formed on the surface of the thus obtained hollow cylindrical printing original plate using a carbon dioxide laser engraving machine.
- the number of scum removals after laser engraving was good at 3 times or less, and the shape of the halftone dot was conical and good.
- the number of times of scrap removal after engraving is the number of times of wiping processing necessary to remove viscous liquid residue generated after engraving.
- the linear thermal expansion coefficient of the PET film used as the rigid body layer (G) was 100 ppm Z ° C by a thermomechanical measurement method (TMA (manufactured by Shimadzu Corporation, trademark “TMA-50”)).
- the photosensitive resin composition shown in Table 1 was applied on the cushion layer with a doctor blade to a thickness of about 1.5 mm while rotating the air cylinder as a cylindrical support in the circumferential direction using a doctor blade.
- a photosensitive resin composition layer having no odor was formed.
- the ultraviolet light of a metallometer and a ride lamp (trade name “M056-L21” manufactured by Eye Graphics Co., Ltd.) was 4000 mi / cm 2 (UV meter).
- UV-M02 UV Seisakusho's trademark “UV-M02”
- a filter Oak Seisakusho's trademark “UV-35-APR filter”.
- the number of scum wipings after engraving in Table 2 is the number of wiping treatments required to remove viscous liquid scum generated after engraving.
- styrene-butadiene copolymer manufactured by Asahi Kasei Chemicals Co., Ltd., trade name “Taphrene A”, number average molecular weight: 73,000), liquid polybutadiene (Nippon Petrochemical Co., trade name “B-2000”, number average) Molecular weight: 2000) 29 parts by weight, 1,9-nonanediol diatalylate (molecular weight: 268) 7 parts by weight, 2,2 dimethoxy-phenyl-acetophenone 2 parts by weight, and 2,6-di-tert-butyl p-talesol 1 Parts by weight are kneaded with a kneader, and the resulting kneaded material 10 Toluene was mixed with 20 parts by weight of toluene to obtain a highly viscous liquid photosensitive resin composition.
- a PET film was stuck on the cushion layer (a) in the same manner as in Example 1, and the obtained liquid photosensitive resin composition was applied thereon using a doctor blade, and the cylindrical support was slowly put on.
- the solvent, toluene, was scattered while rotating, and dried to obtain a seamless solid photosensitive resin layer having a thickness of 1.14 mm.
- a film-like exposure mask having a release layer on the surface was wound around the obtained solid photosensitive resin layer, and a chemical lamp was irradiated through the exposure mask to form a latent image.
- the film-shaped exposure mask was peeled off, and developed using a hydrocarbon solvent to form a concavo-convex pattern on the surface, thereby producing a cylindrical printing plate. In the fine halftone dot pattern portion, a good conical pattern was formed.
- the liquid photosensitive resin composition (XI) was applied to one side of a PET film having a width of 50 mm and a thickness of 25 ⁇ m to a thickness of 50 ⁇ m, and the surface was subjected to a release treatment.
- the PET film was spirally wound three times from the surface on which the photosensitive resin composition was applied so that the edges of the PET film slightly overlapped.
- light from a metal nitride lamp (trade name “M056-L21”, manufactured by Eye Graphics Co., Ltd.) was applied to a 2000 mjZcm 2 (UV meter (trade name, “UV-M02” manufactured by Oak Manufacturing Co., Ltd.)) and filter under a nitrogen atmosphere.
- the photosensitive resin composition was light-cured to form a hollow cylindrical core material.
- the height difference of the thickness of the obtained hollow cylindrical core material was 80 / zm.
- the inner surface of the obtained hollow cylindrical core material had a smooth surface, as if copying the smoothness of the air cylinder surface.
- the linear thermal expansion coefficient of the PET film used to produce the hollow cylindrical core material was 90 ppmZ ° C.
- the light transmittance was 90% in the wavelength range from 360 nm to 370 nm.
- a photosensitive resin composition (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name “APR-G-42”) is applied on the obtained hollow cylindrical core material with a doctor blade to a thickness of about 1.1 mm. , off then, Metaruno ⁇ halide lamp (eye 'graphics Co., Ltd., trademark "M056- L21”) and 4000miZcm 2 a light under a nitrogen atmosphere of (UV meter (Oak Seisakusho Co., Ltd., trademark "UV-M02”) Illuminance measured with a filter (Oak Mfg. Co., Ltd., trademark "UV-35-APR filter”) Irradiation was performed to obtain a cured photosensitive resin layer.
- the lamp illuminance on the surface of the photosensitive resin composition layer was measured using a UV meter (trade name “UV-M02” manufactured by Oak Manufacturing Co., Ltd.).
- Filter (Oak Seisakusho Co., Ltd., trademark "UV- 35- APR filter”) lamp illumination was measured by use is, lOOmW / cm 2, using a filter (Oak Seisakusho Co., Ltd., trademark "UV- 25 Filter”)
- the measured lamp illuminance was 14 mWZcm 2 . Thereafter, cutting was performed using a carbide tool so that the thickness became 1.026 mm, and a circumferential length adjusting layer was obtained.
- a cushion tape with a double-sided adhesive layer (manufactured by 3M, trademark “1820”) was attached on the obtained circumference adjustment layer for one circumference while taking care not to allow air bubbles to enter.
- the used photosensitive resin composition for forming the resin layer (B) was applied and cured by light to obtain a cured photosensitive resin that can be engraved with a laser. Furthermore, by grinding and polishing to adjust the film thickness, a laser engravable hollow cylindrical printing original plate with a surface height difference of 20 m or less was prepared.
- An irregular pattern was formed on the surface of the prepared hollow cylindrical printing original plate using a carbon dioxide laser engraving machine.
- the shape of the formed halftone dot pattern was conical and good.
- a printing test was performed using a hollow cylindrical printing substrate having a pattern formed on its surface and a flexographic printing machine, it was possible to obtain a printed material having an excellent halftone dot pattern.
- the printing test was performed using a combination of UV ink and coated paper at a printing speed of 200 mZ. The UV ink transferred onto the coated paper was cured by irradiating light from an ultraviolet lamp, and fixed on the coated paper.
- a liquid photosensitive resin composition (trade name "APR-G-42", manufactured by Asahi Kasei Chemicals Co., Ltd.) with a thickness of about 0.5 mm was placed on an air cylinder with an outer diameter of 213.384 mm whose surface was released. A glass cloth having a width of 50 mm and a thickness of 300 m was spirally wound thereon three times. Further, the liquid photosensitive resin composition was applied to the surface of the glass cloth and the mesh of the glass cloth, and the glass cloth was not present at a depth of 0.5 mm from the surface.
- APR-G-42 manufactured by Asahi Kasei Chemicals Co., Ltd.
- the light of a metal nitride lamp (trade name “M056-L21” manufactured by I-Darafix Co., Ltd.) is emitted in the atmosphere at 4000 mj / cm 2 (UV meter Irradiation with a UV-M02 (trade name, manufactured by Oak Manufacturing Co., Ltd.) and a UV-35-APR filter were performed to obtain a cured photosensitive resin layer (1).
- the lamp illuminance on the surface of the photosensitive resin composition layer was measured using a UV meter (trade name “UV-M02” manufactured by Oak Manufacturing Co., Ltd.).
- Example 2 Using the same photosensitive resin as in Example 1, a resin layer (B) capable of laser engraving was formed on the obtained hollow cylindrical core material in the same manner as in Example 1.
- thermosetting two-part epoxy resin was used, and the same procedure as in Example 1 was repeated except that the mixture was heated to 50 ° C. Attempted fabrication. It took a day for the epoxy resin to completely cure.
- styrene-butadiene copolymer manufactured by Asahi Kasei Chemicals Co., Ltd., trade name “Taphrene A”, number average molecular weight: 73,000
- liquid polybutadiene Nippon Petrochemical Co., trade name “B-2000”, number average
- Molecular weight: 2000 20 parts by weight were kneaded in one step, and 10 parts by weight of the obtained kneaded product was mixed with 20 parts by weight of toluene to obtain a highly viscous liquid resin composition.
- the obtained liquid resin composition is applied to one side of a 50 mm, 25 ⁇ m thick polysulfone film to a thickness of 50 m, and the surface is released on a 213.384 mm outer diameter cylinder with an outer diameter of 213.384 mm. While heating with an infrared heater, polish from the surface where the resin composition was applied. The film was spirally wound three times with the ends of the film slightly overlapping. After cooling, a hollow cylindrical core material was obtained.
- styrene-butadiene copolymer manufactured by Asahi Kasei Chemicals Co., Ltd., trade name “Taphrene A”, number average molecular weight: 73,000), liquid polybutadiene (Nippon Petrochemical Co., trade name “B-2000”, number average) Molecular weight: 2000) 29 parts by weight, 1,9-nonanediol diatalylate (molecular weight: 268) 7 parts by weight, 2,2 dimethoxy-phenyl-acetophenone 2 parts by weight, 2,6 di-t-butyl p-talesol 1 part by weight Parts were kneaded in a kneader to obtain a solid photosensitive resin composition at 20 ° C.
- the solid photosensitive resin composition was applied using an extruder while being heated to 140 ° C. After cooling, it was visually observed that the hollow cylindrical core material was greatly deformed due to the generation of bubbles and the like.
- a liquid unsaturated polyester resin containing a volatile solvent is applied to a thickness of about 0.5 mm on an air cylinder with an outer diameter of 213.384 mm, the surface of which has been release-molded.
- a 300 m thick glass cloth was spirally wound five times. Further, the liquid unsaturated polyester resin was applied to the surface of the glass cloth and the mesh of the glass cloth.
- a 25 m-thick PET film that had been release-treated was wound around the surface thus obtained, and cured for 1 day in an oven heated to 70 ° C. After cooling, the PET film on the surface was peeled off to obtain a hollow cylindrical core material. The difference in height of the surface was greater than 500 / zm, and the surface was polished to obtain a smooth surface. The time required for this step was 60 minutes. There was a part where the glass cloth was exposed, and it was difficult to polish due to the scattering of dust.
- a thin adhesive is applied to the surface of the hollow cylindrical core material whose surface has been polished, and a hard urethane rubber sheet mixed with a cross-linking agent with a width of 50 mm and a thickness of 200 m is used to adjust the circumference. It was wound while heating and pressing. Thereafter, the release-treated PET film was wound around the obtained rubber surface, heated in an oven, and left for one day. After cooling, the rubber surface was polished and smoothed. The time required for this step was 40 minutes. After that, when left at room temperature for several days, the thickness of the rubber layer was partially reduced by about 30 m, so the surface was polished again.
- a resin layer (B) capable of laser engraving was formed on the surface of the obtained rubber layer.
- Example 2 aa ⁇ 3 Conical shape good
- Example 3 aaa ⁇ 3 Conical shape good
- Example 4 ⁇ a ⁇ ⁇ 3 Conical shape good
- Example 5 ⁇ ⁇ ⁇ 3 Conical shape good
- Example 6 r ⁇ ⁇ ⁇ 3 Conical shape is good
- the present invention relates to a method for forming a relief image for a flexographic printing plate by laser engraving, forming a surface processing pattern such as embossed color, forming a relief image for printing such as a tile, and forming a pattern of a conductor, semiconductor, or insulator in forming an electronic circuit.
- Printing, patterning of functional materials such as anti-reflective coatings for optical components, color filters, (near) infrared cut filters, etc., and alignment films in the manufacture of display devices such as liquid crystal displays or organic electroluminescent displays. It is suitable for a cylindrical printing original plate used for forming a coating film 'pattern' of an underlayer, a light emitting layer, an electron transporting layer, and a sealing material layer, and a production method thereof.
- FIG. 1 is a conceptual sectional view of a hollow cylindrical printing substrate of the present invention.
Abstract
Description
Claims
Priority Applications (6)
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CN2005800108551A CN1938162B (zh) | 2004-03-30 | 2005-03-28 | 中空圆柱状印刷元件及其生产方法、中空圆柱状芯材料 |
AT05727408T ATE458624T1 (de) | 2004-03-30 | 2005-03-28 | Hohlzyindrisches druckelement |
DE602005019550T DE602005019550D1 (de) | 2004-03-30 | 2005-03-28 | Hohlzyindrisches druckelement |
EP05727408A EP1731325B1 (en) | 2004-03-30 | 2005-03-28 | Hollow cylindrical printing element |
JP2006511646A JP4530367B2 (ja) | 2004-03-30 | 2005-03-28 | 中空円筒状印刷基材 |
US10/592,867 US20080156212A1 (en) | 2004-03-30 | 2005-03-28 | Hollow Cylindrical Printing Element |
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JP2004099099 | 2004-03-30 | ||
JP2004-099099 | 2004-03-30 |
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WO2005095115A1 true WO2005095115A1 (ja) | 2005-10-13 |
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PCT/JP2005/005751 WO2005095115A1 (ja) | 2004-03-30 | 2005-03-28 | 中空円筒状印刷基材 |
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US (1) | US20080156212A1 (ja) |
EP (1) | EP1731325B1 (ja) |
JP (1) | JP4530367B2 (ja) |
CN (1) | CN1938162B (ja) |
AT (1) | ATE458624T1 (ja) |
DE (1) | DE602005019550D1 (ja) |
WO (1) | WO2005095115A1 (ja) |
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JPWO2013176029A1 (ja) * | 2012-05-25 | 2016-01-12 | 株式会社シンク・ラボラトリー | パターン付ロール及びその製造方法 |
US10889100B2 (en) | 2014-10-16 | 2021-01-12 | Windmöller & Hölscher Kg | Method for producing an image structure |
Also Published As
Publication number | Publication date |
---|---|
CN1938162A (zh) | 2007-03-28 |
EP1731325A4 (en) | 2008-06-25 |
CN1938162B (zh) | 2011-06-01 |
DE602005019550D1 (de) | 2010-04-08 |
EP1731325A1 (en) | 2006-12-13 |
EP1731325B1 (en) | 2010-02-24 |
JP4530367B2 (ja) | 2010-08-25 |
US20080156212A1 (en) | 2008-07-03 |
ATE458624T1 (de) | 2010-03-15 |
JPWO2005095115A1 (ja) | 2008-02-21 |
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