USRE42593E1 - Photo-curable resin composition used for photo-fabrication of three-dimensional object - Google Patents
Photo-curable resin composition used for photo-fabrication of three-dimensional object Download PDFInfo
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- USRE42593E1 USRE42593E1 US10/671,438 US67143803A USRE42593E US RE42593 E1 USRE42593 E1 US RE42593E1 US 67143803 A US67143803 A US 67143803A US RE42593 E USRE42593 E US RE42593E
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- 0 [1*]C1(CC[2*])COC1 Chemical compound [1*]C1(CC[2*])COC1 0.000 description 5
- FMYKTVLFNBBKNU-UHFFFAOYSA-N C.CCC1(COCCC[SiH](C)CO[SiH3])COC1 Chemical compound C.CCC1(COCCC[SiH](C)CO[SiH3])COC1 FMYKTVLFNBBKNU-UHFFFAOYSA-N 0.000 description 1
- RVGLUKRYMXEQAH-UHFFFAOYSA-N CC1(C)COC1 Chemical compound CC1(C)COC1 RVGLUKRYMXEQAH-UHFFFAOYSA-N 0.000 description 1
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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
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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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
- G03F7/0037—Production of three-dimensional images
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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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
- G03F7/075—Silicon-containing compounds
- G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
Definitions
- the present invention relates to a photo-curable resin composition used for photo-fabrication of three-dimensional objects.
- a typical example of such a photo-fabrication process comprises forming a curable resin layer having a specified pattern by selectively irradiating with light using, for example, an ultraviolet radiation laser on the surface of a liquid photo-curable material (photo-curable resin composition) in a container, feeding the photo-curable resin composition equivalent to one layer to form another thin layer of the composition over this cured resin layer, and selectively irradiating this thin layer with light to form a new cured resin layer which is integrally laminated over the previously formed cured resin layer.
- This step is repeated a number of times, with or without changing the pattern in which the light is irradiated to form a three-dimensional object consisting of integrally laminated multiple cured resin layers.
- This photo-fabrication process has been attracting considerable attention, because the target three-dimensional object can easily be prepared in a short period of time even if it has a complicated shape.
- resin compositions (A) to (C) represent photo-curable resin compositions conventionally used in the photo-fabrication process.
- a radically polymerizable organic compound such as urethane(meth)acrylate, oligoester(meth)acrylate, epoxy(meth)acrylate, thiol-ene compounds, photosensitive polyimide, and the like
- the characteristics required of the photo-curable resin composition used for these photo-fabrication processes include a low viscosity to quickly form a smooth liquid surface and the capability of being rapidly cured by irradiation with light. Also, the required characteristics of the photo-curable resin composition are minimal swelling of the cured products and minimal deformation due to shrinkage during curing with light, so as to minimize the production of defective parts such as warped parts, indented parts (sinkmark), or stretched parts (overhanging parts).
- Three-dimensional objects prepared by photo-fabrication methods have conventionally been used for design models, trial mechanical parts for confirming the functionality, or masters for molds.
- this process for trial mechanical parts it is important that the three-dimensional object has high dimensional accuracy in accordance with the design in fine processing, mechanical strength and heat resistance sufficient to withstand conditions of use.
- a radical polymerizable organic compound such as urethane(meth)acrylate, oligoester(meth)acrylate, or epoxy(meth)acrylate
- problems of deformation with the passage of time can be partly solved by the correction of the input data to the CAD.
- CAD corrections are insufficient to compensate for modern trial mechanical parts which have intricate and complicated shapes, or for circumstantial variations of use.
- the above-mentioned conventional resin composition (B) include a cationically photo-polymerizable compound containing an epoxy compound have drawbacks that the photo-curing rate of the resin solution is lower than that of resin compositions including a radically photo-polymerizable compound in photo-fabrication processes, necessitating the processing time to be prolonged. Also, three-dimensional objects prepared by photo-fabrication using resin compositions including a cationically photo-polymerizable compound containing a conventionally known epoxy compound are not provided with sufficient toughness required for the trial mechanical parts used for confirming the functionality.
- the present invention has been achieved in view of this situation and has an object of providing a photo-curable resin composition used for photo-fabrication, which can be rapidly cured to ensure reduction in the period of time required for photo-fabrication processes. Also, the present invention has an object of providing a photocurable composition used for photo-fabrication, which can provide three-dimensional objects which have high toughness and dimensional accuracy.
- a photo-curable resin composition used for photo-fabrication of three-dimensional objects comprising,
- FIGURE is a front elevation view of a three-dimensional object for evaluating the fabricating capability of the resin compositions prepared in the Examples and the Comparative Examples.
- a compound having an oxetane ring (herein referred to as an oxetane compound) is employed as Component (A) of the photo-curable resin composition of the present invention.
- the oxetane compound of the present invention is a compound having one or more oxetane rings represented by the following formula (1). This compound can be polymerized or crosslinked by radiation from light in the presence of a cationic photo-initiator.
- the oxetane compound h may contain 1 or more oxetane groups. Preferably, the compound has less than 20, and in particular less than 10 oxetane groups. In particularly preferred embodiments, the oxetane compound has two oxetane groups. It may also be useful to use mixtures of oxetane compounds, in particular those having 1, 2, 3, 4 or 5 oxetane groups.
- the oxetane compound preferably has a molecular weight of about 100 or more, preferably of about 200 or more. Generally, this compound will have a molecular weight of about 10,000 or lower, preferably of about 5,000 or lower.
- the oxetane groups preferably constitute the terminus of radiation curable oligomers having a phenyl, (oligo)-bis-phenyl, polysiloxane or polyether, backbone.
- polyethers are poly-THF, polypropylene glycol, alkoxylated trimethylolpropane, alkoxylated pentaerythritol and the like.
- the oxetane compound has one or more groups according to formula (2):
- Z is oxygen or sulfur, most preferably oxygen, and in which R 1 and R 2 constitute the remainder of a molecule.
- Examples of the compound having one oxetane ring used as component(A) are the compounds represented by the above formula (2), wherein Z represents an oxygen atom or a sulfur atom, R 1 represents a hydrogen atom; fluorine atom; alkyl group having from 1 to 6 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or the like; fluoroalkyl group having from 1 to 6 carbon atoms such as a trifluromethyl group, perfluoroethyl group, perfluoropropyl group, or the like; aryl group having from 6 to 18 carbon atoms such as a phenyl group, naphthyl group, or the like; furyl group, or thienyl group, and R 2 represents a hydrogen atom, alkyl group having from 1 to 6 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or the like; alkeny
- oxetane compounds having two oxetane rings include, for example, those compounds represented by the following formula (3):
- R 1 independently represents a group represent by formula (2)
- R 3 represents a linear or branched alkylene group having from 1 to 20 carbon atoms such as an ethylene group, propylene group, butylene group, or the like; linear or branched poly(alkylenoxy) group having from 1 to 120 carbon atoms such as poly(ethylenoxy) group, poly(propylenoxy) group, or the like; linear or branched unsaturated hydrocarbon group such as a propenylene group, methylpropenylene group, butenylene group, or the like; carbonyl group, alkylene group containing a carbonyl group, alkylene group containing a carboxyl group in the middle of a molecular chain, and alkylene group containing a carbamoyl group in the middle of a molecular chain.
- R 3 may be a polyvalent group represented by any one of the following formulas (4)-(6).
- ⁇ represents a phenyl ring
- R 4 represents an alkyl group having from 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or the like; alkoxy group having from 1 to 4 carbon atoms such as a methoxy group, ethoxy group, propyoxy group, butoxy group, or the like; halogen atom such as a chlorine atom, bromine atom, or the like; nitro group, cyano group, mercapto group, lower alkylcarboxyl group, carboxyl group, or carbamoyl group, and x is an integer of from 0 to 4.
- R 5 represents an oxygen atom, sulfur atom, methylene group, and groups represented by the formulae —NH—, —SO—, —SO 2 —, —C(CF 3 ) 2 —, or —C(CH 3 ) 2 —.
- R 6 represents an alkyl group having from 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or the like, or aryl group having from 6 to 18 carbon atoms such as a phenyl group, naphthyl group, or the like
- y denotes an integer of from 0 to 200
- R 7 represents an alkyl group having from 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or the like or aryl group having from 6 to 18 carbon atoms such as a phenyl group, naphthyl group, or the like.
- R 7 may be a group represented by the following formula (7). —O—[—Si(R 8 ) 2 —O—] z —Si(R 8 ) 2 —R 8 (7) wherein R 8 represents an alkyl group having from 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or the like, or aryl group having from 6 to 18 carbon atoms such as a phenyl group, naphthyl group, or the like, and z is an integer of from 0 to 100.
- R 1 represents the same group as defined in the formula (2).
- R 2 is a polyfunctional organic group with a valence of from 3 to 10, such as linear or branched alkylene groups having from 1 to 30 carbon atoms or linear or branched disiloxane or polysiloxane groups.
- polyfunctional compounds include linear or branched poly(alkyleneoxy) groups, for example, alkoxylated trimethylolpropane, or linear or branched polysiloxane containing groups with 2-10 dimethyl siloxane groups.
- alkylene groups having a valence of 3 or more include trimethylol alkane in which the alkyl group has from 1 to 6 carbon atoms such as a methyl group, ethyl group, propyl group, or the like, pentaerythritol, dipentaerythritol, glucose, and the like.
- the compound having oxetane rings used as component(A) may include compounds with a high molecular weight, e.g. a number average molecular weight reduced polystyrene of 1,000 to 5,000, measured using gel permeation chromatography.
- a high molecular weight e.g. a number average molecular weight reduced polystyrene of 1,000 to 5,000, measured using gel permeation chromatography.
- R 1 of formula (2) is e.g. methyl, ethyl or propyl
- R 2 is polyethyleneglycol with a polymerisation degree of between 20-200
- R 3 is polyTHF
- compounds which are based on alkoxylated pentaerythritol and the like are based on alkoxylated pentaerythritol and the like.
- component(A) Given as specific examples of the compounds having an oxetane ring used as component(A) are the following compounds:
- Typical examples of the compounds having one oxetane ring are as follows.
- Typical examples of the compounds having two or more oxetane rings are as follows.
- preferred compounds having oxetane rings which can be used as component (A) contained in the resin composition of the present invention, are (3-ethyl-3-oxetanylmethoxy)methylbenzene shown by the formula (12) illustrated below, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene shown by the formula (13) illustrated below, 1,2-bis(3-ethyl-3-oxetanylmethoxy)ethane shown by the formula (14) illustrated below, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl) ether shown by the formula (15) illustrated below, and the compounds represented by formula (16) shown below.
- R 1 represents the same group as defined in the formula (2)
- R 8 represents the same group as defined in the formula (7)
- R 11 represents an alkyl group having from 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or the like or a trialkylsilyl group, wherein the alkyl groups may be either the same or different and have from 3 to 12 carbon atoms, such as a trimethylsilyl group, triethylsilyl group, tripropylsilyl group, or tributylsilyl group, and z′ is an integer from 1 to 10.
- These compounds having oxetane rings may be used either individually or in combinations of two or more.
- the proportion of component, (A) in the resin composition of the present invention is usually 30-97% by weight, preferably 40-96% by weight, and more preferably 50-95% by weight. If the proportion of component (A) is too low, the rate (curing rate) of the cationic polymerization reaction is so reduced that molding time may be extended and the resolution may tend to be lower. On the other hand, if the proportion of component (A) is too high, there are tendencies that the toughness of the cured product is lower and the rate (curing rate) of the cationic polymerization reaction is reduced.
- a compound having an epoxy group (herein referred to as an epoxy compound) is employed as Component (B) of the photo-curable resin composition of the present invention.
- the epoxy compound of the present invention is a compound having an epoxy group and a number average molecular weight reduced to polystyrene of 1,000-20,000, preferably 1,500-10,000, and more preferably 2,000-5,000, measured using gel permeation chromatography.
- the molecular weight of this range is preferable to improve the characteristics of the resin composition, such as the viscosity of the resin composition, the period of time required for photo-fabrication, and the toughness of the cured product.
- epoxy compounds suitable for the present invention are (1) epoxidated compounds obtained by a process which comprises epoxidating a double bond between carbons of a corresponding compound having an ethylenically unsaturated bond using an appropriate oxidizing agent such as hydrogen peroxide or peroxy acid process (1); (2) polymers having an epoxy group prepared by a process which comprises polymerizing a radically polymerizable monomer containing an epoxy group in a molecule process (2); and (3) compounds having an epoxy group prepared by a known process, e.g. a process comprising reacting a compound having a functional group, e.g. hydroxyl group, with epichlorohydrin process (3).
- a compound having a number average molecular weight of 1,000-20,000 may be used as the raw material compound having an ethylenically unsaturated bond when using the above process (1).
- a known method may be used to prepare a polymer with a desired polymerization degree.
- a compound having a number average molecular weight reduced to polystyrene of 1,000-20,000 may be used as the raw material compound having a functional group, e.g. hydroxyl group.
- epoxidated compounds of above-mentioned (1) are polymers of conjugated diene monomers, copolymers of conjugated diene monomers and compounds having an ethylenically unsaturated bond, copolymers of diene monomers and compounds having an ethylenically unsaturated bond, and compounds prepared by epoxidating a copolymer such as natural rubber.
- examples of these compounds are compounds produced by epoxidating a polymer of conjugated diene monomers such as a butadiene monomer or isoprene monomer; compounds prepared by epoxidating a copolymer of a conjugated diene monomer and a compound having an ethylenically unsaturated bond, e.g. ethylene, propylene, butene, isobutylene, styrene; compounds prepared by epoxidating a copolymer of a compound having an ethylenically unsaturated bond and a diene monomer, e.g.
- epoxidated polybutadiene examples include Poly bd R-45 EPI (manufactured by Idemitsu Petrochemical Co., Ltd.), R-15EPI, R-45EPI (manufactured by Nagase Chemicals Ltd.), and Epolead PB3600, PB4700 (manufactured by Daicel Chemical Industries Ltd.).
- Epofriend ESBS AT014, AT015, AT000 manufactured by Daicel Chemical Industris Ltd.
- polymers of the above-mentioned process (2) having an epoxy group are homopolymers produced from monomers such as glycidyl (meth)acrylate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, 3,4-epoxycyclohexylmethyl (meth)acrylate, or caprolactone modified 3,4-epoxycyclohexylmethyl (meth)acrylate, and copolymers of these monomers and other vinyl monomers.
- the number average molecular weight of these compounds is in the range of 1,000-20,000 as converted into polystyrene.
- the above epoxy compounds may be used as component (B) either individually or in combinations of two or more.
- the proportion of component (B) in the resin composition of the present invention is usually 3-50% by weight, preferably 4-40% by weight, and more preferably 5-30% by weight. If the proportion of component (B) is too low, the rate (curing rate) of the cationic polymerization reaction is so reduced that molding time may be extended and the resolution and toughness of the cured product may tend to be reduced. On the other hand, if the proportion of component (B) is too high, the viscosity the resin composition is increased and molding time may tend to be prolonged.
- the cationic photo-initiator (hereinafter may be called from time to time component (C)) contained in the resin composition of the present invention is a compound capable of generating a molecule initiating cationic polymerization of components (A) and (B) upon exposure to radiation such as light.
- the cationic photo-initiator are onium salts represented by the following formula (17), which are compounds releasing Lewis acid on exposure to light: [R 12 a R 13 b R 14 c R 15 d W] +m [MX n ] ⁇ m (17) wherein the cation is an onium ion; W represents S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, or N ⁇ N; R 12 , R 13 , R 14 , and R 15 represent individually the same or different organic group; a, b, c, and d independently represent an integer from 0 to 3, and provided that a+b+c+d is equal to the valence number of W.
- formula (17) are compounds releasing Lewis acid on exposure to light: [R 12 a R 13 b R 14 c R 15 d W] +m [MX n ] ⁇ m (17) wherein the cation is an onium ion; W represents S, Se, Te, P, As, S
- M represents a metal or metalloid which constitutes a center atom of a halide complex.
- M are B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, and Co.
- X represents a halogen atom such as a fluorine atom, chlorine atom, or bromine atom.
- m is a substantial electric charge of the halide complex ion and n is the valence of M.
- onium salts represented by the formula (17) are diphenyliodonium, 4-methoxydiphenyliodonium, bis(4-methylphenyl) iodonium, bis(4-tert-butylphenyl) iodonium, bis(dodecylphenyl)-iodonium, triphenylsulfonium, diphenyl-4-thiophenoxy-phenylsulfonium,bis[4-(diphenylsulfonio)-phenyl]-sulfide, bis[4-(di(4-(2-hydroxyethyl)phenyl)sulfonio)-phenyl]sulfide, and ⁇ 5 -2,4-(cyclopentadienyl)-[(1,2,3,4,5,6- ⁇ )-(methylethyl)-benzene]-iron(1+).
- MX n negative ion
- BF 4 ⁇ tetrafluoroborate
- PF 6 ⁇ hexafluorophosphate
- SbF 6 ⁇ hexafluoroantimonate
- AsF 6 ⁇ hexafluoroarsenate
- SbCl 6 ⁇ hexachloroantimonate
- onium salts represented by the general formula [MX n (OH) ⁇ ] can be used instead of those represented by the formula [MX n ].
- onium salts including a negative ion for example, perchloric acid ion (ClO 4 ⁇ ), trifluoromethane sulfonate ion (CF 3 SO 3 ⁇ ), fluorosulfonate ion (FSO 3 ⁇ ), toluene sulfonate ion, trinitrobenzene sulfonate negative ion, and trinitrotoluene sulfonate ion, are given as other examples of onium salts.
- aromatic onium salts can be used as the cationic photo-initiator (C).
- aromatic onium salts the following compounds are preferred: aromatic halonium salts described, for example, in Japanese Patent Applications Laid-open No. 151996/1975 and No. 158680/1975; VIA group aromatic onium salts described, for example, in Japanese Patent Applications Laid-open No. 151997/1975, 30899/1977, No. 55420/1981, and No. 125105/1980; VA group aromatic onium salts described, for example, in Japanese Patent Application Laid-open No. 158698/1975; oxosulfoxonium salts described, for example, in Japanese Patent Applications Laid-open No. 8428/1981, No.
- UVI-6950 UVI-6970(bis[4-(di(2-hydroxyethyl)phenyl)sulfonio]-phenylsulfide), UVI-6974 (bis[4-diphenylsulfonio)-phenyl]sulfidebishexafluoro-antimonate, UVI-6990 (hexafluorophosphate salt of UVI-6974) (manufactured by Union Carbide Corp), Adekaoptomer SP-151, SP-170 (bis[4-(di(4-(2-hydroxyethyl)phenyl)sulfonio]-phenylsul fide), SP-171 (manufactured by Asahi Denka Kogyo Co., Ltd.), Irgacure 261 ( ⁇ 5 -2,4-(cyclopentadien-1-yl
- cationic photo-initiators can be used as component (C) either individually or in combinations of two or more.
- the proportion of component (C) in the resin composition of the present invention is 0.1-10% by weight, preferably 0.2-5% by weight, and more preferably 0.3-3% by weight. If the proportion of component (C) is too low, the photo-curing characteristic of the resin composition obtained is insufficient. It is becomes difficult to form a three-dimensional object having sufficient mechanical strength from such a resin composition. Similarly, if the proportion of component (C) is too high, it becomes difficult to obtain the appropriate light capability (curing depth) when the resulting resin composition is used in the photo-fabrication process. In addition, the mechanical strength such as toughness of the three-dimensional object prepared from such a resin composition tends to be reduced.
- cationically polymerizable organic compounds other than components (A) and (B) may be given.
- a cationically polymerizable compound is defined as a compound having an organic group which can polymerize or crosslink by photo-irradiation in the presence of an acid or a cation.
- Such cationically polymerizable organic compounds include epoxy compounds other than component (B), oxolane compounds, cyclic acetal compounds, cyclic lactone compounds, thiirane compounds, thietane compounds, vinylether compounds, spiro-ortho ester compounds which are reaction products of an epoxy compound and lactone, ethylenically unsaturated compounds, cyclic ether compounds, cyclic thioether compounds, and vinyl compounds.
- epoxy compounds other than component (B) are, in particular, epoxy compounds with a molecular weight of less than about 1000 which include alicyclic epoxy compounds such as 3,4-epoxycyclohexylmethyl-3′,4′-epoxy-cyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-metha-dioxane, bis(3,4-epoxy-cyclohexylmethyl)adipate, vinylcyclohexene oxide, 4-vinyl epoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methyl cyclohexyl-3′,4′-epoxy-6′-methyl-cyclohexane carboxylate, methylenebis(3,4-epoxy- cyclohexane), dicyclopentadiene diepoxide
- oxolane compounds such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran
- cyclic acetals such as trioxane, 1,3-dioxolane, and 1,3,6-trioxan cyclooctane
- cyclic lactones such as ⁇ -propiolactone and ⁇ -caprolactone
- thiiranes such as ethylene sulfide, 1,2-propylene sulfide, and thioepychlorohydrin
- thiethanes such as 3,3-dimethyl thiethane
- vinyl ethers such as ethylene glycol divinyl ether, triethylene glycol divinyl ether, and trimethylolpropane trivinyl ether
- spiro-ortho esters which are obtained by a reaction of epoxy compound and lactone
- ethylenically unsaturated compounds such as vinyl cyclohexolane compounds
- the resin composition of the present invention may contain polyols for developing photo-curability of the resin composition, and the shape stability (resistance to deformation with time) and characteristic stability (resistance to change in mechanical performance with time) of the three-dimensional object obtained from the resin composition.
- the polyether polyol has three or more, preferably from 3 to 6 hydroxyl groups in one molecule. If polyether polyols (polyether diols)having less than three hydroxyl groups are used, the object of developing the photo-curing characteristics can not be achieved and a three-dimensional object with sufficient mechanical strength can not be produced. On the other hand, if polyether polyols having 7 or more hydroxyl groups are used, the elongation and toughness of the three-dimensional object obtained from the resin composition tends to be lower.
- suitable polyols are polyether polyols prepared by modifying polyhydric alcohol of more than 3 valences such as trimethylolpropane, glycerol, pentaerythritol, sorbitol, sucrose, quodorol, or the like by a cyclic ether compound such as ethylene oxide (EO), propylene oxide (PO), butylene oxide, tetrahydrofuran, or the like; caprolactone polyols prepared by modifying caprolactone; and polyester polyols prepared by modifying polyesters consisting of a dibasic acid and a diol.
- polyether polyols prepared by modifying polyhydric alcohol of more than 3 valences such as trimethylolpropane, glycerol, pentaerythritol, sorbitol, sucrose, quodorol, or the like by a cyclic ether compound such as ethylene oxide (EO), propylene oxide (PO), butylene oxide,
- polyether polyols are EO modified trimethylolpropane, PO modified trimethylolpropane, tetrahydrofuran modified trimethylolpropane, caprolactone modified trimethylolpropane, EO modified glycerol, PO modified glycerol, tetrahydrofuran modified glycerol, caprolactone modified glycerol, EO modified pentaerythritol, PO modified pentaerythritol, tetrahydrofuran modified pentaerythritol, caprolactone modified pentaerythritol, EO modified sorbitol, PO modified sorbitol, caprolactone modified sorbitol, EO modified sucrose, PO modified sucrose, and EO modified quodor.
- EO modified trimethylolpropane PO modified trimethylolpropane, caprolactone modified trimethylolpropane, PO modified glycerol, caprolactone modified glycerol, and PO modified sorbitol are preferred.
- the present invention is not limited to these examples.
- Specific examples of commercially available products polyols are Sunnix TP-400, Sunnix GP-600, Sunnix GP-1000, Sunnix SP-750, Sunnix GP-250, Sunnix GP-400, Sunnix GP-600 (manufactured by Sanyo Chemical Industries, Ltd.), TMP-3 Glycol, PNT-4 Glycol, EDA-P-4, EDA-P-8 (manufactured by Nippon Nyukazai Co., Ltd.), G-300, G-400, G-700, T-400, EDP-450, SP-600, SC-800 (manufactured by Asahi Denka Kogyo Co., Ltd.), TONE 0301, TONE 0305, TONE 0310 (manufactured by Union Carbide Corp.), and PLACCEL 303, PLACCEL 305, PLACCEL 308 (manufactured by Daicel Chemical Industries, Ltd.).
- the resin composition of the present invention may include an ethylenically unsaturated monomer, which is a radically polymerizable compound, to improve the mechanical strength of the cured product and to reduce the time required for fabrication.
- the ethylenically unsaturated monomer is a compound having ethylenically unsaturated groups (C ⁇ C) in the molecule.
- component (C) are mono-functional monomers having one ethylenically unsaturated bond in one molecule, and polyfunctional monomers having two or more ethylenically unsaturated bonds in one molecule.
- Examples of mono-functional monomers are acrylamide, (meth)acryloyl morpholine, 7-amino-3,7-dimethyloctyl (meth)acrylate, isobutoxymethyl (meth)acrylamide, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyldiethylene glycol (meth)acrylate, t-octyl (meth)acrylamide, diacetone (meth)acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, lauryl (meth)acrylate, dicyclopentadiene (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, N,N-dimethyl (meth)acrylamide tetrach
- isobornyl (meth)acrylate, lauryl (meth)acrylate, and phenoxyethyl (meth)acrylate are particularly preferred, although the present invention is not limited to these examples.
- Examples of commercially available products of the monofunctional monomers are Aronix M-101, M-102, M-111, M-113, M-117, M-152, TO-1210 (manufactured by Toagosei Chemical Industry Co., Ltd.), KAYARAD TC-110S, R-564, R-128H (manufactured by Nippon Kayaku Co., Ltd.), and Viscoat 192, Viscoat 220, Viscoat 2311HP, Viscoat 2000, Viscoat 2100, Viscoat 2150, Viscoat 8F, Viscoat 17F (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
- Preferred examples of polyfunctional monomers are ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol diacrylate, tetra ethylene glycol di(meth)acrylate, tricyclodecanediyl-dimethylene di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, caprolactone modified tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO modified trimethylolpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, both terminal (meth)acrylic acid adduct of bisphenol A dig
- polyfunctional monomers can be selected from the above-mentioned tri(meth)acrylate compounds, tetra(meth)acrylate compounds, penta(meth)acrylate compounds, and hexa(meth)acrylate compounds.
- preferred polyfunctional monomers are trimethylolpropane tri(meth)acrylate, EO modified trimethylolpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol
- a radical photo-initiator When compounding an ethylenically unsaturated monomer into a resin composition, a radical photo-initiator is usually added to the resin composition to initiate the radical polymerization reaction of the ethylenically unsaturated monomer.
- the radical photo-initiator is a compound which decomposes and generates radicals by photo-irradiation and initiates a radical reaction of the ethylenically unsaturated monomer by generating free radicals.
- Conventionally known radical photo-initiators may be used in the present invention.
- radical photo-initiators are acetophenone, acetophenone benzyl ketal, anthraquinone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, carbazole, xanthone, 4-chlorobenzo-phenone, 4,4′-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3′-dimethyl-4-methoxybenzophenone, thioxanethone compounds, 2-methyl-1-4-(methylthio) phenyl-2-morpholino-propane-2-on, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, triphenylamine, 2,4,6-trimethylbenzoyl diphenylphosphine oxides, bis (2,6-dimethoxybenzoyl)-2,4,4-tri-methylpentyl-phosphine oxide,
- benzyl dimethyl ketal 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and the like are particularly preferred.
- the present invention is not limited to these examples.
- Additives other than the cationically polymerizable compound and the radical photo-initiator, which may be employed in the resin composition as required, are photosensitizers (polymerization promoters) of amine compounds such as triethanolamine, methyl diethanolamine, triethylamine, diethylamine; photosensitizers including thioxantone or its derivatives, anthraquinone or its derivatives, anthracene or its derivatives, perillene and its derivatives, benzophenone, benzoin isopropylether, and the like; and reaction diluents such as vinyl ether, vinyl sulfide, vinyl urethane, or vinyl urea.
- photosensitizers polymerization promoters
- amine compounds such as triethanolamine, methyl diethanolamine, triethylamine, diethylamine
- photosensitizers including thioxantone or its derivatives, anthraquinone or its derivative
- additives include polymers or oligomers, such as epoxy resins other than the above-mentioned compound having an epoxy group used as component(B) and other epoxy compounds, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene-styrene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine oligomer, silicon oligomer, and polysulfide oligomer; polymerization inhibitors such as phenothiazine or 2,6-di-t-butyl-4-methyl phenol, polymerization initiation adjuvants, age resisters, leveling agents, wettability improvers, surfactants, plasticers, UV stabilizers, UV absorbers, silane coupling agents, pigments, dyes and the like.
- epoxy resins other than the above-mentioned compound having an epoxy group used as component(B) and other
- the resin composition of the present invention may include inorganic fillers, organic fillers, or the like.
- inorganic tillers are solid microparticles of inorganic compounds, such as glass beads, talc microparticles, and silicon oxide, and whiskers of basic magnesium sulfonate, aluminum oxide, or silicon oxide.
- organic fillers are organic solid microparticles of crosslinked polystyrene high polymer, crosslinked polymethacrylate high polymer, crosslinked polyethylene high polymer, and crosslinked polypropylene high polymer.
- silane coupling agent such as aminosilane, epoxysilane, and acrylsilane can be utilized.
- compositions of the present invention will have a dimensional accuracy value of less than 0.15, preferably less than 0.12, more preferable less than 0.10 mm (reference dimensional accuracy test procedure, below).
- the curability of the resin compositions of the present invention, as measured by the difference in Young's modulus at different curing doses is substantially the same.
- the resin composition preferably is formulated to have a Young's modulus after curing of a film, of 80 kg/mm 2 or higher, preferably fo 100 kg/mm 2 or higher.
- the Young's modulus of a cured film will be about 400 kg/mm 2 or less.
- this Young's modulus is substantially the same when exposed to an irradiation dose of 100 and 500 mJ/cm 2 , which means that the difference between the two Young's modulus values is less than 20%, more preferably less than 10% of the highest value measured.
- the difference in Young's modulus is typically less than 25, preferably less than 10, and more preferably is 4 kg/mm 2 or less (reference test procedure, below).
- the tensile elongation of the cured film preferably is between about 10-40%, more preferably, between about 13-30%.
- the resin composition of the present invention can be manufactured by homogeneously blending the above-mentioned components (A) to (C), the optional components which are added as required, and the various additives.
- the resulting resin compositions are useful for photocurable resin compositions for photo-fabrication. It is desirable for the photo-curable resin composition of the present invention to possess a viscosity at 25° C. in the range of 50-10,000 cps, preferably 100-5,000 cps.
- the photo-curable resin composition of the present invention prepared in the manner discussed herein is suitable as a photo-curable (liquid) material used in photo-fabrication processes.
- a three-dimensional object with a desired shape can be obtained by using the photo-fabrication process, including selectively irradiating visible light, ultraviolet light, or infrared light on the photo-curable resin composition of the present invention, and feeding the energy required to cure the resin composition.
- Such light irradiation means include, for example, a laser beam, a means for irradiating the composition with light and the like converged by a lens, mirror, or the like, while scanning, a means irradiating the composition with non-convergent light through a mask provided with a fixed pattern through which light is transmitted, and a means for irradiating the composition with light via a number of optical fibers bundled in a light conductive member corresponding to a fixed pattern.
- a mask electrooptically produces a mask image consisting of a light transmitting area and non-light-transmitting area according to a prescribed pattern by the same theory as that of the liquid crystal display apparatus.
- a means using a scanning laser beam with a small spot size is preferred for selectively irradiating the resin composition with light, when a resulting three-dimensional object possesses minute parts or when high dimensional accuracy is required to form the three-dimensional object.
- the irradiated surface (for example, a plane scanned by light) of the resin composition placed in a vessel is either the liquid surface of the resin composition or the interface of the liquid and a translucent wall of the vessel.
- the irradiated surface is the liquid surface or the interface of the liquid and the wall of the vessel, the light can be shone directly out of the vessel or through the vessel.
- a desired solid shape can be made by curing fixed parts of the resin composition and then moving the light spot from the cured parts to the uncured parts continuously or stepwise to laminate the cured parts.
- moving the light spot for example, a method for moving any of the light source, the vessel for the resin composition, or the cured parts of the resin composition.
- a fresh resin composition is supplied to the cured resin composition in the vessel.
- the surface of a support stage capable of being optionally elevated in the vessel is slightly lowered from the liquid surface to form a thin layer (1) of the resin composition.
- the thin layer (1) is selectively irradiated with light to form a solid cured resin layer (1′).
- the resin composition is supplied over this thin layer (1′) to form a second thin layer (2), and this thin layer (2) is selectively irradiated with light to laminate a new solid cured resin layer (2′) on the thin layer (1′).
- This step is repeated for a prescribed number of times, with or without changing the pattern subjected to light irradiation, to produce a three-dimensional object consisting of a multiple number of cured resin layers (1′) to (n′) which are integrally laminated.
- the three-dimensional object fabricated in this manner is discharged from the vessel and processed to remove the unreacted photo-curable resin composition remaining on the surface, and washed by a solvent, as required.
- solvents are an organic solvent which is represented by an alcohol, such as isopropyl alcohol or ethyl alcohol, an organic solvent such as acetone, ethyl acetate, methylethyl ketone, an aliphatic organic solvent such as a terpene, or a low viscosity liquid thermosetting resin or photo-curable resin.
- the cured product be washed using the thermosetting resin or photo-curable resin.
- This post-curing treatment is effective not only for curing the resin remaining uncured on the surface of the laminated body, but also for curing the resin composition which remains uncured inside the laminated body.
- the post-curing treatment is also effective in the case where the fabricated three-dimensional object is washed with an organic solvent.
- the three-dimensional object obtained in this manner has high mechanical strength, high dimensional accuracy, and excellent heat resistance. Also, the three-dimensional object exhibits high stability in maintaining a fixed shape and lasting stable properties. Therefore, the three-dimensional object prepared from the resin composition is preferably used for trial mechanical parts for confirming the functions.
- a heat-curable or photo-curable hard coating agent it is desirable to cover the surface of the three-dimensional object by a heat-curable or photo-curable hard coating agent to improve the strength and heat resistance of the surface.
- a hard coating agent an organic coating agent such as acrylic resin, epoxy resin, silicone resin, or the like, or an inorganic coating agent can be used. These hard coating agents may be used individually or in combinations of two or more.
- Transparent liquid compositions were prepared in the same manner as in Example 1 according to the formulations shown in Table 1, except that the different components were used.
- Transparent liquid compositions were prepared in the same manner as in Example 1 according to the formulations shown in Table 1, except that the different components and optional components were used. These comparative resin compositions had the following characteristics.
- polyester diol (trade mark: P-1010, manufactured by Kuraray Co., Ltd.) which was consisting of 3-methyl-1,5-pentane diol and adipic acid and which has a number average molecular weight of 1,000 was then added to the mixture, keeping the temperature at 40-50° C. The reaction was terminated after the agitation was further continued for five hours at 50-60° C. to obtain urethane acrylate (U-1) with a number average molecular weight of 1,680.
- P-1010 manufactured by Kuraray Co., Ltd.
- the curability of the resin solution shows a degree (curing rate) of polymerization reaction and crosslinking reaction of the resin composition with respect to the energy of photo-irradiation.
- the curing rate has influences on the dynamic properties of the cured products, such as Young's modulus, bending elasticity, and the like. Specifically, excellent photocurability is thought to ensure minimal change in the dynamic properties of the cured product to be produced.
- the curability of the resin solution is evaluated by measuring the Young's modulus of the cured resin film formed by irradiation of lights at different doses.
- a coated film with a thickness of 200 ⁇ m was prepared by applying a resin composition to a glass plate using an applicator.
- the surface of the film was irradiated with ultraviolet light at doses of 100 mJ/cm 2 and 500 mJ/cm 2 using a conveyer curing apparatus equipped with a metal halide lamp (UB0311-00 type, manufacture by Eye Graphics Co., Ltd.) to prepare a cured resin film.
- the cured resin film was allowed to stand in an air conditioned room maintained at 23° C. and RH 50% for one hour to produce test specimens. These test specimens were subjected to measurement.
- the toughness of the cured product shows resistance to external stress.
- One indicia of the resins toughness is tensile elongation.
- toughness of the cured film was evaluated by measuring the tensile elongation of the cured resin film.
- a coated film with a thickness of 200 ⁇ m was prepared by applying a resin composition to a glass plate using an applicator.
- the surface of the film was irradiated with ultraviolet light at a dose of 500 mJ/cm 2 using a conveyer curing apparatus equipped with a metal halide lamp.
- the irradiation was terminated before the resin composition was completely cured to prepare a half-cured resin film.
- the half cured resin film was peeled from the glass plate and placed on releasable paper.
- the side opposite to that first cured by irradiation was irradiated with ultraviolet light at a dose of 500 mJ/cm 2 to prepare a completely cured resin film.
- the cured resin film was allowed to stand in an air-conditioned room maintained at a temperature of 23° C. and a humidity of 50% for 24 hours.
- the tensile elongation of the test specimen was measured at a temperature of 23° C. under a humidity of 50% and the conditions of a drawing rate of 1 mm/min and a bench mark distance of 25 mm using the above tension tester. The results are shown in Table 2.
- the fabricating capability of the three-dimensional objects was evaluated by measuring the dimensional accuracy of the three-dimensional object prepared from each resin composition and time required for the fabrication.
- the resin compositions prepared in the Examples 1-5 and Comparative Examples 1-5 were fabricated according to the following conditions to produce three-dimensional objects each having an H-shape configuration as shown in the Figure.
- the two columns and the horizontal beam constituting the H shaped object 10 were all made of a prism with a 6.4 mm ⁇ 6.4 mm square cross section.
- the lengths of the columns 11 & 12 and horizontal beam 13 were 44.5 mm and 88.8 mm, respectively.
- Other target dimensions are shown in the Figure.
- the fabricated three-dimensional object was allowed to stand in an air-conditioned room maintained at 23° C. and RH 50% to condition.
- the actual widths 14 and 16 at positions 14 a and 16 a were measured using calipers having a measuring accuracy of 0.01 mm to calculate the differences between the lengths 14 and 15 , measured at 15 a, and the lengths 16 and 15 , similarly measured at 15 a, according to the equations (I) and (II) illustrated below.
- the dimensional accuracy was evaluated based on these differences. The results are shown in Table 2.
- Dimensional difference between A and B (A ⁇ B) (I)
- Dimensional difference between C and B (C ⁇ B) (II)
- the resin composition prepared in the Comparative Example 2 excluding component (A) exhibited only insufficient curability and mechanical strength because the Young's modulus of a cured film of the resin composition was small similarly to that obtained in the Comparative Example 1.
- the Young's modulus of the photocurable resin composition of the epoxy/acryl monomer hybrid type, which was prepared in the Example 4 was so low that the curability of the resin composition was insufficient for photo-fabricating applications.
- the tensile elongation bf the cured films prepared from the resin compositions of the Examples 1-5 ranged from 17% to 19%, indicating sufficient toughness for photo-fabricating applications.
- the tensile elongation of the resin compositions excluding component (B) which were prepared in the Comparative Examples 1 and 3 was 5% and 7% respectively. Therefore, the toughness of the resin compositions excluding component (B) was insufficient for photo-fabricating applications.
- the tensile elongation of the resin composition prepared in the Comparative Example 4 was 6% so that sufficient toughness for photo-fabricating applications could not be provided.
- the photocurable resin compositions prepared in the Examples 1-5 and the urethane acrylate type photocurable resin composition prepared in the comparative Example 5 required less than 10 hours to be optically molded.
- the strength of the resin cured by laser irradiation which was called “Green strength”
- Green strength was so small that a target three-dimensional object could not be produced.
- the resin compositions prepared in the Comparative Examples 2 and 4 required more than 20 hours to be optically molded.
- the photocurable resin composition used for photo-fabrication in the present invention has excellent photocurability, by which the resin composition can be promptly cured by irradiation with lights so that the time required for fabrication can be reduced. Also, shrinkage during curing is so small, so that three-dimensional objects having high dimensional accuracy and excellent mechanical characteristics, especially excellent toughness, can easily be prepared.
Abstract
Description
in which Z is oxygen or sulfur, most preferably oxygen, and in which R1 and R2 constitute the remainder of a molecule.
wherein R1 independently represents a group represent by formula (2), R3 represents a linear or branched alkylene group having from 1 to 20 carbon atoms such as an ethylene group, propylene group, butylene group, or the like; linear or branched poly(alkylenoxy) group having from 1 to 120 carbon atoms such as poly(ethylenoxy) group, poly(propylenoxy) group, or the like; linear or branched unsaturated hydrocarbon group such as a propenylene group, methylpropenylene group, butenylene group, or the like; carbonyl group, alkylene group containing a carbonyl group, alkylene group containing a carboxyl group in the middle of a molecular chain, and alkylene group containing a carbamoyl group in the middle of a molecular chain. Also, in the formula (3), R3 may be a polyvalent group represented by any one of the following formulas (4)-(6).
—CH2—Ø(R4)x—CH2— (4)
wherein Ø represents a phenyl ring, R4 represents an alkyl group having from 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or the like; alkoxy group having from 1 to 4 carbon atoms such as a methoxy group, ethoxy group, propyoxy group, butoxy group, or the like; halogen atom such as a chlorine atom, bromine atom, or the like; nitro group, cyano group, mercapto group, lower alkylcarboxyl group, carboxyl group, or carbamoyl group, and x is an integer of from 0 to 4.
—CH2—Ø—R5—Ø—CH2— (5)
wherein R5 represents an oxygen atom, sulfur atom, methylene group, and groups represented by the formulae —NH—, —SO—, —SO2—, —C(CF3)2—, or —C(CH3)2—.
—(—CH2)3—Si(R6)2—O—[Si(R7)2—O]y—Si(R6)2—(CH2)3— (6)
wherein R6 represents an alkyl group having from 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or the like, or aryl group having from 6 to 18 carbon atoms such as a phenyl group, naphthyl group, or the like, y denotes an integer of from 0 to 200, and R7 represents an alkyl group having from 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or the like or aryl group having from 6 to 18 carbon atoms such as a phenyl group, naphthyl group, or the like. Alternatively, R7 may be a group represented by the following formula (7).
—O—[—Si(R8)2—O—]z—Si(R8)2—R8 (7)
wherein R8 represents an alkyl group having from 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or the like, or aryl group having from 6 to 18 carbon atoms such as a phenyl group, naphthyl group, or the like, and z is an integer of from 0 to 100.
- 3-ethyl-3-hydroxymethyloxetane
- 3-(meth)-allyloxymethyl-3-ethyloxetane
- (3-ethyl-3-oxetanylmethoxy)methylbenzene
- 4-fluoro-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene
- 4-methoxy-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene
- [1-(3-ethyl-3-oxetanylmethoxy)ethyl]phenyl ether
- isobutoxymethyl(3-ethyl-3-oxetanylmethyl) ether
- isobornyloxyethyl(3-ethyl-3-oxetanylmethyl) ether
- isobornyl(3-ethyl-3-oxetanylmethyl) ether
- 2-ethylhexyl(3-ethyl-3-oxetanylmethyl) ether
- ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether
- dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether
- dicyclopentenyloxyethyl(3-ethyl-3-oxetanylmethyl) ether
- dicyclopentenyl(3-ethyl-3-oxetanylmethyl) ether
- tetrahydrofurfuryl(3-ethyl-3-oxetanylmethyl) ether
- tetrabromophenyl(3-ethyl-3-oxetanylmethyl) ether
- 2-tetrabromophenoxyethyl(3-ethyl-3-oxetanylmethyl) ether
- tribromophenyl(3-ethyl-3-oxetanylmethyl) ether
- 2-tribromophenoxyethyl(3-ethyl-3-oxetanylmethyl) ether
- 2-hydroxyethyl(3-ethyl-3-oxetanylmethyl) ether
- 2-hydroxypropyl(3-ethyl-3-oxetanylmethyl) ether
- butoxyethyl (3-ethyl-3-oxetanylmethyl) ether
- pentachlorophenyl(3-ethyl-3-oxetanylmethyl) ether
- pentabromophenyl(3-ethyl-3-oxetanylmethyl) ether
- bornyl(3-ethyl-3-oxetanylmethyl) ether
Compounds Having Two or More Oxetane Rings
- 3,7-bis(3-oxetanyl)-5-oxa-nonan
- 3,3′-(1,3-(2-methylenyl)propanediylbis-(oxymethylene))-bis-(3-ethyloxetane)
- 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene
- 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane
- 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane
- ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether
- dicyclopentenylbis(3-ethyl-3-oxetanylmethyl) ether
- triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether
- tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether
- tricyclodecanediyldimethylene bis(3-ethyl-3-oxetanylmethyl) ether
- trimethylolpropane tris(3-ethyl-3-oxetanylmethyl) ether
- 1,4-bis(3-ethyl-3-oxetanylmethyl)butane
- 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane
- pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether
- pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether
- polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether
- dipentaerythritol hexakis(3-ethyl-3-oxetanylmethyl)
- ether,dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether
- dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether
- caprolactone modified dipentaerythritol hexakis(3-ethyl-3-oxetanylmethyl) ether
- caprolactone modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether
- ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether
- EO modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether
- PO modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether
- EO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether
- PO modified hydrogenated bis(3-ethyl-3-oxetanylmethyl) ether
- EO modified bisphenol F bis(3-ethyl-3-oxetanylmethyl) ether
wherein R1 represents the same group as defined in the formula (2), R8 represents the same group as defined in the formula (7), R11 represents an alkyl group having from 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or the like or a trialkylsilyl group, wherein the alkyl groups may be either the same or different and have from 3 to 12 carbon atoms, such as a trimethylsilyl group, triethylsilyl group, tripropylsilyl group, or tributylsilyl group, and z′ is an integer from 1 to 10.
[R12 aR13 bR14 cR15 dW]+m[MXn]−m (17)
wherein the cation is an onium ion; W represents S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, or N≡N; R12, R13, R14, and R15 represent individually the same or different organic group; a, b, c, and d independently represent an integer from 0 to 3, and provided that a+b+c+d is equal to the valence number of W. M represents a metal or metalloid which constitutes a center atom of a halide complex. Typical examples of M are B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, and Co. X represents a halogen atom such as a fluorine atom, chlorine atom, or bromine atom. m is a substantial electric charge of the halide complex ion and n is the valence of M.
- Comparative Example 1: component (B) was not used.
- Comparative Example 2: 3,4-Epoxycyclohexylmethyl-3′,4′-epoxyhexane carboxylate was used instead of component (A).
- Comparative Example 3: component (B) was not used.
- Comparative Example 4: An epoxy/acryl monomer hybrid-type photocurable resin composition.
- Comparative Example 5: Urethane acrylate photocurable resin composition.
TABLE 1 | ||
Example | Comparative Example |
1 | 2 | 3 | 4 | 5 | 1 | 2 | 3 | 4 | 5 | |
Component A | 90 | 75 | 70 | 63 | 58 | 99 | 75 | |||
1,4-bis[(3-ethyl-3- | ||||||||||
oxetanylmethoxy)- | ||||||||||
methylbenzene | ||||||||||
Component B | 9 | 24 | 9 | 21 | 18 | 24 | ||||
Epoxidated poly- | ||||||||||
butadiene (Epolead | ||||||||||
PB3600) | ||||||||||
Component C | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | |
UVI-6974 | ||||||||||
3,4-epoxycyclohexyl- | 20 | 75 | 24 | 49 | ||||||
methyl-3',4'-epoxycyclo- | ||||||||||
hexane carboxylate | ||||||||||
1,4-butanediol diglycidyl | 21 | |||||||||
ether | ||||||||||
Caprolactone modified | 8 | 14 | ||||||||
| ||||||||||
Trimethylolpropane | ||||||||||
14 | 14 | 14 | ||||||||
triacrylate | ||||||||||
1-hydroxyphenyl ketone | 1 | 1 | 1 | 7 | ||||||
Urethane acrylate (U-1) | 36 | |||||||||
Tricyclodecanediyl | 18 | |||||||||
dimethylene diacrylate | ||||||||||
Isobornyl acrylate | 23 | |||||||||
| 16 | |||||||||
Evaluation of the Resin Composition
- (i) Laser beam intensity on the liquid surface: 10 mW
- (ii) Scanning velocity: the optimum velocity for the cured depth of the composition to be 0.15 mm.
- (iii) Thickness of cured resin layer: 0.1 mm
- (iv) Number of lamination: 445
Dimensional difference between A and B=(A−B) (I)
Dimensional difference between C and B=(C−B) (II)
TABLE 2 | ||
Example | Comparative Example |
1 | 2 | 3 | 4 | 5 | 1 | 2 | 3 | 4 | 5 | |
[Curability of resin solution] | ||||||||||
Young's modulus of cured film (kg/mm2) | ||||||||||
Irradiation dose | 112 | 115 | 134 | 113 | 106 | 17 | 25 | 134 | 60 | 104 |
100 mJ/cm2 | ||||||||||
500 mJ/cm2 | 115 | 119 | 137 | 116 | 107 | 42 | 63 | 137 | 132 | 104 |
[Toughness of cured product] | 17 | 18 | 17 | 19 | 18 | 5 | 13 | 7 | 6 | 30 |
Tensile elongation of cured film (%) | ||||||||||
[Fabrication capability] | ||||||||||
Dimensional accuracy (mm) | ||||||||||
Difference | ||||||||||
A-B | −0.10 | −0.09 | −0.09 | −0.10 | −0.09 | — | −0.09 | −0.15 | −0.07 | −0.32 |
C-B | 0.07 | 0.08 | 0.08 | 0.09 | 0.08 | — | 0.11 | 0.24 | 0.10 | 0.65 |
Time for fabrication (hour) | 8.1 | 8.5 | 9.0 | 8.5 | 8.5 | * | 35 | 8.5 | 22 | 7.2 |
*The Green strength of the fabricated product was so low that a target three-dimensional object could not be produced. |
Claims (31)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/671,438 USRE42593E1 (en) | 1996-12-13 | 2003-09-26 | Photo-curable resin composition used for photo-fabrication of three-dimensional object |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8-352893 | 1996-12-13 | ||
JP35289396A JP3765896B2 (en) | 1996-12-13 | 1996-12-13 | Photocurable resin composition for optical three-dimensional modeling |
US08/989,407 US5981616A (en) | 1996-12-13 | 1997-12-12 | Photo-curable resin composition used for photo fabication of three-dimensional objects |
US09/394,031 US6365644B1 (en) | 1996-12-13 | 1999-09-13 | Photo-curable resin composition used for photo-fabrication of three-dimensional object |
US10/671,438 USRE42593E1 (en) | 1996-12-13 | 2003-09-26 | Photo-curable resin composition used for photo-fabrication of three-dimensional object |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/394,031 Reissue US6365644B1 (en) | 1996-12-13 | 1999-09-13 | Photo-curable resin composition used for photo-fabrication of three-dimensional object |
Publications (1)
Publication Number | Publication Date |
---|---|
USRE42593E1 true USRE42593E1 (en) | 2011-08-02 |
Family
ID=26579727
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/989,407 Expired - Lifetime US5981616A (en) | 1996-12-13 | 1997-12-12 | Photo-curable resin composition used for photo fabication of three-dimensional objects |
US09/394,031 Ceased US6365644B1 (en) | 1996-12-13 | 1999-09-13 | Photo-curable resin composition used for photo-fabrication of three-dimensional object |
US10/671,438 Expired - Lifetime USRE42593E1 (en) | 1996-12-13 | 2003-09-26 | Photo-curable resin composition used for photo-fabrication of three-dimensional object |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/989,407 Expired - Lifetime US5981616A (en) | 1996-12-13 | 1997-12-12 | Photo-curable resin composition used for photo fabication of three-dimensional objects |
US09/394,031 Ceased US6365644B1 (en) | 1996-12-13 | 1999-09-13 | Photo-curable resin composition used for photo-fabrication of three-dimensional object |
Country Status (4)
Country | Link |
---|---|
US (3) | US5981616A (en) |
EP (1) | EP0848294B1 (en) |
JP (1) | JP3765896B2 (en) |
DE (1) | DE69706816T2 (en) |
Families Citing this family (91)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040137734A1 (en) * | 1995-11-15 | 2004-07-15 | Princeton University | Compositions and processes for nanoimprinting |
US8603386B2 (en) * | 1995-11-15 | 2013-12-10 | Stephen Y. Chou | Compositions and processes for nanoimprinting |
JP3765896B2 (en) | 1996-12-13 | 2006-04-12 | Jsr株式会社 | Photocurable resin composition for optical three-dimensional modeling |
US6261665B1 (en) * | 1997-09-16 | 2001-07-17 | Tomoegawa Paper Co., Ltd. | Anti-reflection material and method for producing the same |
DE69940916D1 (en) | 1998-02-18 | 2009-07-09 | Dsm Ip Assets Bv | Photohardenable liquid resin composition |
ES2232176T5 (en) * | 1998-09-28 | 2007-09-16 | Novo Nordisk A/S | PEG-BASED MACROMONOMERS, CHEMICALLY INERT POLYMERS PREPARED FROM THEMSELVES AND THE USE OF THESE POLYMERS FOR ORGANIC SYNTHESIS AND ENZYMATIC REACTIONS. |
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JP4350832B2 (en) * | 1999-04-19 | 2009-10-21 | Jsr株式会社 | Photocurable resin composition for three-dimensional modeling and a modeled product obtained by curing the same |
CN1203150C (en) | 1999-08-12 | 2005-05-25 | 三井化学株式会社 | Photocurable resin composition for sealing material and method of sealing |
GB9921779D0 (en) | 1999-09-16 | 1999-11-17 | Ciba Sc Holding Ag | UV-Curable compositions |
US6631021B2 (en) | 2000-03-20 | 2003-10-07 | Ppg Industries Ohio, Inc. | Polyfunctional thiirane compounds |
US6375887B1 (en) | 2000-04-18 | 2002-04-23 | Victor Joyner | Method and apparatus for creating cast parts and investment models |
WO2001095030A2 (en) * | 2000-06-09 | 2001-12-13 | Dsm N.V. | Resin composition and three-dimensional object |
JP2002060484A (en) * | 2000-08-23 | 2002-02-26 | Toagosei Co Ltd | Photocurable composition, bonding method using the same and bonded product |
DE10044840A1 (en) * | 2000-09-11 | 2002-04-04 | Siemens Ag | Photostructurable new organic semiconductor materials |
US6376148B1 (en) | 2001-01-17 | 2002-04-23 | Nanotek Instruments, Inc. | Layer manufacturing using electrostatic imaging and lamination |
US6794451B2 (en) | 2001-02-13 | 2004-09-21 | Toagosei Co., Ltd. | Cationically polymerizable liquid composition and tacky polymer |
US6780368B2 (en) | 2001-04-10 | 2004-08-24 | Nanotek Instruments, Inc. | Layer manufacturing of a multi-material or multi-color 3-D object using electrostatic imaging and lamination |
US7217375B2 (en) * | 2001-06-04 | 2007-05-15 | Ophthonix, Inc. | Apparatus and method of fabricating a compensating element for wavefront correction using spatially localized curing of resin mixtures |
KR20030007186A (en) * | 2001-07-17 | 2003-01-23 | 미쯔이카가쿠 가부시기가이샤 | Photocationic-curable resin composition and uses thereof |
EP1429325A4 (en) * | 2001-09-13 | 2006-05-31 | Tdk Corp | Optical recording medium manufacturing method |
TWI246525B (en) * | 2001-11-06 | 2006-01-01 | Wako Pure Chem Ind Ltd | Hybrid onium salt |
WO2003087187A1 (en) * | 2002-04-15 | 2003-10-23 | Toagosei Co., Ltd. | Actinic radiation hardenable resin composition and hardening product thereof |
US20030198824A1 (en) * | 2002-04-19 | 2003-10-23 | Fong John W. | Photocurable compositions containing reactive polysiloxane particles |
GB0212062D0 (en) * | 2002-05-24 | 2002-07-03 | Vantico Ag | Jetable compositions |
JP2004035862A (en) * | 2002-07-08 | 2004-02-05 | Polyplastics Co | Photocurable resin composition containing cyclic acetal compound and its cured product |
JP2005274587A (en) * | 2002-08-14 | 2005-10-06 | Konica Minolta Holdings Inc | Optical image recording material, and recording method thereof and manufacturing method thereof |
US20040077745A1 (en) * | 2002-10-18 | 2004-04-22 | Jigeng Xu | Curable compositions and rapid prototyping process using the same |
US20040137368A1 (en) * | 2003-01-13 | 2004-07-15 | 3D Systems, Inc. | Stereolithographic resins containing selected oxetane compounds |
EP1440984B1 (en) * | 2003-01-27 | 2007-10-17 | Nippon Shokubai Co., Ltd. | Method of manufacturing water-absorbing shaped body |
TWI340763B (en) | 2003-02-20 | 2011-04-21 | Nippon Kayaku Kk | Seal agent for photoelectric conversion elements and photoelectric conversion elements using such seal agent |
DE602004000780T2 (en) * | 2003-03-13 | 2006-10-05 | Air Products And Chemicals, Inc. | Acid-catalized copolymerization of water, tetrahydrofuran and multifunctional epoxides and their uses |
US7034064B2 (en) * | 2003-05-06 | 2006-04-25 | National Starch And Chemical Investment Holding Corporation | Method of attaching a die to a substrate using a hybrid oxetane compound |
EP1687343B1 (en) * | 2003-08-04 | 2014-07-23 | Matrix Innovation Inc. | New polyether based monomers and highly cross-linked amphiphile resins |
US7495035B2 (en) * | 2003-08-12 | 2009-02-24 | Mitsui Chemicals, Inc. | Photo-curable resin composition and sealing agent for flat panel display using the same |
US7232850B2 (en) | 2003-10-03 | 2007-06-19 | Huntsman Advanced Materials Americas Inc. | Photocurable compositions for articles having stable tensile properties |
US20050101684A1 (en) * | 2003-11-06 | 2005-05-12 | Xiaorong You | Curable compositions and rapid prototyping process using the same |
JP2005153273A (en) * | 2003-11-25 | 2005-06-16 | Nitto Denko Corp | Resin sheet, liquid crystal cell substrate, liquid crystal display device, substrate for electroluminescence display device, electroluminnescence display device and substrate for solar cell |
US20050158660A1 (en) * | 2004-01-20 | 2005-07-21 | Dsm Desotech, Inc. | Solid imaging compositions for preparing polypropylene-like articles |
US7671114B2 (en) * | 2004-01-26 | 2010-03-02 | Henkel Corporation | Adhesive of substituted oxirane or oxetane compound with silver-based, lead-free solder |
US7112635B2 (en) * | 2004-03-12 | 2006-09-26 | Air Products And Chemicals, Inc. | Acid catalyzed copolymerization of water, tetrahydrofuran and multifunctional epoxides and uses thereof |
US20060223978A1 (en) * | 2005-04-04 | 2006-10-05 | Shengqian Kong | Radiation- or thermally-curable oxetane barrier sealants |
US7479247B2 (en) * | 2005-05-12 | 2009-01-20 | Victor Joyner | Method and apparatus for creating sacrificial patterns and cast parts |
JP4744200B2 (en) | 2005-06-20 | 2011-08-10 | シーメット株式会社 | Solid modeling object with smoothed modeling end face |
JP4702784B2 (en) * | 2005-08-08 | 2011-06-15 | ソニー株式会社 | Liquid discharge type recording head flow path constituent material |
KR101341081B1 (en) * | 2005-09-29 | 2013-12-12 | 씨메트 가부시키가이샤 | Resin composition for optical three-dimensional molded object |
JP5352087B2 (en) * | 2005-12-26 | 2013-11-27 | 株式会社フジシールインターナショナル | Shrink label |
JP5539605B2 (en) * | 2006-04-19 | 2014-07-02 | 株式会社ダイセル | Active energy ray-curable coating agent and use thereof |
US20080121845A1 (en) * | 2006-08-11 | 2008-05-29 | General Electric Company | Oxetane composition, associated method and article |
US20080103226A1 (en) | 2006-10-31 | 2008-05-01 | Dsm Ip Assets B.V. | Photo-curable resin composition |
JP5321781B2 (en) * | 2007-01-09 | 2013-10-23 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
KR101433413B1 (en) * | 2007-03-20 | 2014-08-26 | 디에스엠 아이피 어셋츠 비.브이. | Stereolithography resin compositions and three-dimensional objects made therefrom |
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JP5205018B2 (en) * | 2007-09-06 | 2013-06-05 | シーメット株式会社 | Optical three-dimensional resin composition |
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WO2010104603A2 (en) | 2009-03-13 | 2010-09-16 | Dsm Ip Assets B.V | Radiation curable resin composition and rapid three-dimensional imaging process using the same |
US8488994B2 (en) | 2011-09-23 | 2013-07-16 | Stratasys, Inc. | Electrophotography-based additive manufacturing system with transfer-medium service loops |
CA2847351C (en) | 2011-09-23 | 2017-02-21 | Stratasys, Inc. | Layer transfusion for additive manufacturing |
US20130186558A1 (en) | 2011-09-23 | 2013-07-25 | Stratasys, Inc. | Layer transfusion with heat capacitor belt for additive manufacturing |
US8879957B2 (en) | 2011-09-23 | 2014-11-04 | Stratasys, Inc. | Electrophotography-based additive manufacturing system with reciprocating operation |
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US9029058B2 (en) | 2013-07-17 | 2015-05-12 | Stratasys, Inc. | Soluble support material for electrophotography-based additive manufacturing |
US9023566B2 (en) | 2013-07-17 | 2015-05-05 | Stratasys, Inc. | ABS part material for electrophotography-based additive manufacturing |
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US9643357B2 (en) | 2014-03-18 | 2017-05-09 | Stratasys, Inc. | Electrophotography-based additive manufacturing with powder density detection and utilization |
US10011071B2 (en) | 2014-03-18 | 2018-07-03 | Evolve Additive Solutions, Inc. | Additive manufacturing using density feedback control |
US9868255B2 (en) | 2014-03-18 | 2018-01-16 | Stratasys, Inc. | Electrophotography-based additive manufacturing with pre-sintering |
US9770869B2 (en) | 2014-03-18 | 2017-09-26 | Stratasys, Inc. | Additive manufacturing with virtual planarization control |
US10144175B2 (en) | 2014-03-18 | 2018-12-04 | Evolve Additive Solutions, Inc. | Electrophotography-based additive manufacturing with solvent-assisted planarization |
US9688027B2 (en) | 2014-04-01 | 2017-06-27 | Stratasys, Inc. | Electrophotography-based additive manufacturing with overlay control |
US9919479B2 (en) | 2014-04-01 | 2018-03-20 | Stratasys, Inc. | Registration and overlay error correction of electrophotographically formed elements in an additive manufacturing system |
US10683381B2 (en) | 2014-12-23 | 2020-06-16 | Bridgestone Americas Tire Operations, Llc | Actinic radiation curable polymeric mixtures, cured polymeric mixtures and related processes |
WO2016153711A1 (en) * | 2015-03-23 | 2016-09-29 | Dow Global Technologies Llc | Photocurable compositions for three-dimensional printing |
EP3390006B1 (en) | 2015-12-17 | 2021-01-27 | Bridgestone Americas Tire Operations, LLC | Additive manufacturing cartridges and processes for producing cured polymeric products by additive manufacturing |
US11453161B2 (en) | 2016-10-27 | 2022-09-27 | Bridgestone Americas Tire Operations, Llc | Processes for producing cured polymeric products by additive manufacturing |
JP2019056044A (en) * | 2017-09-20 | 2019-04-11 | 富士ゼロックス株式会社 | Shaped-article manufacturing ink composition, method of manufacturing shaped-article manufacturing ink composition, shaped article, and shaped-article manufacturing apparatus |
TWI692502B (en) | 2017-12-29 | 2020-05-01 | 法商阿科瑪法國公司 | Curable compositions |
US11681218B2 (en) * | 2018-02-14 | 2023-06-20 | Sumitomo Chemical Company, Limited | Compound, resist composition and method for producing resist pattern |
JP6603004B1 (en) * | 2019-08-21 | 2019-11-06 | ナミックス株式会社 | Epoxy resin composition |
EP4206820A1 (en) | 2021-12-30 | 2023-07-05 | Arkema France | Hybrid photocurable composition |
Citations (57)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4917040A (en) | 1972-06-10 | 1974-02-15 | ||
US3835003A (en) | 1968-08-20 | 1974-09-10 | American Can Co | Photopolymerization of oxetanes |
JPS50151996A (en) | 1974-05-02 | 1975-12-06 | ||
JPS50151997A (en) | 1974-05-02 | 1975-12-06 | ||
JPS50158680A (en) | 1974-05-08 | 1975-12-22 | ||
JPS50158698A (en) | 1974-05-02 | 1975-12-22 | ||
JPS5230899A (en) | 1975-09-02 | 1977-03-08 | Minnesota Mining & Mfg | Photoocopolymerizable composite consisting of epoxy and hydroxyl radicallcontaining organic substance |
US4139655A (en) | 1978-05-09 | 1979-02-13 | W. R. Grace & Co. | Photocurable epoxy compositions containing thiopyrylium salts |
JPS55125105A (en) | 1979-03-14 | 1980-09-26 | American Can Co | Manufacture of biss*44*diphenylsulfonio*phenyl* sulfidebissmx6 initiator and cationic polymerization of monomer blend thereby |
JPS5555420Y2 (en) | 1976-05-14 | 1980-12-22 | ||
JPS568428A (en) | 1979-06-19 | 1981-01-28 | Ciba Geigy Ag | Photopolymerizing and thermopolymerizing composition |
JPS5655420A (en) | 1979-09-28 | 1981-05-16 | Gen Electric | Depth hardening of photohardenable composition |
JPS56149402A (en) | 1980-03-07 | 1981-11-19 | Ciba Geigy Ag | Photopolymerizable composition and polymerization thereof |
JPS57192429A (en) | 1981-05-06 | 1982-11-26 | Ciba Geigy Ag | Thermally porimerizable composition consisting of epoxide resin, aromatic sulfoxonium salt and organic oxidizing agent and polymerization |
US4374751A (en) | 1980-08-08 | 1983-02-22 | General Electric Company | Polymerization initiator compositions |
JPS60247515A (en) | 1984-05-23 | 1985-12-07 | Oosakafu | Optical shaping method |
US4575330A (en) | 1984-08-08 | 1986-03-11 | Uvp, Inc. | Apparatus for production of three-dimensional objects by stereolithography |
JPS62101408A (en) | 1985-10-29 | 1987-05-11 | Osaka Pref Gov | Optical shaping |
US4694029A (en) | 1985-04-09 | 1987-09-15 | Cook Paint And Varnish Company | Hybrid photocure system |
JPS6337034A (en) | 1986-07-28 | 1988-02-17 | Mitsubishi Electric Corp | Separating and feeding device for semiconductor device |
JPH01204915A (en) | 1988-01-27 | 1989-08-17 | Desoto Inc | Optical stereoscopic modeling resin composition |
JPH01213304A (en) | 1988-02-19 | 1989-08-28 | Asahi Denka Kogyo Kk | Resin composition for photochemical molding |
JPH0228261A (en) | 1988-07-15 | 1990-01-30 | Asahi Denka Kogyo Kk | Resin composition for optical forming |
JPH0275618A (en) | 1988-09-13 | 1990-03-15 | Asahi Denka Kogyo Kk | Resin composition for optical molding |
EP0360869A1 (en) | 1988-02-19 | 1990-04-04 | Asahi Denka Kogyo Kabushiki Kaisha | Resin composition for optical modeling |
JPH02208305A (en) | 1989-02-07 | 1990-08-17 | Mitsui Eng & Shipbuild Co Ltd | Photocurable composition |
JPH03160013A (en) | 1989-10-27 | 1991-07-10 | Ciba Geigy Ag | Photosensitive mixture |
US5073643A (en) | 1990-08-30 | 1991-12-17 | Polyset Corporation | High yield synthesis of hydroxyl-containing cationic photoinitiators |
JPH0524119A (en) | 1991-07-25 | 1993-02-02 | Matsushita Electric Works Ltd | Formation of three-dimensional shape |
EP0535828A1 (en) | 1991-09-30 | 1993-04-07 | Zeneca Limited | Photostereolithographic process |
JPH06228413A (en) | 1992-12-21 | 1994-08-16 | Ciba Geigy Ag | Photosensitive composition |
US5387304A (en) | 1988-09-27 | 1995-02-07 | Ciba-Geigy Corporation | Application of a painted carrier film to a three-dimensional substrate |
JPH0753711A (en) * | 1993-08-17 | 1995-02-28 | Toagosei Co Ltd | Composition curable by actinic radiation |
JPH0762082A (en) * | 1993-08-09 | 1995-03-07 | Rensselaer Polytechnic Inst | Active-energy-ray-curable composition |
US5434196A (en) * | 1988-02-19 | 1995-07-18 | Asahi Denka Kogyo K.K. | Resin composition for optical molding |
US5437964A (en) | 1991-05-01 | 1995-08-01 | Alliedsignal Inc. | Stereolithography using vinyl ether-epoxide polymers |
US5463084A (en) | 1992-02-18 | 1995-10-31 | Rensselaer Polytechnic Institute | Photocurable silicone oxetanes |
JPH0885775A (en) * | 1994-09-16 | 1996-04-02 | Toagosei Co Ltd | Composition for producing precoated steel sheet |
JPH08143806A (en) | 1994-11-18 | 1996-06-04 | Toagosei Co Ltd | Composition for ink curable by actinic ray |
JPH08208832A (en) * | 1995-02-08 | 1996-08-13 | Toagosei Co Ltd | Active energy ray curing type composition for coating plastics |
JPH08218296A (en) * | 1995-02-15 | 1996-08-27 | Toagosei Co Ltd | Active energy beam-curable composition for paper coating |
EP0732625A2 (en) | 1995-03-13 | 1996-09-18 | Ciba-Geigy Ag | Stabilization of liquid radiation-curable compositions against premature polymerization |
WO1996030182A1 (en) | 1995-03-30 | 1996-10-03 | Crivello James V | Methods and compositions related to stereolithography |
JPH08269392A (en) | 1995-03-31 | 1996-10-15 | Toagosei Co Ltd | Active energy beam-curing type composition for primary coating of optical fiber |
JPH08277385A (en) * | 1995-04-05 | 1996-10-22 | Toagosei Co Ltd | Active energy ray curing type tacky agent composition |
WO1996035756A1 (en) * | 1995-05-12 | 1996-11-14 | Asahi Denka Kogyo Kabushiki Kaisha | Stereolithographic resin composition and stereolithographic method |
GB2305919A (en) | 1995-10-02 | 1997-04-23 | Kansai Paint Co Ltd | Ultraviolet curing coating composition for cans |
US5639802A (en) | 1991-05-20 | 1997-06-17 | Spectra Group Limited, Inc. | Cationic polymerization |
US5674922A (en) * | 1995-07-21 | 1997-10-07 | Toagosei Co., Ltd. | Active energy beam-curable compositions comprising oxetane compounds |
US5721289A (en) | 1994-11-04 | 1998-02-24 | Minnesota Mining And Manufacturing Company | Stable, low cure-temperature semi-structural pressure sensitive adhesive |
EP0831373A2 (en) | 1996-09-20 | 1998-03-25 | Dsm N.V. | Photo-curable resin compositions and process for preparing a resin-based mold |
EP0837366A1 (en) | 1996-10-14 | 1998-04-22 | Dsm N.V. | Photocurable resin composition |
JPH10158385A (en) | 1996-12-02 | 1998-06-16 | Asahi Denka Kogyo Kk | Resin composition for forming optical solid and formation of the same solid |
EP0848292A1 (en) | 1996-12-10 | 1998-06-17 | Dsm N.V. | Photo-curable resin composition |
EP0848293A1 (en) | 1996-12-10 | 1998-06-17 | Dsm N.V. | Photo-curable resin composition |
JPH10168165A (en) | 1996-12-13 | 1998-06-23 | Jsr Corp | Photocurable resin composition for optical three-dimensional shaping |
US5985510A (en) * | 1996-11-26 | 1999-11-16 | Asahi Denka Kogyo Kabushiki Kaisha | Energy beam curable epoxy resin composition, stereolithographic resin composition and stereolithographic method |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5555420A (en) | 1978-10-18 | 1980-04-23 | Toshiba Corp | Vertical magnetization recording device |
-
1996
- 1996-12-13 JP JP35289396A patent/JP3765896B2/en not_active Expired - Lifetime
-
1997
- 1997-12-12 US US08/989,407 patent/US5981616A/en not_active Expired - Lifetime
- 1997-12-12 EP EP97203898A patent/EP0848294B1/en not_active Revoked
- 1997-12-12 DE DE69706816T patent/DE69706816T2/en not_active Expired - Lifetime
-
1999
- 1999-09-13 US US09/394,031 patent/US6365644B1/en not_active Ceased
-
2003
- 2003-09-26 US US10/671,438 patent/USRE42593E1/en not_active Expired - Lifetime
Patent Citations (68)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3835003A (en) | 1968-08-20 | 1974-09-10 | American Can Co | Photopolymerization of oxetanes |
JPS4917040A (en) | 1972-06-10 | 1974-02-15 | ||
JPS50151996A (en) | 1974-05-02 | 1975-12-06 | ||
JPS50151997A (en) | 1974-05-02 | 1975-12-06 | ||
JPS50158698A (en) | 1974-05-02 | 1975-12-22 | ||
US4394403A (en) | 1974-05-08 | 1983-07-19 | Minnesota Mining And Manufacturing Company | Photopolymerizable compositions |
JPS50158680A (en) | 1974-05-08 | 1975-12-22 | ||
JPS5230899A (en) | 1975-09-02 | 1977-03-08 | Minnesota Mining & Mfg | Photoocopolymerizable composite consisting of epoxy and hydroxyl radicallcontaining organic substance |
JPS5555420Y2 (en) | 1976-05-14 | 1980-12-22 | ||
US4139655A (en) | 1978-05-09 | 1979-02-13 | W. R. Grace & Co. | Photocurable epoxy compositions containing thiopyrylium salts |
JPS55125105A (en) | 1979-03-14 | 1980-09-26 | American Can Co | Manufacture of biss*44*diphenylsulfonio*phenyl* sulfidebissmx6 initiator and cationic polymerization of monomer blend thereby |
JPS568428A (en) | 1979-06-19 | 1981-01-28 | Ciba Geigy Ag | Photopolymerizing and thermopolymerizing composition |
JPS5655420A (en) | 1979-09-28 | 1981-05-16 | Gen Electric | Depth hardening of photohardenable composition |
JPS56149402A (en) | 1980-03-07 | 1981-11-19 | Ciba Geigy Ag | Photopolymerizable composition and polymerization thereof |
US4374751A (en) | 1980-08-08 | 1983-02-22 | General Electric Company | Polymerization initiator compositions |
JPS57192429A (en) | 1981-05-06 | 1982-11-26 | Ciba Geigy Ag | Thermally porimerizable composition consisting of epoxide resin, aromatic sulfoxonium salt and organic oxidizing agent and polymerization |
JPS60247515A (en) | 1984-05-23 | 1985-12-07 | Oosakafu | Optical shaping method |
JPS6235966A (en) | 1984-08-08 | 1987-02-16 | スリーデイー、システムズ、インコーポレーテッド | Method and apparatus for generating 3-d object |
US4575330B1 (en) | 1984-08-08 | 1989-12-19 | ||
US4575330A (en) | 1984-08-08 | 1986-03-11 | Uvp, Inc. | Apparatus for production of three-dimensional objects by stereolithography |
US4694029A (en) | 1985-04-09 | 1987-09-15 | Cook Paint And Varnish Company | Hybrid photocure system |
JPS62101408A (en) | 1985-10-29 | 1987-05-11 | Osaka Pref Gov | Optical shaping |
JPS6337034A (en) | 1986-07-28 | 1988-02-17 | Mitsubishi Electric Corp | Separating and feeding device for semiconductor device |
JPH01204915A (en) | 1988-01-27 | 1989-08-17 | Desoto Inc | Optical stereoscopic modeling resin composition |
JPH01213304A (en) | 1988-02-19 | 1989-08-28 | Asahi Denka Kogyo Kk | Resin composition for photochemical molding |
EP0360869A1 (en) | 1988-02-19 | 1990-04-04 | Asahi Denka Kogyo Kabushiki Kaisha | Resin composition for optical modeling |
US5434196A (en) * | 1988-02-19 | 1995-07-18 | Asahi Denka Kogyo K.K. | Resin composition for optical molding |
US5525645A (en) * | 1988-02-19 | 1996-06-11 | Asahi Denka Kogyo K.K. | Resin composition for optical molding |
JPH0228261A (en) | 1988-07-15 | 1990-01-30 | Asahi Denka Kogyo Kk | Resin composition for optical forming |
JPH0275618A (en) | 1988-09-13 | 1990-03-15 | Asahi Denka Kogyo Kk | Resin composition for optical molding |
US5387304A (en) | 1988-09-27 | 1995-02-07 | Ciba-Geigy Corporation | Application of a painted carrier film to a three-dimensional substrate |
JPH02208305A (en) | 1989-02-07 | 1990-08-17 | Mitsui Eng & Shipbuild Co Ltd | Photocurable composition |
JPH03160013A (en) | 1989-10-27 | 1991-07-10 | Ciba Geigy Ag | Photosensitive mixture |
US5073643A (en) | 1990-08-30 | 1991-12-17 | Polyset Corporation | High yield synthesis of hydroxyl-containing cationic photoinitiators |
US5437964A (en) | 1991-05-01 | 1995-08-01 | Alliedsignal Inc. | Stereolithography using vinyl ether-epoxide polymers |
US5639802A (en) | 1991-05-20 | 1997-06-17 | Spectra Group Limited, Inc. | Cationic polymerization |
JPH0524119A (en) | 1991-07-25 | 1993-02-02 | Matsushita Electric Works Ltd | Formation of three-dimensional shape |
EP0535828A1 (en) | 1991-09-30 | 1993-04-07 | Zeneca Limited | Photostereolithographic process |
US5463084A (en) | 1992-02-18 | 1995-10-31 | Rensselaer Polytechnic Institute | Photocurable silicone oxetanes |
JPH06228413A (en) | 1992-12-21 | 1994-08-16 | Ciba Geigy Ag | Photosensitive composition |
JPH0762082A (en) * | 1993-08-09 | 1995-03-07 | Rensselaer Polytechnic Inst | Active-energy-ray-curable composition |
JPH0753711A (en) * | 1993-08-17 | 1995-02-28 | Toagosei Co Ltd | Composition curable by actinic radiation |
JPH0885775A (en) * | 1994-09-16 | 1996-04-02 | Toagosei Co Ltd | Composition for producing precoated steel sheet |
US5721289A (en) | 1994-11-04 | 1998-02-24 | Minnesota Mining And Manufacturing Company | Stable, low cure-temperature semi-structural pressure sensitive adhesive |
JPH08143806A (en) | 1994-11-18 | 1996-06-04 | Toagosei Co Ltd | Composition for ink curable by actinic ray |
JPH08208832A (en) * | 1995-02-08 | 1996-08-13 | Toagosei Co Ltd | Active energy ray curing type composition for coating plastics |
JPH08218296A (en) * | 1995-02-15 | 1996-08-27 | Toagosei Co Ltd | Active energy beam-curable composition for paper coating |
EP0732625A2 (en) | 1995-03-13 | 1996-09-18 | Ciba-Geigy Ag | Stabilization of liquid radiation-curable compositions against premature polymerization |
US5783358A (en) | 1995-03-13 | 1998-07-21 | Ciba Specialty Chemicals Corporation | Stabilization of liquid radiation-curable compositions against undesired premature polymerization |
EP0732625B1 (en) | 1995-03-13 | 2001-09-12 | Vantico AG | Stabilization of liquid radiation-curable compositions against premature polymerization |
WO1996030182A1 (en) | 1995-03-30 | 1996-10-03 | Crivello James V | Methods and compositions related to stereolithography |
JPH08269392A (en) | 1995-03-31 | 1996-10-15 | Toagosei Co Ltd | Active energy beam-curing type composition for primary coating of optical fiber |
JPH08277385A (en) * | 1995-04-05 | 1996-10-22 | Toagosei Co Ltd | Active energy ray curing type tacky agent composition |
WO1996035756A1 (en) * | 1995-05-12 | 1996-11-14 | Asahi Denka Kogyo Kabushiki Kaisha | Stereolithographic resin composition and stereolithographic method |
US6130025A (en) * | 1995-05-12 | 2000-10-10 | Asahi Denka Kogyo Kabushiki Kaisha | Stereolithographic resin composition and stereolithographic method |
EP0831127A1 (en) | 1995-05-12 | 1998-03-25 | Asahi Denka Kogyo Kabushiki Kaisha | Stereolithographic resin composition and stereolithographic method |
US5674922A (en) * | 1995-07-21 | 1997-10-07 | Toagosei Co., Ltd. | Active energy beam-curable compositions comprising oxetane compounds |
US5721020A (en) | 1995-10-02 | 1998-02-24 | Kansai Paint Co., Ltd. | Ultraviolet-curing coating composition for cans |
GB2305919A (en) | 1995-10-02 | 1997-04-23 | Kansai Paint Co Ltd | Ultraviolet curing coating composition for cans |
EP0831373A2 (en) | 1996-09-20 | 1998-03-25 | Dsm N.V. | Photo-curable resin compositions and process for preparing a resin-based mold |
EP0837366A1 (en) | 1996-10-14 | 1998-04-22 | Dsm N.V. | Photocurable resin composition |
US6127085A (en) * | 1996-10-14 | 2000-10-03 | Dsm N.V. | Photo-curable resin composition |
US5985510A (en) * | 1996-11-26 | 1999-11-16 | Asahi Denka Kogyo Kabushiki Kaisha | Energy beam curable epoxy resin composition, stereolithographic resin composition and stereolithographic method |
JPH10158385A (en) | 1996-12-02 | 1998-06-16 | Asahi Denka Kogyo Kk | Resin composition for forming optical solid and formation of the same solid |
EP0848292A1 (en) | 1996-12-10 | 1998-06-17 | Dsm N.V. | Photo-curable resin composition |
EP0848293A1 (en) | 1996-12-10 | 1998-06-17 | Dsm N.V. | Photo-curable resin composition |
JPH10168165A (en) | 1996-12-13 | 1998-06-23 | Jsr Corp | Photocurable resin composition for optical three-dimensional shaping |
EP0848294B1 (en) | 1996-12-13 | 2001-09-19 | Dsm N.V. | Photo-curable resin composition used for photo-fabrication of three-dimensional objects |
Non-Patent Citations (8)
Title |
---|
"Statement of Grounds of Opposition Including Facts and Arguments in Support" submitted by Vantico AG in opposition to EP 848,294, dated May 28, 2002 (11 pages). |
EP 0848294 B1 opposition , Test Report No. 2 (appeal); pp. 1-4. |
European Search Report of EP 848,294; Mar. 1998. |
Feb. 26, 2008 Submissions of the Opponent for EP0848294B1. |
Japanese Patent Abstract, vol. 014, No. 261 (c-0725), Mar. 15, 1990. |
Minutes and Decision of EP Appeals Board for EP0848294B1. |
Nuyken et al., Macromol. Symp. 107, 125-138 (1996), "Oxetane Photopolymerization-A System with Low Volume Shrinkage". |
Sasaki et al., J. Polymer Sci. Part A, Polymer Chemistry, 33, 1807-1816 (1995), "Photoinitiated Cationic Polymerization of Oxetane Formulated with Oxirane". |
Also Published As
Publication number | Publication date |
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JPH10168165A (en) | 1998-06-23 |
DE69706816D1 (en) | 2001-10-25 |
DE69706816T2 (en) | 2002-04-25 |
US5981616A (en) | 1999-11-09 |
EP0848294B1 (en) | 2001-09-19 |
JP3765896B2 (en) | 2006-04-12 |
US6365644B1 (en) | 2002-04-02 |
EP0848294A1 (en) | 1998-06-17 |
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