CN102675833A - Color concentrate used for making colorized polymer and preparation method for color concentrate - Google Patents
Color concentrate used for making colorized polymer and preparation method for color concentrate Download PDFInfo
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- CN102675833A CN102675833A CN2012101695992A CN201210169599A CN102675833A CN 102675833 A CN102675833 A CN 102675833A CN 2012101695992 A CN2012101695992 A CN 2012101695992A CN 201210169599 A CN201210169599 A CN 201210169599A CN 102675833 A CN102675833 A CN 102675833A
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Abstract
The invention relates to a composition. The composition comprises a) a mixture consisting of at least one dye and at least one dye dispersant, and b) at least one main polymer which is one or a mixture of at least two of polyester, polycarbonate, polyimide, polyamide and styrene plastics. The invention also relates to a preparation method for the composition. A pigment in the prior art is replaced by the dye; and the affinity of the dye and substances is relatively high, and the pigment is attached to the surface of an object only by means of a viscous substance or in other ways, so the colorizing composition, namely a color concentrate is high in concentration and uniform in colorization, and has a good colorizing effect.
Description
Technical field
The present invention relates to a kind of colour batch that is used to make coloured polymer, particularly, the present invention relates to a kind of colour masterbatch that is used to make coloured polymer and preparation method thereof.
Background technology
About making paints is known in the art.During making paints, generally produce aqueous pigment dispersions and must make these aqueous pigment dispersions through water squeezing technology so that anhydrate from wherein removing.Yet, remove through simple drying process and to anhydrate, the agglomeration of the granules of pigments that occurs can take place not hope.So, only remove portion water in force, and stay finely divided pigment with the form of wet block.Known in the art, from this wet block, remove residual water and they are implemented through water squeezing technology through adopting polymeric dispersant.The water squeezing prepared goes out the dispersion-s that pigment keeps finely divided state, and it is and the form of the intimate mixture of pigment dispersing agent, is used for further processing as sneaks into polymer compsn and printing ink.Pigment water squeezing method is described in the English Patent 915,453.
Also know the painted of high-melting-point polymer.English Patent 1; 044,378 has narrated the technology of homodisperse pigment in high-melting-point polymer, promptly implements by means of formation intimate mixture granular or powdered pigment; Said granular or polymer powder is compatible with high-melting-point polymer, but its fusing point is lower than high-melting-point polymer.This method comprises: heating and mixing are evenly distributed in the low melting point polymer pigment, and the gained material is solidified, and the gained solid is mixed with high-melting-point polymer, and be fused together them.Each high-melting-point polymer has identical chemical type with low melting point polymer.USP 4,279,802 have processed the masterbatch of a kind of pigment and polyester, and this masterbatch is applied to painted linear polyesters then.USP 5,336,314 use polyester or the acrylic polymers that contains phthalimide or naphthalimido group, as pigment dispersion vehicle and pigment press cake flushing agent, prepare coating.
CN 1208376C discloses a kind of wet pigment water squeezing and low-molecular-weight polyester and the polymeric amide of making colour masterbatch.More particularly, this invention compsn is for wet pigment water squeezing, the dispersion-s that makes paints and and then to make coloured polymer with pigment dispersion be effective.But owing to adopt pigment, and pigment just leans on viscous substance or other aspects to depend on body surface, causes its coloring effect even inadequately in this invention.
The present invention adopts dyestuff to replace pigment, forms dye dispersion through wet dyestuff press cake is mixed with dye dispersant mutually.Making the gained mixture coagulates, and remove water, generally is the method for taking to heat said composition, chooses wantonly under vacuum and carries out.Institute's dispersive dyestuff can be chosen wantonly and pulverized.Then; Powder dye/mixture of dispersing agents can dilute by enough polarity main polymers; Said main polymer is polyester, polycarbonate, polyimide, polymeric amide and styrene plastic for example, obtains the high quality colour masterbatch and is used for making at last finished product consumption component and goods.This colour masterbatch is the dye dispersion that is of high quality, and can obtain the highest painted with the dyestuff content of minimum through effective use equipment and machinery.Dye dispersant of the present invention is low melting glass, low viscous vehicle, plays a part dye acceptor, and in water squeezing technology, separates water outlet.On the other hand, dispersion agent plays low viscosity fluid under molten state, its wetting equably pigment, and through the mechanical effect dispersed dye such as mixing equipment such as single screw rod or twin screw extruders.Colorize method is generally implemented through following step, that is, make contain dispersion agent, through water squeezing, drying and the dyestuff and main polymer blend mutually pulverized, and extrude this blend and carry out granulation.Satisfied performance requriements: selected dye dispersant and blended polymer-compatible subsequently so that in coloring process dispersed dye effectively; Good dyestuff dissemination is arranged, so that obtain the darkest tone or tone intensity and uniform dye distribution; Have good extrusion characteristics,, make production efficiency and output reach the highest so that produce flexible wires material with good strength and granulation characteristic.
Summary of the invention
One of the object of the invention is to provide a kind of colour masterbatch that is used to make coloured polymer, and dyestuff and vector resin consistency are good in the said colour batch, and dyestuff is good dispersion in polymkeric substance, and tinctorial property is excellent.
In order to achieve the above object, the present invention has adopted following technical scheme:
The said compsn that comprises following compositions, it comprises: a) a kind of mixture of being made up of at least a dyestuff and at least a dye dispersant; And b) at least a main polymer, it is selected from the mixture of a kind of in polyester, polycarbonate, polyimide, polymeric amide and the styrene plastic or at least two kinds.
Said dye dispersant is selected from the mixture of a kind of in naphthalene sulfonic formaldehyde condensation compound, lignosulfonic acid salt, the polymeric dispersant class or at least two kinds.Said mixture is the mixture of polymeric dispersant and lignosulfonic acid salt for example; The mixture of naphthalene sulfonic formaldehyde condensation compound and polymeric dispersant; The mixture of lignosulfonic acid salt and naphthalene sulfonic formaldehyde condensation compound, the mixture of lignosulfonic acid salt, polymeric dispersant and naphthalene sulfonic formaldehyde condensation compound.The polymeric dispersant arbitrarily that those skilled in the art can be known, lignosulfonic acid salt and naphthalene sulfonic formaldehyde condensation compound all can be realized the present invention, and the present invention does not enumerate at this one by one.
As optimal technical scheme, said dye dispersant is selected from the mixture of a kind of in phenol, formaldehyde, carbonate condenses, the polyethylene terephthalate or at least two kinds.Said mixture is the mixture of polyethylene terephthalate and carbonate condenses for example; The mixture of formaldehyde and phenol; The mixture of phenol and polyethylene terephthalate, the mixture of carbonate condenses and formaldehyde, the mixture of polyethylene terephthalate and formaldehyde; The mixture of carbonate condenses and phenol; The mixture of polyethylene terephthalate, carbonate condenses and formaldehyde, the mixture of phenol, polyethylene terephthalate and carbonate condenses, the mixture of formaldehyde, phenol and polyethylene terephthalate.
Compsn according to the invention can only be made up of component a and components b, and as optimal technical scheme, said compsn also comprises additive; Said additive is selected from a kind of in dispersion agent, compatilizer, the lubricant or its mixture of at least two kinds.Said mixture is the mixture of dispersion agent and compatilizer for example, the mixture of dispersion agent and lubricant, the mixture of compatilizer and lubricant, the mixture of dispersion agent, compatilizer and lubricant.
Said dispersion agent is selected from the mixture of a kind of in polyethylene wax and copolymer waxes thereof, OPE, ethylene-acrylic acid copolymer ion salt, micro mist wax, the diffusion oil or at least two kinds, the mixture of optimal ethylene-vinyl acetate copolymer wax, diffusion oil, OPE a kind of or at least two kinds.Said mixture is the mixture of polyethylene wax and OPE for example; The mixture of ethylene-acrylic acid copolymer ion salt and micro mist wax; The mixture of diffusion oil and polyethylene wax; The mixture of OPE and PEMULEN TR2 ion salt, the mixture of micro mist wax and diffusion oil, the mixture of polyethylene wax, OPE and PEMULEN TR2 ion salt; The mixture of micro mist wax, diffusion oil and polyethylene wax, the mixture of OPE, PEMULEN TR2 ion salt and diffusion oil.
Said compatilizer is selected from the mixture of a kind of among PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g-MAH, the PP-g-MAH or at least two kinds.Said mixture is the mixture of PP-g-MAH and PE-g-MAH for example; The mixture of ABS-g-MAH and PP-g-ST, the mixture of PE-g-ST and PP-g-MAH, the mixture of PE-g-MAH and ABS-g-MAH; The mixture of PP-g-ST and PE-g-ST; The mixture of PP-g-MAH, PE-g-MAH and ABS-g-MAH, the mixture of PP-g-ST, PE-g-ST and PP-g-MAH, the mixture of PE-g-MAH, ABS-g-MAH, PP-g-ST and PE-g-ST; The mixture of PP-g-MAH, PE-g-MAH, ABS-g-MAH and PP-g-ST, the mixture of PE-g-ST, PP-g-MAH, PE-g-MAH, ABS-g-MAH and PP-g-ST.
Said lubricant is selected from metallic soap class, aliphatic amide and verivate thereof; The class of metallic soap arbitrarily, aliphatic amide and verivate thereof that those skilled in the art can be known all can be realized the present invention; As optimal technical scheme, the mixture of a kind of in the preferred calcium stearate of said lubricant, Zinic stearas, Magnesium Stearate, erucicamide, amine hydroxybenzene, EBS and the verivate thereof or at least two kinds.Said mixture is the mixture of EBS and amine hydroxybenzene for example, the mixture of erucicamide and Magnesium Stearate, the mixture of Zinic stearas and calcium stearate; The mixture of amine hydroxybenzene and erucicamide; The mixture of Magnesium Stearate and Zinic stearas, the mixture of calcium stearate and EBS, the mixture of EBS, amine hydroxybenzene and erucicamide; The mixture of Magnesium Stearate, Zinic stearas and calcium stearate, the mixture of amine hydroxybenzene, EBS, erucicamide and Magnesium Stearate.
Said compsn also comprises coupling agent or/and oxidation inhibitor.
Said coupling agent is selected from the mixture of a kind of in silane coupling agent, titanate coupling agent, aluminate coupling agent, metal composite coupling agent, phosphate coupling agent, the boric acid ester coupler or at least two kinds; Said mixture is the mixture of boric acid ester coupler and phosphate coupling agent for example; The mixture of metal composite coupling agent and aluminate coupling agent; The mixture of titanate coupling agent and silane coupling agent; The mixture of boric acid ester coupler, phosphate coupling agent and metal composite coupling agent; The mixture of aluminate coupling agent, titanate coupling agent and silane coupling agent; The mixture of phosphate coupling agent, metal composite coupling agent, aluminate coupling agent and titanate coupling agent, the mixture of silane coupling agent, boric acid ester coupler, phosphate coupling agent, metal composite coupling agent, aluminate coupling agent and titanate coupling agent, preferred titanate coupling agent and/or aluminate coupling agent.
Said oxidation inhibitor is selected from the mixture of a kind of in antioxidant 1010, antioxidant 1076, oxidation inhibitor 168, antioxidant BHT, the antioxidant 264 or at least two kinds.Said mixture is the mixture of antioxidant 264 and antioxidant BHT for example; The mixture of oxidation inhibitor 168 and antioxidant 1076, the mixture of antioxidant 1010 and antioxidant 264, the mixture of antioxidant BHT and oxidation inhibitor 168; The mixture of antioxidant 1076 and antioxidant 1010; The mixture of antioxidant 264, antioxidant BHT and oxidation inhibitor 168, the mixture of antioxidant 1076, antioxidant 1010 and antioxidant 264, the mixture of antioxidant BHT, oxidation inhibitor 168, antioxidant 1076 and antioxidant 1010.
The present invention provides a kind of dyestuff/dye dispersant compsn, and it is a kind of mixture, the prefabricated intimate mixture of preferably at least a dyestuff and at least a dye dispersant as stated.Dyestuff can be organic or inorganic.Median diameter is generally less than 1 μ m.Dyestuff example of the present invention has: anthraquinone class vat dyes.
The final color that the planner of plastics is required is depended in the selection of tinting material.
Color science is well-known to those skilled in the art.Do not need too much experiment, just can use the color-match technology to confirm the particular location in spherical color space.For example, those skilled in the art can use the explanation of PCT patented claim US2004/012233 to come to make to use concrete polymer support and the tinting material color space figure as material composition digitally.Perhaps, can prepare small sample, promptly be used for the colour table (plaques) of visual inspection.
The amount of dyestuff in dyestuff/disperser composition is preferably about 10wt%～about 75wt% of dyestuff/disperser composition, more preferably about 10wt%～about 70wt%, most preferably from about 25wt%～about 60wt%.The amount of dispersion agent in dyestuff/disperser composition is preferably about 25wt%～about 90wt% of dyestuff/disperser composition, more preferably about 35wt%～about 85wt%, most preferably from about 40wt%～about 75wt%.
Dyestuff/disperser composition of the present invention is used to prepare the coloured polymer composition with HMW main polymer.Main polymer comprises the mixture of a kind of in polyester, polycarbonate, polyimide, polymeric amide and the styrene plastic or at least two kinds.
The amount of main polymer in coloured polymer composition is preferably about 45wt%～about 95wt% of coloured polymer composition, and more preferably about 65wt%～about 90wt% most preferably is about 92wt%～about 95wt%.
The amount of dyestuff/disperser composition in coloured polymer composition is preferably about 2wt%～about 55wt% of coloured polymer composition, and more preferably about 3wt%～about 35wt% most preferably is about 2wt%～about 8wt%.
Dyestuff/disperser composition and coloured polymer composition can form through mixing and heating each component.Mix and heating can be carried out in forcing machine, like single screw rod, twin screw and multiple screw extruder, forcing machine-mixer combination, mixer-Banbury mixer, kneader-Banbury mixer, planetary stirrer, Banbury Banbury mixer, high-power mixer, twin-roll plastic mixing mill, injection moulding machine, static mixer, helical-ribbon type and V-mixing machine, three-roll mill, colloidal mill, super mixer and ball mill in batches with mixing screw.
The present invention also provides a kind of method that forms coloured composition, and this method comprises:
(a) moisture dye dispersion or moisture wet dyestuff block are contacted with at least a dye dispersant; The brookfield viscosity of said dye dispersant under 140 ℃ is about 3, and 000cps～about 400,000cps; The highest about 120 ℃ with its melt temperature; Its condition is to be enough to from the water outlet of moisture dye dispersion displace and to form dyestuff and the intimate mixture of dye dispersant;
(b) remove the water that is displaced;
(c) then, make gained mixture and at least a main polymer that is selected from polyester, polycarbonate, polyimide, polymeric amide and styrene plastic carry out melt blending.
Preferably; Said contact is carried out under 80 ~ 145 ℃; For example 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 140 ℃, 138 ℃, 137 ℃, 135 ℃, 133 ℃, 131 ℃, 129 ℃, 127 ℃; Preferred 85 ~ 135 ℃, further preferred 90 ~ 130 ℃.
Compared with prior art, the present invention has following beneficial effect:
The present invention adopts dyestuff to substitute pigment of the prior art, because the affinity of dyestuff and material is higher, and pigment just leans on viscous substance or other aspects to depend on body surface; Therefore; Coloured composition according to the invention is that colour batch concentration is high, and coloring effect is good, uniform coloring.
Embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical case of the present invention but non-restrictive example is following:
Embodiment 1
Will about 5kg formaldehyde, the wet dyestuff of 5kg (is the basis in the dried material) p-diaminodiphenyl places HS Baker-Perkins mixing tank.Start then and mix the cell-type impeller, and be heated to about 80 ℃.Water outlet is evaporated in decant water outlet from wet dyestuff then easily earlier.When most of water evaporated, dyestuff and dye dispersant formed homogenizing mixture, can be with its discharge and cooling.At this moment product is ground to form the suitable size that is suitable for PS and forcing machine.
Embodiment 2
Make prepared water squeezing of about 5kg such as embodiment 1 and the dyestuff that ground carry out preparatory blend, adopt conventional list or twin screw extruder to extrude then with the pure PS of about 5kg.Make extrudate be configured as many line material, and quenching in water, granulation then.This line material is level and smooth and flexibility is arranged, and tendency does not almost fracture.This granulation line material product is prone to cut off, and has outward appearance very uniformly.
Embodiment 3
Will about 5kg phenol, the wet dyestuff of 5kg (is the basis in the dried material) azo class places HS Baker-Perkins mixing tank.Start then and mix the cell-type impeller, and be heated to about 145 ℃.Water outlet is evaporated in decant water outlet from wet dyestuff then easily earlier.When most of water evaporated, dyestuff and dye dispersant formed homogenizing mixture, can be with its discharge and cooling.At this moment product is ground to form the suitable size that is suitable for polyimide and forcing machine.
Embodiment 4
Make prepared water squeezing of about 5kg such as embodiment 3 and the dyestuff that ground carry out preparatory blend, adopt conventional list or twin screw extruder to extrude then with the pure polyimide of about 5kg.Make extrudate be configured as many line material, and quenching in water, granulation then.This line material is level and smooth and flexibility is arranged, and tendency does not almost fracture.This granulation line material product is prone to cut off, and has outward appearance very uniformly.
Embodiment 5
Will about 5kg PET, the wet dyestuff of 5kg (is the basis in the dried material) azo class places HS Baker-Perkins mixing tank.Start then and mix the cell-type impeller, and be heated to about 125 ℃.Water outlet is evaporated in decant water outlet from wet dyestuff then easily earlier.When most of water evaporated, dyestuff and dye dispersant formed homogenizing mixture, can be with its discharge and cooling.At this moment product is ground to form the suitable size that is suitable for polycarbonate and forcing machine.
Embodiment 6
Make prepared water squeezing of about 5kg such as embodiment 5 and the dyestuff that ground carry out preparatory blend, adopt conventional list or twin screw extruder to extrude then with the pure polycarbonate of about 5kg.Make extrudate be configured as many line material, and quenching in water, granulation then.This line material is level and smooth and flexibility is arranged, and tendency does not almost fracture.This granulation line material product is prone to cut off, and has outward appearance very uniformly.
Comparative Examples 1
Comparative Examples 1 is CN 1208376C the disclosed embodiments 5 and embodiment 6.
Utilize DSC that colour batch described in embodiment 6 gained colour batches and the above-mentioned Comparative Examples is carried out the introduction of second-order transition temperature; Through experiment; Can find; In the colour batch according to the invention since only vector resin be polymkeric substance, and polymkeric substance and dyestuff good dispersivity have only a second-order transition temperature value.And in the Comparative Examples, two second-order transition temperatures that are close have then appearred, explain that its consistency is good inadequately.Therefore, compared with prior art, colour batch good dispersivity according to the invention, it is high depth of shade, and coloring effect is good.
The preparation method of colour batch according to the invention has avoided in final manufacturing step, handling the deuce to pay of dried dye, in said treatment step, exists unallowable pollution.Product of the present invention is very effective in dyestuff/colour masterbatch of specifically processing such as polymkeric substance such as PS and styrol copolymers.As polar polymer, this performance is unexpected.
Should be noted that and understand, under the situation that does not break away from the desired the spirit and scope of the present invention of accompanying Claim, can make various modifications and improvement the present invention of above-mentioned detailed description.Therefore, the scope of the technical scheme of requirement protection does not receive the restriction of given any specific exemplary teachings.
Applicant's statement, the present invention explains detailed method of the present invention through the foregoing description, but the present invention is not limited to above-mentioned detailed method, does not mean that promptly the present invention must rely on above-mentioned detailed method and could implement.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. a compsn that comprises following compositions is characterized in that it comprises: a) a kind of mixture of being made up of at least a dyestuff and at least a dye dispersant; And b) at least a main polymer, it is selected from the mixture of a kind of in polyester, polycarbonate, polyimide, polymeric amide and the styrene plastic or at least two kinds.
2. compsn as claimed in claim 1 is characterized in that, said dye dispersant is selected from the mixture of a kind of in naphthalene sulfonic formaldehyde condensation compound, lignosulfonic acid salt, the polymeric dispersant class or at least two kinds.
3. according to claim 1 or claim 2 compsn is characterized in that, said dye dispersant is selected from the mixture of a kind of in phenol, formaldehyde, carbonate condenses, the polyethylene terephthalate or at least two kinds.
4. like the described compsn of one of claim 1-3, it is characterized in that said compsn also comprises additive;
Preferably, said additive is selected from a kind of in dispersion agent, compatilizer, the lubricant or its mixture of at least two kinds.
5. like the described compsn of one of claim 1-4; It is characterized in that; Said dispersion agent is selected from the mixture of a kind of in polyethylene wax and copolymer waxes thereof, OPE, ethylene-acrylic acid copolymer ion salt, micro mist wax, the diffusion oil or at least two kinds, the mixture of optimal ethylene-vinyl acetate copolymer wax, diffusion oil, OPE a kind of or at least two kinds.
6. like the described compsn of one of claim 1-5, it is characterized in that said compatilizer is selected from the mixture of a kind of among PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g-MAH, the PP-g-MAH or at least two kinds.
7. like the described compsn of one of claim 1-6; It is characterized in that; Said lubricant is selected from the metallic soap class or/and aliphatic amide and verivate thereof, the mixture of a kind of in preferred calcium stearate, Zinic stearas, Magnesium Stearate, erucicamide, amine hydroxybenzene, EBS and the verivate thereof or at least two kinds.
8. like the described compsn of one of claim 1-7, it is characterized in that said compsn also comprises coupling agent or/and oxidation inhibitor.
9. like the described compsn of one of claim 1-8; It is characterized in that; Said coupling agent is selected from the mixture of a kind of in silane coupling agent, titanate coupling agent, aluminate coupling agent, metal composite coupling agent, phosphate coupling agent, the boric acid ester coupler or at least two kinds, preferred titanate coupling agent and/or aluminate coupling agent;
Preferably, said oxidation inhibitor is selected from the mixture of a kind of in antioxidant 1010, antioxidant 1076, oxidation inhibitor 168, antioxidant BHT, the antioxidant 264 or at least two kinds.
10. one kind like the said preparation of compositions method of one of claim 1-9, it is characterized in that this method comprises:
(a) moisture dye dispersion or moisture wet dyestuff block are contacted with at least a dye dispersant; The brookfield viscosity of said dye dispersant under 140 ℃ is about 3, and 000cps～about 400,000cps; The highest about 120 ℃ with its melt temperature; Its condition is to be enough to from the water outlet of moisture dye dispersion displace and to form dyestuff and the intimate mixture of dye dispersant;
(b) remove the water that is displaced;
(c) then, make gained mixture and at least a main polymer that is selected from polyester, polycarbonate, polyimide, polymeric amide and styrene plastic carry out melt blending;
Preferably, said contact is carried out under 80 ~ 145 ℃, and preferred 85 ~ 135 ℃, further preferred 90 ~ 130 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105155309A (en) * | 2015-09-23 | 2015-12-16 | 泉州市新宏化工贸易有限公司 | Dyeing technology for polyester fabric and finishing agent named Dishubao |
| CN108017895A (en) * | 2018-01-12 | 2018-05-11 | 上海晨光文具股份有限公司 | Masterbatch, the preparation method of Masterbatch and polymeric material |
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Application publication date: 20120919 |