CN101281370B - Light-sensitive polymer composition with low surface stickiness and application thereof - Google Patents
Light-sensitive polymer composition with low surface stickiness and application thereof Download PDFInfo
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- CN101281370B CN101281370B CN2007100392563A CN200710039256A CN101281370B CN 101281370 B CN101281370 B CN 101281370B CN 2007100392563 A CN2007100392563 A CN 2007100392563A CN 200710039256 A CN200710039256 A CN 200710039256A CN 101281370 B CN101281370 B CN 101281370B
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Abstract
The invention relates to a phototonus resin composite of low surface adhesiveness and its application. The composite comprises a 0.1 to 50 wt percent mixing silica powder, 0.1 to 50 wt percent water solubility bond polymer, 0.1 to 50 wt percent photocureable compound, 0.5 to 40 wt percent thermosetting compound, 0.1 to 10 wt percent diazonium resin or bichromate and proper additive. Compared with the prior art, the invention has the characteristics of improving water resistance and solvent resistance, without damage to image resolution and low surface adhesiveness.
Description
Technical field
The present invention relates to the high-molecular organic material science and technology field, be specifically related to photosensitive polymer combination of a kind of low surface tackiness and uses thereof.
Background technology
At present; Can use the photosensitive material kind of water development a lot, but all be the water soluble resin that contains the water wettability base, so can not get the image of water-tolerant; Since for water development property good; Added water soluble compound, interfacial agent, but held the emulsified compound of water wettability base, its as a result behind the photocuring water wettability still residual.So enough water tolerance can not be arranged, also have in right-falling stroke and catch when using, press down the pigment, the dyestuff that dye in the paste and infiltrate in the image hydroxy reaction pollution image that forms the water-soluble polymers in the thing with image and must not get expected effect.
For fear of these shortcomings, at present also hardening characteristics is good, the dichromate rigidizer of water-tolerant using.But the state of the 6 valency chromium of dichromate in sensitization liquid and light-sensitive surface is toxic; The wastewater treatment difficulty is high; Half tone after the use will recycle; Big to environmental disruption property, be used in rotary screen and press down and dye the aspect because its water tolerance, anti-solvent aspect superior performance, still at the photosensitive polymer combination that uses polyvinyl alcohol (PVA) vinyl acetate base emulsion with the low surface tackiness of dichromate formation.On the other hand, just in practicability, but it is all poor to compare dichromate water tolerance, organic solvent resistance, resolution as the photosensitive polymer combination of the low surface tackiness of rigidizer stibazole base or styryl quinolyl or diazonium.
Remedy performance part so be added on the compound of the vinyl base of ability polymerization under the light action than dichromate difference., the compound that contains the vinyl base that can photocuring, its surface tackiness of the light-sensitive surface before photocuring is strong, and exposure is difficult to peel off with the original copy egative film, because surface tackiness is strong, not only egative film location difficulty, and surface is clung foreign matters such as dust easily.
Summary of the invention
The object of the invention is exactly to provide a kind of when improving water tolerance, solvent resistance for the defective that overcomes above-mentioned prior art existence, does not damage photosensitive polymer combination of the low surface tackiness of separating picture and uses thereof.
The object of the invention can be realized through following technical scheme: a kind of photosensitive polymer combination of low surface tackiness; It is characterized in that said composition comprises that synthetic silica powder 0.1～50wt%, water-soluble binder polymkeric substance 0.1～50wt%, photo-curing compound 0.1～50wt%, heat curing compound 0.5～40wt%, diazo resin or dichromate 0.1～10wt%, adjuvant are an amount of.
Described synthetic silica powder is one or more the water-insoluble inanimate matter solids in synthetic silica, carclazyte, the talcum; That the form of this inanimate matter solid comprises is fibrous, slit-like, laminar, granular, spherical, hollow spheres, Powdered, tabular, preferred tabular or laminar.
Described synthetic silica powder is the synthetic silica powder that the surface covers with the hydroxide base, and its content is 1～25wt%, and its particle diameter is 0.1～40 μ m mean grain size, preferred 3.5～9.0 μ m particle diameters.
Described water-soluble binder polymkeric substance is for adding the condensate of sensitization base stibazole base or styryl quinolyl; The vinyl polymerization body that comprises basicity 60～100mol%; Carboxyl sex change, kation, anionic all modified polyvinyl alcohols, preferred 70～100% vinyl acetate base condensate; Its degree of polymerization 200～5000, preferred 300～4000, its content is 1～25wt%.
Described photo-curing compound for dissolving or mix contain trigger for optical solidification vinyl-based more than can photocuring compound; The preferred free radical cure initiating agent of this trigger for optical solidification; Comprise thioxanthones inductor or the Benzophenone inductor of holding water-soluble ammonium, the diphenylhydroxyethanone and the diphenylhydroxyethanone alkyl ether of oil-soluble trigger for optical solidification such as diphenylhydroxyethanone, diphenylhydroxyethanone methyl ether, diphenylhydroxyethanone ether, diphenylhydroxyethanone isopropyl ether class; Acetophenone, 2; This ethyl ketone of 2-dimethoxy-2-, 2; 2-diethoxy-acetophenone, 1, the acetophenones of 1-dichloroacetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1,1-(4-propyloxy phenyl ester)-2-hydroxyl 2-methylpropane 1-1,1-(4-dodecanol phenyl)-2-hydroxy-2-methyl propane-1-1,4-(2-hydroxy ethoxy)-phenyl (2-hydroxyl 2-propyl group) ketone, 1-hydroxy-cyclohexyl phenyl ketone etc.; The aminoacenaphthene class of 2-methyl isophthalic acid-[4-(first sulphur) phenyl]-2-morpholine acetone 1,2-phenyl 2-dimethylamino (4-morpholinyl phenyl)-butanone 1 etc.; The anthraquinone class of 2-methylanthraquinone, 2-ethyl group anthraquinone, 2-tert-butyl anthraquinone, 1-chloroanthraquinone etc.; 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2, the thioxanthene ketone of 4-diisopropyl thioxanthones etc.; The ketals of acetophenone dimethyl ketone acetal, benzyl Ketene dimethyl acetal etc.; The Benzophenone class of Benzophenone or oxygen folder anthracene class; A kind of in the 3rd level amine or several kinds are through dissolving or disperse to use.
Described vinylic is acryloyl base class or the single amount of metering system class body; Comprise: the 2-ethylacrylic acid is ester, isodecyl acrylate, 2-hydroxy acrylic acid ethyl ester, 2-hydroxy acrylic acid propyl ester, acrylic acid-2-butyric ester, acrylic acid-2-ethoxy ethyl ester, 2 (2-hydroxyethyl)-acrylic ester, acrylic acid-n-butoxy ethyl ester, morpholinyl acrylic ester, benzyl acrylic ester, phenyl acrylate, methoxyl diglycol acrylic ester, methoxy acrylic acid triglycol ester, methoxy acrylic acid TEG ester, methoxy acrylic acid macrogol ester, ethoxydiglycol acrylic ester, ethoxy propylene triethylenetetraminehexaacetic acid diol ester, ring ethyl propylene acid esters, tetrahydrochysene chaff acrylic ester, iso-bornyl acrylate, cyclopentadienyl group acrylic ester, N; TMSDMA N dimethylamine base ethanol acrylic ester, N; TMSDEA N diethylamine base ethanol acrylic ester, hexanediyl ester, diethylene glycol diacrylate, 1; Ammediol diacrylate, 1; 4-butanediol diacrylate, 1; 6-hexanediyl ester, neopentylglycol diacrylate, two (acryloyl neopentyl glycol) hexanedioic acid ester, two (methacrylyl neopentyl glycol) hexanedioic acid ester, chloropropylene oxide sex change 1; The pivalic acid neopentylglycol diacrylate polyoxyethylene diacrylate of 6-hexanediyl ester hydroxyl pivalic acid neopentylglycol diacrylate, caprolactone sex change hydroxyl, propylene glycol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, dodecyl glycol diacrylate, polypropyleneglycol diacrylate, trimethylolpropane triacrylate, three hydrogen methylpropane triacrylates, neopentyl glycol sex change three hydrogen methyl diacrylates, ethylene oxide,1,2-epoxyethane sex change three hydrogen methyl triacrylates, epoxypropane sex change three hydrogen methyl triacrylates, tetramethylol methane tetraacrylate, stearic acid sex change pentaerythritol diacrylate, dipentaerythritol acrylate, dipentaerythritol monohydroxy five acrylic ester, alkyl sex change dipentaerythritol acrylic ester, caprolactone sex change dipentaerythritol polyacrylate, glycerine diacrylate, chloropropylene oxide sex change glycerine triacrylate, three (acryloyl group ethoxy) isocyanuric acid ester, three (acryloyl group methoxy) isocyanuric acid ester, caprolactone sex change three (acryloyl group ethoxy) isocyanuric acid ester, caprolactone sex change three (acryloyl group methoxy) isocyanuric acid ester, become ester and pay epoxy acrylate, the urethanes acrylic ester that adds acrylic ester, line style phenolic epoxy acrylic ester, methyl phenol aldehyde type epoxy acrylate etc. oligomer class such as polyester acrylate oligomer, bisphenol-a epoxy acrylate; Its content is 1～25wt%.
Described heat curing compound is a compound of holding the functional group, and described functional group comprises aldehyde-base, NCO, alkoxy, glycidyl, ethene property unsaturated group, amino, diester class; Described compound comprises the amino-compound of thiourea, melamine etc.; The alkoxide compound of methylolation melamine, butyral melamine etc.; The dialdehyde compounds of glyoxal, valeral etc., the vinyl-based compound of the metal chelate compound of block isocyanate compound, cobalt, titanium, molybdenum, acryloyl group, S-acrylamido, vinyl ether; Described block isocyanate compound is the pellicle of the NCO of isocyanate compound with block agent formation, when normal temperature, is stable, is heated to and resolves into active NCO more than 120 ℃; Described isocyanate compound is to have the NCO more than 2, the compound of 2 above NCOs at least; Comprise 2; 6-toluene diisocyanate (2; The 6-toluene diisocyanate), 2; 4-toluene diisocyanate (2; The 4-toluene diisocyanate), 4,4-'-diphenylmethane diisocyanate, naphthalene diisocyanate ,-XDI ,-aromatic diisocyanate, the methyl ring di-isocyanate, 2,2 of tetramethylxylene diisocyanate etc.; 4-trimethyl hexamethylene diisocyanate, 2; 4, the trimethylolpropane of the alicyclic diisocyanate of the aliphatic isocyanates of 4-trimethyl hexamethylene diisocyanate, hydrogen interpolation 4,4 ' '-diphenylmethane diisocyanate, hydrogen interpolation m-XDI etc., triphenylmethane triisocyanate, polymethylene polyphenyl isocyanates, toluene diisocyanate adds the multifunctional aromatic isocyanate compound of zoarium, isocyanates body, polymerization methane diisocyanate, other prepolymer isocyanates; Described block agent includes the compound of caprolactam, active methylene group, oxime of reactive hydrogen etc.; Its content is 1～20wt%.
Described diazo resin or dichromate content are 0.2～5wt%; Described diazo resin comprises the poly-formaldehyde condensate, 4 of P-diazonium diphenylamine; The poly-formaldehyde condensate, 4 of 4 ' dimethoxy diphenyl ether condensation product, 4-diazonium-3-methoxy diphenylamine, 4 ' dimethyl diphenyl ether condensation product etc.; Described dichromate comprises ammonium dichromate, potassium dichromate and dichromic acid sylvite.
Described adjuvant comprises foam-breaking agent, measurement of the level agent, colorant, antiseptic, organic/inorganic filler, organic solvent, plasticizer, interfacial agent; Its content is 0.1～50wt%.
The purposes of the photosensitive polymer combination of above-mentioned a kind of low surface tackiness; It is characterized in that this photosensitive resin composition is coated in 0.1～2000 μ m thickness on the silk screen order, the light-sensitive surface of preferred 1～1000 μ m thickness with scraper; Be dried to the dull and stereotyped silk screen PS version of not exposure at Wen Fengzhong; With the egative film exposure of finishing figure, wash exposure is partly stayed when using then, just become dull and stereotyped serigraphy with the brush version; Perhaps described photosensitive resin composition with colyliform scraper gluing on metal rotary tube silk screen, its dry film thickness 0.1～1000 μ m, preferred 1～400 μ m; The drying process of temperature wind once or is repeatedly processed the PS version of rotary screen repeatedly; On the PS of not exposure version,, wash exposure and partly stay, use 50 ℃～220 ℃ again with the egative film exposure of finishing figure; Preferred 130 ℃～200 ℃ heat treated obtain the tube serigraphy of rotary-type garden with the brush version; Be 0.5～4 hour heat time heating time, preferred 1～3 hour, or use laser scribing shape after the first heat treated.
Compared with prior art, add the synthetic silica powder that the surface covers with the hydroxide base in the photoresist of the present invention, the granularity of photosensitive polymer combination adjustment synthetic silica makes and reduces surface adhesion force when not influencing resolution; In addition, the surface hydroxyl of synthetic silica makes the reaction that increases with diazonium or block isocyanates, strengthens solidifying, and improves water tolerance and solvent resistance more.
Embodiment
Below in conjunction with embodiment the present invention is described further.
Comparative example 1
Polyethylene vinyl acetate emulsion [NICHGO (Co., Ltd.) MOVINYL206 solids content of 50 wt%] 30 parts and a polymerization degree of 1700, a polyvinyl alcohol 88mol% basicity [Japan Synthetic (Corp.), PVA-210] of 12 wt. % aqueous solution of 40 parts of a mixture in the blocked isocyanate (Japanese isocyanate industrial manufacturing CORONATE2513) 10 parts and a photopolymerization initiator ethylthioxanthone [Nippon Kayaku (Corp.), KAUACURE? BP-100] 0.2 parts, and a polymerization promoter agent is an amine compound [Nippon Kayaku (Corp.), KAYACURE-EPA] 0.1 parts of an acrylate monomer mixed solution [Shin-Nakamura Chemical (Co., Ltd.) A-TMM-3] 10 parts of curing agent emulsions and two P-Diazo phenyl-amine sulfate condensate paraformaldehyde 1, were mixed to obtain a photosensitive resin composition.Coat the thick emulsion of 20 μ m with the scraper of colyliform above making this photoresists electricity consumption forming method the silk screen garden tube 120 order/inches of rotation, 1 hour drying of 40 ℃ warm wind is not then used the egative film of finishing figure to roll up above the garden shape PS version of exposure at this and is sticked; With the interval of 3kw mercury vapor lamp apart from 300mm; The traveling time of light source is to come and go in 6 minutes 30 seconds/one, the revolution that the garden net is 20 seconds/10 times, exposure 2 come and go; Wash then; Stay figure, 180 ℃ of following thermal treatment is 90 minutes again, has accomplished the garden reticulated printing with the brush version.
Comparative example 2
After 10 parts of emulsifications of acrylate monomer [Xin Zhong village chemical (strain) made A-TMM-3] of 10 parts of block isocyanates (the industrial CORONATE2513 that makes of Japanese isocyanates) and 0.2 part of trigger for optical solidification diethyl thia anthracene [Japanese chemical drug (strain) is made KAYACURE BP-100] and 0.1 part of dissolving mixing of polymerization accelerant amines [Japanese chemical drug (strain) is made KAYACURE-EPA] in the mixed liquor that the sensitization aqueous solution polymerization body of 12 weight % of the stibazole salt of the polyvinyl alcohol (PVA) of 30 parts of tygon vinyl acetate base emulsions [NIGHIGO (strain) MOVINYL206 solids content 50 weight %] and the degree of polymerization 1700 basicity 88mol% [Japan synthesizes the PVA-210 of (strain) manufacturing] linings adding 1.4mol% is 40 parts; The photosensitive polymer combination of obtaining, it as a rule 1 method processed the rotary screen printing with brush version.
Comparative example 3
The synthetic silica that adds mean grain size 14.1 μ m in the photosensitive polymer combination shown in the comparative example 1, [SYLYSIA470 of the SYLYSIA of Fuji chemistry (strain) society system] 10 parts uses the same method and made garden reticulated printing version.
Comparative example 4
The synthetic silica that adds mean grain size 2.7 μ m in the photosensitive polymer combination shown in the comparative example 1, [SYLYSIA310P of the SYLYSIA of Fuji chemistry (strain) society system] 10 parts uses the same method and made garden reticulated printing version.
Embodiment 1
Light-fixing agent P-diazonium diphenylamine sulfate poly-formaldehyde condensate together mixed photosensitive polymer combination for 1 part after 10 parts of WS with polyvinyl alcohol (PVA) [PVA-210 that Japanese synthetic (strain) makes] the 12 weight % of the degree of polymerization 1700 basicity 88mol% of the synthetic silica of mean grain size 6.4 μ m [SYLYSIA370P of the SYLYSIA of Fuji chemistry (strain) society system] mixed the 10 parts of emulsifications of acrylate monomer [A-TMM-3 that Xin Zhong village chemistry (strain) is made] that add 10 parts of block isocyanates (CORONATE2513 of Japanese polycarbamate industry system) and 0.2 part of trigger for optical solidification diethyl thia anthracene [KAYACURE-BP-100 of Japanese chemical drug (strain) system] and 0.1 part of dissolving mixing of polymerization accelerant amines [KAYACURE-EPA of Japanese chemical drug (strain) system] again for 40 parts, had then made garden reticulated printing version with the method for comparative example 1.
Embodiment 2
10 parts of polyvinyl alcohol (PVA) [PVA-210 of Japan's synthetic (strain) system] with the degree of polymerization 1700 basicity 88mol% of the synthetic silica of mean grain size 6.4 μ m [SYLYSIA370P of the SYLYSIA of Fuji chemistry (strain) society system] are combined into photosensitive polymer combination after going up in the mixed liquor of 40 parts of photonasty aqueous solution polymerization bodies of additional 12 weight %, 1.4mol% stibazole salt 0.2 part of 10 parts of block isocyanates (CORONATE2513 of Japanese polycarbamate industry system) and Photoepolymerizationinitiater initiater diethyl thia anthracene [KAYACURE-BP-100 of Japanese chemical drug (strain) system] and 10 parts of emulsifications of polymerization accelerant amines [A-TMM-3 of Japanese chemical drug (strain) system], have then made garden reticulated printing version with the method for comparative example 1.
The comparative evaluation result of comparative example 1～4 and embodiment 1,2 representes with table 1.Expansivity is that the garden reticulated printing that comparative example, embodiment make soaks the expansivity of measuring in 24 hours with the size of getting test film 3cm * 3cm on the brush version in various solution.The more little water tolerance solvent resistance of weight expansion is strong more, and printing evaluation is that garden reticulated printing machine [R-200 type of industry (strain) system is stretched in east] upward uses the emulsion paste that contains chemically-reactive dyes at the portrait state that prints the photoresist of observing behind the 10000m on the continuous cloth.
Table one
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Embodiment 1 | Embodiment 2 | |
| Surface adhesion force | By force | By force | Do not have | Little have | Do not have | Do not have |
| Resolution (um) | 125 | 150 | 200 | 125 | 125 | 150 |
| Expansivity (weight %) | ||||||
| Water | 10.1 | 12.5 | 8.0 | 8.2 | 8.0 | 9.2 |
| 5% aqueous sulfuric acid | 11.2 | 13.8 | 8.1 | 8.0 | 8.1 | 9.9 |
| The 5%NaOH WS | 18.8 | 21.2 | 11.8 | 12.4 | 12.0 | 13.3 |
| Acetone | 27 | 38.4 | 12.8 | 14.8 | 13.3 | 15.0 |
| Acetic acid ethane | 42.5 | 50.2 | 15.3 | 17.6 | 16.6 | 18.5 |
| Printing back portrait | Partial destruction | Partial destruction | Do not have and destroy | Do not have and destroy | Do not have and destroy | Do not have and destroy |
Embodiment 3
The polyvinyl of the water miscible basicity that contains stibazole base or styryl quinolyl more than 60%, the surface coverage of averaged particles footpath 3.5～9.0 μ m the synthetic silica powder (changing 2) of hydroxy and the compound that under the effect of heat, can harden, the photosensitive polymer combination of formation.This photosensitive polymer combination comprises synthetic silica powder (A) 0.1wt%, water-soluble binder polymkeric substance (B) 50wt%, photo-curing compound (C) 0.1wt%, heat curing compound (D) 40wt%, diazo resin or dichromate (E) 0.1wt%, foam-breaking agent 0.2wt%, measurement of the level agent 0.5wt%, colorant 0.5wt%, antiseptic 0.1wt%, organic/inorganic filler 5wt%, organic solvent 3.2wt%, plasticizer 0.1wt%, interfacial agent 0.1wt%.
Embodiment 4
The polyvinyl alcohol (PVA) of basicity more than 60%, the synthetic silica powder of averaged particles footpath 3.5～9.0 μ m that contain the light curing agent diazo resin, the photosensitive polymer combination that under heat effect, solidify to form.This photosensitive polymer combination comprises synthetic silica powder 50wt%, water-soluble binder polymkeric substance 0.1wt%, photo-curing compound 25wt%, heat curing compound 0.5wt%, diazo resin or dichromate 10wt%, foam-breaking agent 0.2wt%, measurement of the level agent 0.5wt%, colorant 0.5wt%, antiseptic 0.1wt%, organic/inorganic filler 5wt%, organic solvent 8.1wt%.
Embodiment 5
The polyvinyl alcohol (PVA) of basicity more than 60%, the synthetic silica powder of averaged particles footpath 3.5～9.0 μ m that contain the light curing agent dichromate, the photosensitive polymer combination that the compound that under heat effect, can solidify is died.This photosensitive polymer combination comprises synthetic silica powder 1wt%, water-soluble binder polymkeric substance 25wt%, photo-curing compound 1wt%, heat curing compound 1wt%, diazo resin or dichromate 5wt%, foam-breaking agent 1wt%, measurement of the level agent 5wt%, colorant 5wt%, antiseptic 1wt%, organic/inorganic filler 25wt%, organic solvent 25wt%, plasticizer 4wt%, interfacial agent 1wt%.
Contain dissolve in advance or mixed Photoepolymerizationinitiater initiater can be photopolymerisable, contain any one above-mentioned photosensitive polymer combination of the compound of more than one vinyl base at least.
The powder composition (A) that reduces surface tackiness must contain the inanimate matter solid; The water-insoluble inanimate matter solid of one or more that select in synthetic silica, carclazyte, the talcum; Photosensitive polymer combination in above-mentioned synthetic silica, carclazyte, talcum, common particularly adducible synthetic silica, carclazyte, talcum, porcelain earth etc.Preferably the surface surrounds the synthetic silica of hydroxy; Its hydroxy can solidify under the heat effect of composition (D); Perhaps the diazo resin of composition (E) reaction increase cured density makes and improves water tolerance, solvent resistance; These synthetic silicas, carclazyte, talcum can use separately, also can and use and use.Screen printing plate has fibrous, slit-like, laminar, granular, spherical, hollow spheres, Powdered, tabular etc. with the form of the used inorganic solid content of photosensitive polymer combination among the present invention, and usefulness is tabular or laminar usually.The particle diameter of the inanimate matter solids of using among the present invention has 0.1～40 μ m mean grain size, and better have 1～20 μ m mean grain size, preferably 3.5～9.0 μ m particle diameters.The words of the following scope of lower limit can not be improved surface adhesion force, and the above words resolution difference of the upper limit can't be practical.
Described water-soluble binder polymkeric substance is for adding the condensate of sensitization base stibazole base or styryl quinolyl; The vinyl polymerization body that comprises basicity 60～100mol%; Basicity is lower than this standard poorly water-soluble; Carboxyl sex change, kation, anionic all modified polyvinyl alcohols, preferred 70～100% vinyl acetate base condensate; Its degree of polymerization 200～5000, preferred 300～4000, the degree of polymerization is lower than this scope, and light not melting speed is very slow, and sensitivity is not enough, is higher than that this scope viscosity is too high can not be used.
For the water-soluble binder polymkeric substance; When adding sensitization base stibazole base (changing 1) or styryl quinolyl (changing 2) in advance; General 0.2～the 7.0mol% of unit to vinyl alcohol of polyvinyl alcohol, 0.5～5.0mol% preferably, image forms insufficient when being lower than above-mentioned scope; Water-solublely when surpassing above-mentioned scope become very poor, but change 1 and change that R1 representes hydrogen atom in 2.Alkyl or aralkyl can comprise that also hydroxy, carbamyl, ether combine, unsaturated combination.R2 is expression oxygen atom or low alkyl group.X-is expression halide ion, phosphate ion, p-toluenesulfonic acid or these anionic potpourris, and m representes that o or 1, n represent 1～6 integer.
Described photo-curing compound for dissolving or mix contain trigger for optical solidification vinyl-based more than can photocuring compound; The preferred free radical cure initiating agent of this trigger for optical solidification; Comprise thioxanthones inductor or the Benzophenone inductor of holding water-soluble ammonium, the diphenylhydroxyethanone and the diphenylhydroxyethanone alkyl ether of oil-soluble trigger for optical solidification such as diphenylhydroxyethanone, diphenylhydroxyethanone methyl ether, diphenylhydroxyethanone ether, diphenylhydroxyethanone isopropyl ether class; Acetophenone, 2; This ethyl ketone of 2-dimethoxy-2-, 2; 2-diethoxy-acetophenone, 1, the acetophenones of 1-dichloroacetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1,1-(4-propyloxy phenyl ester)-2-hydroxyl 2-methylpropane 1-1,1-(4-dodecanol phenyl)-2-hydroxy-2-methyl propane-1-1,4-(2-hydroxy ethoxy)-phenyl (2-hydroxyl 2-propyl group) ketone, 1-hydroxy-cyclohexyl phenyl ketone etc.; The aminoacenaphthene class of 2-methyl isophthalic acid-[4-(first sulphur) phenyl]-2-morpholine acetone 1,2-phenyl 2-dimethylamino (4-morpholinyl phenyl)-butanone 1 etc.; The anthraquinone class of 2-methylanthraquinone, 2-ethyl group anthraquinone, 2-tert-butyl anthraquinone, 1-chloroanthraquinone etc.; 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2, the thioxanthene ketone of 4-diisopropyl thioxanthones etc.; The ketals of acetophenone dimethyl ketone acetal, benzyl Ketene dimethyl acetal etc.; The Benzophenone class of Benzophenone or oxygen folder anthracene class; A kind of in the 3rd level amine or several kinds are through dissolving or disperse to use.
Described vinylic is acryloyl base class or the single amount of metering system class body; Comprise: the 2-ethylacrylic acid is ester, isodecyl acrylate, 2-hydroxy acrylic acid ethyl ester, 2-hydroxy acrylic acid propyl ester, acrylic acid-2-butyric ester, acrylic acid-2-ethoxy ethyl ester, 2 (2-hydroxyethyl)-acrylic ester, acrylic acid-n-butoxy ethyl ester, morpholinyl acrylic ester, benzyl acrylic ester, phenyl acrylate, methoxyl diglycol acrylic ester, methoxy acrylic acid triglycol ester, methoxy acrylic acid TEG ester, methoxy acrylic acid macrogol ester, ethoxydiglycol acrylic ester, ethoxy propylene triethylenetetraminehexaacetic acid diol ester, ring ethyl propylene acid esters, tetrahydrochysene chaff acrylic ester, iso-bornyl acrylate, cyclopentadienyl group acrylic ester, N; TMSDMA N dimethylamine base ethanol acrylic ester, N; TMSDEA N diethylamine base ethanol acrylic ester, hexanediyl ester, diethylene glycol diacrylate, 1; Ammediol diacrylate, 1; 4-butanediol diacrylate, 1; 6-hexanediyl ester, neopentylglycol diacrylate, two (acryloyl neopentyl glycol) hexanedioic acid ester, two (methacrylyl neopentyl glycol) hexanedioic acid ester, chloropropylene oxide sex change 1; The pivalic acid neopentylglycol diacrylate polyoxyethylene diacrylate of 6-hexanediyl ester hydroxyl pivalic acid neopentylglycol diacrylate, caprolactone sex change hydroxyl, propylene glycol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, dodecyl glycol diacrylate, polypropyleneglycol diacrylate, trimethylolpropane triacrylate, three hydrogen methylpropane triacrylates, neopentyl glycol sex change three hydrogen methyl diacrylates, ethylene oxide,1,2-epoxyethane sex change three hydrogen methyl triacrylates, epoxypropane sex change three hydrogen methyl triacrylates, tetramethylol methane tetraacrylate, stearic acid sex change pentaerythritol diacrylate, dipentaerythritol acrylate, dipentaerythritol monohydroxy five acrylic ester, alkyl sex change dipentaerythritol acrylic ester, caprolactone sex change dipentaerythritol polyacrylate, glycerine diacrylate, chloropropylene oxide sex change glycerine triacrylate, three (acryloyl group ethoxy) isocyanuric acid ester, three (acryloyl group methoxy) isocyanuric acid ester, caprolactone sex change three (acryloyl group ethoxy) isocyanuric acid ester, caprolactone sex change three (acryloyl group methoxy) isocyanuric acid ester, become ester and pay epoxy acrylate, the urethanes acrylic ester that adds acrylic ester, line style phenolic epoxy acrylic ester, methyl phenol aldehyde type epoxy acrylate etc. oligomer class such as polyester acrylate oligomer, bisphenol-a epoxy acrylate.
Can use polyester acrylate oligomer, bisphenol-a epoxy acrylate, become ester and pay the epoxy acrylate that adds acrylic ester, line style phenolic epoxy acrylic ester, methyl phenol aldehyde type epoxy acrylate etc., urethanes acrylic ester etc. as oligomer.
Described heat curing compound is a compound of holding the functional group, and described functional group comprises aldehyde-base, NCO, alkoxy, glycidyl, ethene property unsaturated group, amino, diester class; Described compound comprises the amino-compound of thiourea, melamine etc.; The alkoxide compound of methylolation melamine, butyral melamine etc.; The dialdehyde compounds of glyoxal, valeral etc., the vinyl-based compound of the metal chelate compound of block isocyanate compound, cobalt, titanium, molybdenum, acryloyl group, S-acrylamido, vinyl ether; Make these compound blendings its better effects if together, these are held in functional group's the compound, and its long-time stability aspect of the photosensitive polymer combination of block isocyanate compound is very superior.
Described block isocyanate compound is the pellicle of the NCO of isocyanate compound with block agent formation, when normal temperature, is stable, is heated to and resolves into active NCO more than 120 ℃; Use level exceeds above-mentioned scope and composition photo-curing compound one example edition film surface tackiness is strong, and the original copy egative film is difficult to peel off after the exposure, is lower than scope water tolerance poor solvent resistance.Described isocyanate compound is to have the NCO more than 2, the compound of 2 above NCOs at least; Comprise 2; 6-toluene diisocyanate (2; The 6-toluene diisocyanate), 2; 4-toluene diisocyanate (2; The 4-toluene diisocyanate), 4,4-'-diphenylmethane diisocyanate, naphthalene diisocyanate ,-XDI ,-aromatic diisocyanate, the methyl ring di-isocyanate, 2,2 of tetramethylxylene diisocyanate etc.; 4-trimethyl hexamethylene diisocyanate, 2; 4, the trimethylolpropane of the alicyclic diisocyanate of the aliphatic isocyanates of 4-trimethyl hexamethylene diisocyanate, hydrogen interpolation 4,4 ' '-diphenylmethane diisocyanate, hydrogen interpolation m-XDI etc., triphenylmethane triisocyanate, polymethylene polyphenyl isocyanates, toluene diisocyanate adds the multifunctional aromatic isocyanate compound of zoarium, isocyanates body, polymerization methane diisocyanate, other prepolymer isocyanates; Described block agent includes the compound of caprolactam, active methylene group, oxime of reactive hydrogen etc.
Described diazo resin comprises the poly-formaldehyde condensate, 4 of P-diazonium diphenylamine, the poly-formaldehyde condensate, 4 of 4 ' dimethoxy diphenyl ether condensation product, 4-diazonium-3-methoxy diphenylamine, 4 ' dimethyl diphenyl ether condensation product etc.; Described dichromate comprises ammonium dichromate, potassium dichromate and dichromic acid sylvite.
The serigraphy of the garden shape rotation that above-mentioned any one photosensitive polymer combination makes is with the brush version; This photosensitive resin composition is coated in 0.1～2000 μ m thickness on the silk screen order with scraper; The light-sensitive surface of preferred 1～1000 μ m thickness in the dull and stereotyped silk screen PS version that Wen Fengzhong is dried to not exposure, is used the egative film exposure of finishing figure when using then; Wash exposure is partly stayed, just become dull and stereotyped serigraphy with the brush version.
The brush version that the plane serigraphy that above-mentioned any one photosensitive polymer combination makes is used, this photosensitive resin composition with colyliform scraper gluing on metal rotary tube silk screen, its dry film thickness 0.1～1000 μ m; Preferred 1～400 μ m, the drying process of warm wind once or repeatedly process the PS version of rotary screen repeatedly, on the PS of not exposure version, use the egative film exposure of finishing figure; Washing exposure partly stays; Use 50 ℃～220 ℃ again, preferred 130 ℃～200 ℃ heat treated obtain the tube serigraphy of rotary-type garden with the brush version, and be 0.5～4 hour heat time heating time; Preferred 1～3 hour, use laser scribing shape after the perhaps first heat treated.
Claims (8)
1. the photosensitive polymer combination of a low surface tackiness; It is characterized in that said composition comprises that synthetic silica powder 0.1～50wt%, water-soluble binder polymkeric substance 1～25wt%, photo-curing compound 0.1～50wt%, heat curing compound 0.5～40wt%, diazo resin or dichromate 0.2～5wt%, adjuvant are an amount of;
Described water-soluble binder polymkeric substance is for adding the condensate of sensitization base stibazole base or styryl quinolyl; The vinyl polymerization body that comprises basicity 60～100mol%; The polyvinyl alcohol (PVA) of carboxyl sex change, kation, negative ion sex change, its degree of polymerization 200～5000;
Described diazo resin comprises the poly-formaldehyde condensate of P-diazonium diphenylamine, the poly-formaldehyde condensate of 4-diazonium-3-methoxy diphenylamine; Described dichromate comprises ammonium dichromate, potassium dichromate.
2. the photosensitive polymer combination of a kind of low surface tackiness according to claim 1; It is characterized in that; Described synthetic silica powder is the water-insoluble inanimate matter solid of synthetic silica, and that the form of this inanimate matter solid comprises is fibrous, slit-like, laminar, granular, hollow spheres, Powdered, tabular.
3. the photosensitive polymer combination of a kind of low surface tackiness according to claim 1 and 2; It is characterized in that; Described synthetic silica powder is the synthetic silica powder that the surface covers with the hydroxide base, and its content is 1～25wt%, and its particle diameter is 0.1～40 μ m mean grain size.
4. the photosensitive polymer combination of a kind of low surface tackiness according to claim 1; It is characterized in that; Described photo-curing compound for dissolving or mixed light curing initiator contain an above vinyl can photocuring compound, trigger for optical solidification is diphenylhydroxyethanone, diphenylhydroxyethanone methyl ether, diphenylhydroxyethanone ether, diphenylhydroxyethanone isopropyl ether; Acetophenone, 2,2-dimethoxy-2-acetophenone, 2,2-diethoxy-acetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone; 2-methylanthraquinone, 2-tert-butyl anthraquinone, 1-chloroanthraquinone; 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2,4-diisopropyl thioxanthones; Benzophenone or oxygen folder anthracene.
5. the photosensitive polymer combination of a kind of low surface tackiness according to claim 4; It is characterized in that; Described contain an above vinyl can photocuring compound be acryloyl base class or methyl-prop vinyl monomer; Comprise: 2 ethyl hexyl acrylate, isodecyl acrylate, 2-hydroxy acrylic acid ethyl ester, 2-hydroxy acrylic acid propyl ester, acrylic acid-2-ethoxy ethyl ester, acrylic acid-n-butoxy ethyl ester, methoxy acrylic acid triglycol ester, methoxy acrylic acid TEG ester, methoxy acrylic acid macrogol ester, ethoxy propylene triethylenetetraminehexaacetic acid diol ester, N; TMSDMA N dimethylamine base ethanol acrylic ester, N; TMSDEA N diethylamine base ethanol acrylic ester, hexanediyl ester, diethylene glycol diacrylate, 1; Ammediol diacrylate, 1; 4-butanediol diacrylate, 1,6 hexanediol diacrylate, neopentylglycol diacrylate, two (acryloyl neopentyl glycol) adipate, two (methacrylyl neopentyl glycol) adipate, propylene glycol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, polypropyleneglycol diacrylate, trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, stearic acid sex change pentaerythritol diacrylate, dipentaerythritol acrylate, alkyl sex change dipentaerythritol acrylic ester, glycerine diacrylate, chloropropylene oxide sex change glycerine triacrylate, bisphenol-a epoxy acrylate, line style phenolic epoxy acrylic ester, methyl phenol aldehyde type epoxy acrylate; Its content is 1～25wt%.
6. the photosensitive polymer combination of a kind of low surface tackiness according to claim 1; It is characterized in that; Described heat curing compound is a compound of holding functional group, and described functional group comprises aldehyde-base, NCO, alkoxy, glycidyl, ethene property unsaturated group, amino; Described compound comprises thiourea, melamine, methylolation melamine, butyral melamine, glyoxal, valeral, the vinyl-based compound metal chelate compound of cobalt, titanium, molybdenum, acryloyl group or vinyl ether; Its content is 1～20wt%.
7. the photosensitive polymer combination of a kind of low surface tackiness according to claim 1; It is characterized in that described adjuvant comprises foam-breaking agent, measurement of the level agent, colorant, antiseptic, organic/inorganic filler, organic solvent, plasticizer, interfacial agent; Its content is 0.1～50wt%.
8. the purposes of the photosensitive polymer combination of the described low surface tackiness of claim 1; It is characterized in that; This photosensitive resin composition is coated in 0.1～2000 μ m thickness on the silk screen order with scraper, in the dull and stereotyped silk screen PS version that Wen Fengzhong is dried to not exposure, uses the egative film exposure of finishing figure when using then; Wash exposure is partly stayed, just become dull and stereotyped serigraphy with the brush version; Perhaps described photosensitive resin composition with colyliform scraper gluing on metal rotor silk screen; Its dry film thickness 0.1～1000 μ m, the drying process of warm wind once or is repeatedly processed the PS version of rotary screen repeatedly, on the PS of not exposure version, uses the egative film exposure of finishing figure; Wash exposure is partly stayed; Obtain rotary-type cylinder serigraphy with the brush version with 50 ℃～220 ℃ heat treated again, be 0.5～4 hour heat time heating time, or use laser scribing shape after the first heat treated.
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| CN101833241B (en) * | 2009-03-09 | 2012-07-04 | 村上精密制版（昆山）有限公司 | Photosensitive resin composition |
| JP2015048459A (en) * | 2013-09-04 | 2015-03-16 | Dic株式会社 | Radically polymerizable resin composition and civil engineering building material |
| CN103756516A (en) * | 2013-12-27 | 2014-04-30 | 吴江市东泰电力特种开关有限公司 | Photosensitive water-soluble coating and preparation method thereof |
| CN111856876A (en) * | 2019-04-25 | 2020-10-30 | 田菱智能科技(昆山)有限公司 | Photosensitive resin composition |
| CN111785952B (en) * | 2020-01-19 | 2021-10-29 | 成都拓米电子装备制造有限公司 | Method for preparing nano silicon particles for secondary battery cathode material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1249731A2 (en) * | 2001-04-13 | 2002-10-16 | Fuji Photo Film Co., Ltd. | Photosensitive composition and negative working lithographic printing plate |
| CN1604849A (en) * | 2001-12-13 | 2005-04-06 | 柯达彩色绘图有限公司 | Photosensitive composition and photosensitive planographic printing plate |
| CN1644393A (en) * | 2004-01-23 | 2005-07-27 | 富士胶片株式会社 | Lithographic printing plate precursor and lithographic printing method |
| CN1662388A (en) * | 2002-06-25 | 2005-08-31 | 旭化成化学株式会社 | Photosensitive resin composition for original printing plate capable of being carved by laser |
-
2007
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1249731A2 (en) * | 2001-04-13 | 2002-10-16 | Fuji Photo Film Co., Ltd. | Photosensitive composition and negative working lithographic printing plate |
| CN1604849A (en) * | 2001-12-13 | 2005-04-06 | 柯达彩色绘图有限公司 | Photosensitive composition and photosensitive planographic printing plate |
| CN1662388A (en) * | 2002-06-25 | 2005-08-31 | 旭化成化学株式会社 | Photosensitive resin composition for original printing plate capable of being carved by laser |
| CN1644393A (en) * | 2004-01-23 | 2005-07-27 | 富士胶片株式会社 | Lithographic printing plate precursor and lithographic printing method |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2005-43724A 2005.02.17 |
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