CN105446080A - Coating composition, application thereof and base material using same - Google Patents
Coating composition, application thereof and base material using same Download PDFInfo
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- CN105446080A CN105446080A CN201510944437.5A CN201510944437A CN105446080A CN 105446080 A CN105446080 A CN 105446080A CN 201510944437 A CN201510944437 A CN 201510944437A CN 105446080 A CN105446080 A CN 105446080A
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- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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Abstract
The invention relates to a coating composition, application thereof and a base material using the same. The coating composition comprises as follows: A, 10-40% of photosensitive resin I; B, 10-40% photosensitive resin II; C, 0.5-15% of a photoinitiator; D, 10-70% of a diluents; and an optional additive; wherein the photosensitive resin I is photosensitive resin which simultaneously contains carboxyl and at least two vinyl unsaturated bonds in molecules and has an acid value of 50-150mgKOH/g; the photosensitive resin II is prepared according to the following method of (a), copolymerizing a monomer A containing a double-bond and anhydride B containing a double-bond to obtain resin C; (b) adding an appropriate amount of H2O to carrying out loop opening on the anhydride in the resin C; and (c) adding a monomer F simultaneously containing a double-bond and an epoxy group in the resin D and carrying out reaction to obtain the photosensitive resin II; all constituents are weighted based on the total weight of the composition, and the percentage sum of all constituents is 100%. The coating composition has the advantages of excellent formability, developing performance and photosensitivity, and a membrane layer formed on the base material has high temperature resistance and high surface tension performance.
Description
Technical field
The present invention relates to a kind of coating composition, its application and use its base material, more specifically, relating to a kind of resin coating compositions, its application and use its base material.
Background technology
In liquid crystal display production run, often need functional areas to be divided into plurality of layers, every layer function district is fit together by protective seam, if the surface tension of the protective seam of lower floor is too little, can affect the adhesion of upper strata coating, causes the coating on upper strata to be easy to come off.The surface tension of common protective seam is all less than 32, therefore needs by physics or chemical method process protective layer, increases surface tension, improves adhesion.
Traditional method increases the surface tension after composition solidification by reducing levelling agent consumption, but such method limited efficiency.
Summary of the invention
The present invention is intended to the defect overcoming prior art, and provide a kind of coating composition solved the problem, it comprises
A. photosensitive resin I, it is simultaneously containing carboxyl and at least two ethylene type unsaturated links and its acid number is the photoresist of 50-150mgKOH/g, 10-40% in molecule;
B. photosensitive resin II, it is obtained by following methods: a, the monomer A containing a double bond and the acid anhydrides B copolymerization containing a double bond obtain resin C; B, add appropriate H
2o carries out open loop to the acid anhydrides in resin C, obtains resin D; C, in resin D, add monomer F simultaneously containing a double bond and an epoxide group, be obtained by reacting photosensitive resin II, 10-40%;
C. photoinitiator, 0.5-15%;
D. thinning agent, 10-70%;
Wherein each component is based on composition total weight meter, and the number percent summation of each component is 100%.
Coating composition of the present invention is also optionally containing auxiliary agents such as filler, colorant, epoxy resin curing accelerator, heat polymerization inhibitors, thixotroping tackifier, spreading agent, levelling agent and defoamers.
On the other hand, the present invention also provides the purposes of described coating composition, for coated substrate.
On the other hand, the present invention goes back the base material of the rete that providing package is formed containing described coating composition.
The mouldability of described coating composition tool excellence, developability, photosensitivity and the rete formed on various base material thereof have excellent transmittance, heat-resisting quantity and high capillary performance.
Embodiment
In the present invention, as illustrated without contrary, then all operations is all implemented at room temperature, normal pressure.
In the present invention, as illustrated without contrary, then the percentage composition of each composition component or ratio are based on the total weight of composition, and each component concentration number percent sum is 100%.
The invention provides a kind of coating composition, it comprises
A. photosensitive resin I, it is simultaneously containing carboxyl and at least two ethylene type unsaturated links and its acid number is the photoresist of 50-150mgKOH/g, 10-40% in molecule;
B. photosensitive resin II, it is obtained by following methods: a, the monomer A containing a double bond and the acid anhydrides B copolymerization containing a double bond obtain resin C; B, add appropriate H
2o carries out open loop to the acid anhydrides in resin C, obtains resin D; C, in resin D, add monomer F simultaneously containing a double bond and an epoxide group, be obtained by reacting photosensitive resin II, 10-40%,
C. photoinitiator, 0.5-15%,
D. thinning agent, 10-70%,
Wherein each component is based on composition total weight meter, and the number percent summation of each component is 100%.
Coating composition of the present invention is also optionally containing auxiliary agents such as filler, colorant, epoxy resin curing accelerator, heat polymerization inhibitors, thixotroping tackifier, spreading agent, levelling agent and defoamers.
Term implication used herein is as follows:
" (methyl) acrylate " refers to the general name of acrylate, methacrylate and potpourri, and other similar expression implication is similar.
Each component of coating composition of the present invention will be elaborated below.
Described photosensitive resin I, it is the photoresist simultaneously containing carboxyl and at least two ethylene type unsaturated links in molecule, and described photosensitive resin I can be synthesized by disclosed any one method following of the patent 200810004765.7 of the applicant:
(1) multi-functional epoxy compound (a) and the unsaturated monocarboxylic (b) in molecule with two or more epoxy radicals carry out esterification, and the carboxylate obtained reacts with saturated or undersaturated multi-anhydride (c) again;
(2) (methyl) acrylic acid and other comonomer (d) reaction with ethylene type unsaturated link form multipolymer, partly react with (methyl) glycidyl acrylate;
(3) (methyl) glycidyl acrylate and other has the multipolymer of the comonomer (d) of ethylene type unsaturated link and unsaturated monocarboxylic (b) reacts, the product obtained reacts with saturated or undersaturated multi-anhydride (c) again;
(4) have in molecule in the multi-functional epoxy compound (a) of two or more epoxy radicals, unsaturated monocarboxylic (b) and molecule and at least contain two hydroxyls and have and can react with the compound (e) of of epoxy reaction other group, generate intermediate (I), described intermediate reacts with saturated or undersaturated multi-anhydride (c) again;
(5) unsaturated multi-anhydride and have vinyl aromatic hydrocarbon reaction formed multipolymer, then with hydroxy alkyl (methyl) acrylate reactions; Or
(6) intermediate (I) described in method (4) reacts with saturated or undersaturated multi-anhydride (c) and the monoisocyanates (f) containing unsaturated group again.
In said method (1) and (4), the example of spendable epoxy compound (a) comprising: the novalac epoxies of the solvable epoxy resin of bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, novolac epoxy resins, cresols, bisphenol-A, united phenol-type epoxy resin, di-toluene phenol-type epoxy resin, triphenol methylmethane type epoxy resin and N-diglycidyl type epoxy resin.Above-mentioned epoxy compound can be used alone that two or more may be used in combination.Wherein, the novalac epoxies of the solvable epoxy resin of the novolac epoxy resins in these epoxy compounds, cresols, bisphenol-A, can obtain having the welding resistance etchant resist of the performances such as excellent scolding tin thermotolerance and reagent resistance because of it and preferably use.
In said method (1), (3) and (4), the example of spendable unsaturated monocarboxylic (b) comprising: acrylic acid, acrylic acid dipolymer, methacrylic acid, β-styrene acrylic, β-furfuryl acrylic acid, butenoic acid, alpha-cyano cinnamic acid, cinnamic acid, and the reactant of (methyl) esters of acrylic acid containing a hydroxyl in saturated or unsaturated dicarboxylic acid anhydride and molecule or saturated or unsaturated dibasic acid and unsaturated single glycidyl compound reactant half ester class.Consider photo-curable, in these unsaturated monocarboxylics, preferably use acrylic or methacrylic acid.
In said method (1), (3), (4) and (6), spendable example that is saturated or undersaturated multi-anhydride (c) comprises: maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Jia Qiao-Nei-tetrabydrophthalic anhydride, methyl first bridge-Nei-dibasic acid anhydride such as tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride; The aromatic polycarboxylic acid acid anhydrides such as trimellitic anhydride, pyromellitic dianhydride, benzophenone tetrabasic carboxylic acid dicarboxylic anhydride; And 5-(2,5-dioxidotetrahydro furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, and similar polybasic acid anhydride derivant.These saturated or undersaturated multi-anhydrides can be independent or two or more used in combination.Consider the characteristic of cured coating film, preferably use tetrabydrophthalic anhydride, hexahydrophthalic anhydride and succinic anhydride.Preferred described multi-anhydride (c) consumption is make the solid constituent acid number of resultant of reaction be the consumption of 50-150mgKOH/g.
In said method (2) and (3), other the example with the comonomer (d) of ethylene type unsaturated link spendable comprises: styrene, chlorostyrene, α-methyl styrene; The acrylate replaced by methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, the tert-butyl group, amino, 2-ethylhexyl, octyl group, caprinoyl, nonyl, decyl, dodecyl, cetyl, octadecyl, cyclohexyl, isobornyl, methoxy ethyl, butoxyethyl group, 2-hydroxyethyl, 2-hydroxypropyl and 3-chlorine-2-hydroxyl propyl group or methacrylate; The mono acrylic ester of the mono acrylic ester of polyglycol or monomethacrylates or polypropylene glycol or monomethacrylates; Vinyl acetate, vinyl butyrate or vinyl benzoate; Acrylamide, Methacrylamide, N-hydroxymethylacrylamide, N-methoxy acrylamide, N-ethoxymethyl acrylamide, N-butoxy methyl acrylamide, vinyl cyanide or maleic anhydride etc.These comonomers (d) can be used alone that two or more may be used in combination.
In said method (4) and (6), the example of spendable compound (e) comprising: dihydromethyl propionic acid, dihydroxymethyl acetic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid, dihydroxymethyl caproic acid etc. are containing polyhydric monocarboxylic acid; And the dialkanol such as diethanolamine, diisopropanolamine amine.These compounds (e) can be used alone that two or more may be used in combination.
In described method (4), epoxy radicals 1 molar equivalent of relative epoxy compound (a), the total amount of unsaturated monocarboxylic (b) and compound (e) is preferably about 0.8-1.3 molar equivalent, is particularly preferably about 0.9-1.1 molar equivalent.Wherein the molar equivalent of compound (e) accounts for the 5-50% of (b) and (e) total amount, particularly preferably accounts for 10-30%.For the reaction of described intermediate (I) and multi-anhydride (c), relative to the hydroxyl in intermediate (I), the preferably hydroxyl of 1 molar equivalent and multi-anhydride (c) reaction of 0.1-0.9 molar equivalent.
In said method (4), the example of spendable unsaturated monoisocyanates (f) comprising: (methyl) acrylic compounds in methylacryoyloxyethyl isocyanates or organic diisocyanate and molecule with a hydroxyl, carries out the product be obtained by reacting with about equimolar ratio.These unsaturated monoisocyanates (f) can be used alone that two or more may be used in combination.
Described photoresist I is not limited to above-described material, as long as have carboxyl and at least two ethylene type unsaturated links in molecule and its acid number is the photosensitive resin of 50-150mgKOH/g, can use in the present invention.Above-mentioned substance also can be used in combination.
Described photosensitive resin II, it is prepared by following methods: a, the comonomer A with ethylene type unsaturated link and undersaturated multi-anhydride B copolymerization obtain resin C; B, add appropriate H
2o carries out open loop to the acid anhydrides in resin C, obtains resin D; C, in resin D, add monomer F simultaneously containing a double bond and an epoxide group, be obtained by reacting photosensitive resin II.
Described comonomer A, it has available as follows: styrene, chlorostyrene, α-methyl styrene; The acrylate replaced by methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, the tert-butyl group, amino, 2-ethylhexyl, octyl group, caprinoyl, nonyl, decyl, dodecyl, cetyl, octadecyl, cyclohexyl, isobornyl, methoxy ethyl, butoxyethyl group, 2-hydroxyethyl, 2-hydroxypropyl and 3-chlorine-2-hydroxyl propyl group or methacrylate; The mono acrylic ester of the mono acrylic ester of polyglycol or monomethacrylates or polypropylene glycol or monomethacrylates; Vinyl acetate, vinyl butyrate or vinyl benzoate; Acrylamide, Methacrylamide, N-hydroxymethylacrylamide, N-methoxy acrylamide, N-ethoxymethyl acrylamide, N-butoxy methyl acrylamide, vinyl cyanide etc., above-claimed cpd can be used alone or two or more used in combination.Styrene or methacrylic acid isoborneol fat is preferentially selected in described unsaturated monomer.
The example of described unsaturated multi-anhydride B comprises: maleic anhydride, methylnadic anhydride, carbic anhydride, citraconic anhydride, itaconic anhydride etc., and above-mentioned chemical combination can be used alone or two or more used in combination.Preferential use maleic anhydride or carbic anhydride in described unsaturated polyprotonic acid.
The above-mentioned example simultaneously containing the monomer F of 1 double bond and an epoxide group comprises: 1,2-epoxy radicals-4-vinyl cyclohexane, (methyl) glycidyl acrylate, 3,4-epoxycyclohexyl-methyl (methyl) acrylate, 1,2-epoxy radicals-3-butylene, 1,2-epoxy radicals-5-hexene, 1,2-epoxy-9-certain herbaceous plants with big flowers alkene etc., above-claimed cpd can be used alone or two or more used in combination.Resin C in above-mentioned photosensitive resin II also directly can select business-like product, as the SMA series plastics of Sartomer, and the E098 of Bao Lilong, the SZ4005 of Dutch POLYSCOPE, SZ23110 etc.
The present invention is not particularly limited described photoinitiator, and the example comprises: benzoin and the benzoin alkylethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; The acetophenones such as acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone; 1-(6-o-methyl-benzene formoxyl-9-ethyl-9.H.-carbazole-3 base) ketoxime ester such as-acetophenone oxime-O-acetic acid esters, 1-[4-(thiophenyl) phenyl]-1,2-octanedione 2-(O-benzoyl oxime); 2-methyl isophthalic acid-[4-(methyl thio) phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethyl amido-1-(4-morpholino phenyl)-aminoacetophenone class such as butane-1-ketone, N, N-dimethyl amine benzoylformaldoxime; The Anthraquinones such as 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone; The thioxanthene ketones such as 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthones, CTX, 2,4-diisopropylthioxanthone; The ketal classes such as acetophenone dimethyl ketal, benzyl dimethyl ketal; The organic peroxides such as benzoyl peroxide, dicumyl peroxide base; The mercaptan compounds such as 2,4,5-tri-aromatic radical imidazoles diploid, hibon, 2-sulfenyl benzimidazole, 2-sulfenyl benzoxazole, 2-sulfurio benzo thiazole; The organohalogen compounds such as 2,4,6-tri--s-triazine, 2,2,2-ethobroms, trisbromomethyl phenyl ketone; Benzophenone, 4, Benzophenones or the thioxanthene ketones such as 4 '-bis-diethyl aminobenzophenones; 2,4,6-trimethylbenzoyldiphenyl oxides etc., above-mentioned ultraviolet light photoinitiator can be used alone or two or more used in combination.In addition, also can comprise in described photoinitiator and be selected from N, the light-initiated auxiliary agent of tertiary amines of N-dimethyl amido benzoic acid ethyl ester, N, N-dimethyl amido benzoic acid isopentyl ester, amyl group-4-dimethyl amido benzoic ether, triethylamine, triethanolamine etc.Wherein, the consumption of described photoinitiator is the 0.5-15% of present composition general assembly (TW), preferred 1-10%.
Thinning agent in the present invention can be organic solvent, such as: the ethers such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, DPE, Dipropylene glycol mono-n-butyl Ether; The ester classes such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetic acid esters, dipropylene glycol monomethyl ether acetic acid esters, DPE acetic acid esters, Dipropylene glycol mono-n-butyl Ether acetic acid esters; And conventional ketones solvent, as butanone, cyclohexanone, isophorone; Aromatic solvent, as toluene, dimethylbenzene, durene; And petroleum solvent, as naphtha, oxidation naphtha, solvent naphtha etc., above-mentioned solvent can be used alone or two or more used in combination.
In addition, thinning agent in the present invention also can be photopolymerization monomer, such as: (methyl) esters of acrylic acid containing hydroxyl of (methyl) hydroxy-ethyl acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate etc.; Simple function (methyl) esters of acrylic acids such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) lauryl acrylate; Difunctionality (methyl) esters of acrylic acids such as two (methyl) acrylate of 1,6-hexanediol, two (methyl) acrylate of two contracting/tripropylene glycols, two (methyl) acrylate of two contracting/triethylene Glycols, two (methyl) acrylate of ethoxylated bisphenol A, two (methyl) acrylate of neopentyl glycol diethoxy/propoxyl group; Multifunctional (methyl) esters of acrylic acids such as trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate; And ethoxylation polyfunctional acrylic ester and propoxylation polyfunctional acrylic ester etc., above-claimed cpd can be used alone or two or more used in combination.
In the compositions of the present invention, described thinning agent can be used alone photopolymerization monomer or organic solvent, also can use photopolymerization monomer or organic solvent simultaneously.The consumption of described thinning agent is the 10-70% of present composition general assembly (TW), preferred 20-60%.
Coating composition of the present invention also can comprise customary filler, especially inorganic filler, such as: barium sulphate, barium titanate, calcium dioxide, talcum powder, gas-phase silica, silicon dioxide, clay, magnesium carbonate, calcium carbonate, aluminium oxide, mica powder, porcelain earth etc.The consumption of described filler is the 0-40% of present composition general assembly (TW), and the particle diameter of filler is <15 μm, preferred <5 μm.
Coating composition of the present invention also can comprise conventional colorant, and the example comprises: phthalocyanine green, phthalocyanine blue, crystal violet, titania, carbon black etc., and above-mentioned substance can be used alone or two or more used in combination.Wherein, the consumption of described colorant is the 0-20% of present composition general assembly (TW), preferred 0-10%.
The present invention is one or more adjuvants that coating composition also optionally comprises in epoxy resin curing accelerator, heat polymerization inhibitors, thixotroping tackifier, spreading agent, levelling agent and defoamer etc.The general assembly (TW) of described various adjuvant is the 0-40% of present composition general assembly (TW), preferred 0-10%.
Coating composition of the present invention is mixed by each component.If be not use immediately after preparation, preferably keep in Dark Place, to avoid solidification.Certainly, also photoinitiator can be placed separately, mix with other components again time to be used.
In addition, present invention also offers aforementioned coating composition forms rete on base material purposes by conventional coating techniques.Described coating composition has excellent mouldability, developability and photosensitivity on base material.The substrate of described base material can be metal, plastics or other materials, such as tin indium oxide (ITO) film, chromium material, copper material, aluminium, glass, polyethylene terephthalate (PET), polypropylene (PP) etc.During use, coating composition is applied directly to substrate surface, shoots away into solidification with illumination.
The present invention goes back the base material of providing package containing the rete formed by conventional coating techniques by described coating composition, and described rete has excellent transmittance, heat-resisting quantity and the capillary performance of height.
Below in conjunction with specific embodiment to further illustrate the present invention, but the present invention is not limited thereto.
In the present invention, the acid number of polymer resin measures according to GB/T2895-1989.
In the present invention, the solid content of polymer resin measures according to GB/T7193-1987.
The synthesis of photosensitive resin I
Synthetic example 1
Add 200g phenol aldehyde type epoxy resin CNE-202 (Changchun, Taiwan life insurance resin processing plant in the reactor, epoxide equivalent 210), 250g propylene glycol methyl ether acetate (PMA), 69g acrylic acid, heating melts, add 0.5g p-dihydroxy-benzene, 1.5g triphenylphosphine again, 110 DEG C of reactions 12 hours, obtain the product that acid number is less than 5.Add 85g tetrabydrophthalic anhydride again, be heated to 100 DEG C, react 6 hours, obtain light yellow resin liquid A1 (photosensitive resin I), its acid number is 52mgKOH/g, and solid content is 59%.
Synthetic example 2
The ratio being 1:1:2 according to mol ratio in the reactor adds methyl methacrylate, butyl methacrylate and acrylic acid, solvent uses carbitol acetate, catalyzer uses azoisobutyronitrile (AIBN), stirs 4 hours, obtain resin solution under the condition of 80 DEG C.
Cool this resin solution, use methylnaphthohydroquinone as polymerization inhibitor and tetrabutyl phosphonium bromide phosphorus as catalyzer, addition reaction is carried out with (methyl) glycidyl acrylate under the condition of 90-105 DEG C, wherein said resin carboxyl is 5:1 with the mol ratio of (methyl) glycidyl acrylate, reaction carries out 16 hours, is taken out by product resin liquid A2 after cooling.
In the resin solution A2 (photosensitive resin I) obtained, nonvolatile component is 65%, and the acid number of solid constituent is 120mgKOH/g, M
wfor about 15000.
The synthesis of photosensitive resin II
Synthetic example 3
Add 1mol styrene, 1mol maleic anhydride and 2mol propylene glycol methyl ether acetate in the reactor, 2g azoisobutyronitrile (AIBN) is as catalyzer, stir 4 hours at 80 DEG C ~ 90 DEG C, then add 1mol distilled water, continue reaction 2 hours, then add 1mol glycidyl methacrylate (GMA), successive reaction 14 hours, obtain light yellow resin liquid B1 (photosensitive resin II), its acid number is 89mgKOH/g, and solid content is 58%.
Synthetic example 4
Add 1mol isobornyl methacrylate, 1mol maleic anhydride, 2mol propylene glycol methyl ether acetate, 2g azoisobutyronitrile (AIBN) in the reactor as catalyzer, stir 4 hours at 80 DEG C ~ 90 DEG C, then 1mol distilled water is added, continue reaction 2 hours, then add 1mol3,4-epoxycyclohexyl-methyl methacrylate, successive reaction 14 hours, obtain light yellow resin liquid B2 (photosensitive resin II), its acid number is 72mgKOH/g, and solid content is 66%.
Above-mentioned synthesized resin is mixed by the weight proportion in table 1 with other reagent, utilizes dispersion machine to be uniformly dispersed, obtain the coating composition of embodiment 1-6 and comparative example 1-4.
Hereinafter by requiring the contrast of the transparency and capillary transparent material simultaneously, if only effects on surface tension force has requirement, then filler and pigment can be added in formula.
Application Example
To 10 kinds of coating compositions in the embodiment of above-mentioned acquisition and comparative example, carry out following performance test and assessment, the results are shown in table 1.
(1) mouldability
To form the rete of 2 micron thickness on the glass plate (10cm*10cm*0.1cm) with rolling method obtained coating composition being coated respectively dry cleansing, painting 6 altogether.Whether visual inspection coating surface has the defects such as bubble, pin hole, white point.
Evaluation method: be excellent without any above-mentioned defect, has the above-mentioned defect of any one then for poor.
(2) developability
Preliminary drying 5 minutes in the baking oven glass plate scribbling coating composition in step (1) being put into 75 ± 5 DEG C, taking-up cools naturally, then get wherein a slice and carry out development operation, development conditions is: KOH (potassium hydroxide) aqueous solution of 0.05% (mass ratio), temperature is 30 DEG C, and spray pressure is 1-3kg/cm
2.
Evaluation method: development is clean, and substrate remains as excellent without coating composition, otherwise for poor.
(3) photosensitivity
To be placed on coating composition film with 21 rank exposure guide rules to expose getting a slice in all the other 5 plates except plate in step (2), develop by the condition in developability (2), coat the residual 6 lattice required exposure energy of composition film for standard with glass plate, then judges.
Evaluation method: needed for residual 6 lattice, luminous energy is less than or equal to 80mJ/cm
2for excellent; Needed for residual 6 lattice, luminous energy is greater than 80mJ/cm
2and be less than or equal to 150mJcm
2for good; Needed for residual 6 lattice, luminous energy is greater than 150mJ/cm
2be less than or equal to 300mJ/cm
2for in, needed for residual 6 lattice, luminous energy is greater than 300mJ/cm
2for difference.
(4) transmittance
All the other 4 plates except plate in step (2), (3) are put into 230 DEG C, 250 DEG C, 270 DEG C, 280 DEG C baking ovens respectively and toasts 30min, then transmittance is surveyed with ultraviolet spectrophotometer, observe the transmittance at 400nm place, record data in Table 1.
(5) surface tension
By the plate dyne test surfaces tension force that in step (4), 4 pieces were surveyed transmittance, the data obtained is recorded in table 1.
Photoinitiator 907:2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholinyl-1-acetone, purchased from vapour Bagong department;
Photoinitiator ITX: isopropyl thioxanthone, purchased from Tianjin Jiuri Chemical Co., Ltd.;
DPHA: dipentaerythritol acrylate, purchased from American Sartomer;
Levelling agent BYK-333: purchased from Bi Ke chemistry (BYK) company;
PMA: propylene glycol methyl ether acetate purchased from American Tao Shi solvent company;
The material that in patent, other are not particularly illustrated is all choose the technical grade reagent from commercially available.
As can be seen from Table 1, described coating composition is when as transparent material, owing to employing photosensitive resin I and photosensitive resin II simultaneously in the embodiment of the present invention, there is when the coating composition obtained coats glass substrate excellent mouldability, developability, photosensitivity and rete formed on a glass thereof there is the high surface tension that excellent transmittance, heat-resisting quantity and dyne value are more than 38; With in comparative example use sense photopolymer resin I ratio, obviously improve in transmittance and surface tension, during with in comparative example use sense photopolymer resin II, obviously improve in transmittance.In addition, use two of mol ratio 1:2 ~ 2:1 kinds of photosensitive resin I and II under the same conditions in coating composition along with temperature, to raise the reduction amplitude of transmittance when ratio used in combination is used alone obviously less than when being used alone photosensitive resin I or photosensitive resin II simultaneously, obviously improves in heat-resisting quantity.
Claims (10)
1. a coating composition, it comprises
A. photosensitive resin I, it is simultaneously containing carboxyl and at least two ethylene type unsaturated links and its acid number is the photoresist of 50-150mgKOH/g, 10-40% in molecule;
B. photosensitive resin II, is obtained by following methods: a, the monomer A containing a double bond and the acid anhydrides B copolymerization containing a double bond obtain resin C; B, add appropriate H
2o carries out open loop to the acid anhydrides in resin C, obtains resin D; C, in resin D, add monomer F simultaneously containing a double bond and an epoxide group, be obtained by reacting photosensitive resin II, 10-40%;
C. photoinitiator, 0.5-15%;
D. thinning agent, 10-70%;
And the auxiliary agent such as optional filler, colorant, epoxy resin curing accelerator, heat polymerization inhibitors, thixotroping tackifier, spreading agent, levelling agent and defoamer;
Wherein each component is based on composition total weight meter, and the number percent summation of each component is 100%.
2. the coating composition of claim 1, wherein said monomer A is the comonomer with ethylene type unsaturated link, and it is selected from styrene, chlorostyrene, α-methyl styrene; The acrylate replaced by methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, the tert-butyl group, amino, 2-ethylhexyl, octyl group, caprinoyl, nonyl, decyl, dodecyl, cetyl, octadecyl, cyclohexyl, isobornyl, methoxy ethyl, butoxyethyl group, 2-hydroxyethyl, 2-hydroxypropyl and 3-chlorine-2-hydroxyl propyl group or methacrylate; The mono acrylic ester of the mono acrylic ester of polyglycol or monomethacrylates or polypropylene glycol or monomethacrylates; Vinyl acetate, vinyl butyrate or vinyl benzoate; At least one in acrylamide, Methacrylamide, N-hydroxymethylacrylamide, N-methoxy acrylamide, N-ethoxymethyl acrylamide, N-butoxy methyl acrylamide, vinyl cyanide.
3. the coating composition of claim 1, wherein said acid anhydrides B is unsaturated multi-anhydride, and it is selected from least one in maleic anhydride, methylnadic anhydride, carbic anhydride, citraconic anhydride, itaconic anhydride.
4. the coating composition of claim 1, wherein said monomer F is selected from 1,2-epoxy radicals-4-vinyl cyclohexane, (methyl) glycidyl acrylate, 3,4-epoxycyclohexyl-methyl (methyl) acrylate, 1,2-epoxy radicals-3-butylene, 1, at least one in 2-epoxy radicals-5-hexene, 1,2-epoxy-9-certain herbaceous plants with big flowers alkene.
5. the coating composition of claim 1, wherein said photoinitiator is benzoin and the benzoin alkylethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; The acetophenones such as acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone; 1-(6-o-methyl-benzene formoxyl-9-ethyl-9.H.-carbazole-3 base) ketoxime ester such as-acetophenone oxime-O-acetic acid esters, 1-[4-(thiophenyl) phenyl]-1,2-octanedione 2-(O-benzoyl oxime); 2-methyl isophthalic acid-[4-(methyl thio) phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethyl amido-1-(4-morpholino phenyl)-aminoacetophenone class such as butane-1-ketone, N, N-dimethyl amine benzoylformaldoxime; The Anthraquinones such as 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone; The thioxanthene ketones such as 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthones, CTX, 2,4-diisopropylthioxanthone; The ketal classes such as acetophenone dimethyl ketal, benzyl dimethyl ketal; The organic peroxides such as benzoyl peroxide, dicumyl peroxide base; The mercaptan compounds such as 2,4,5-tri-aromatic radical imidazoles diploid, hibon, 2-sulfenyl benzimidazole, 2-sulfenyl benzoxazole, 2-sulfurio benzo thiazole; The organohalogen compounds such as 2,4,6-tri--s-triazine, 2,2,2-ethobroms, trisbromomethyl phenyl ketone; Benzophenone, 4, Benzophenones or the thioxanthene ketones such as 4 '-bis-diethyl aminobenzophenones; At least one in 2,4,6-trimethylbenzoyldiphenyl oxide.
6. the coating composition of claim 1, wherein said filler is be selected from least one in barium sulphate, barium titanate, calcium dioxide, talcum powder, gas-phase silica, silicon dioxide, clay, magnesium carbonate, calcium carbonate, aluminium oxide, mica powder, porcelain earth.
7. the coating composition of claim 1, the photosensitive resin II in wherein said coating composition and the mol ratio of photosensitive resin II are 1:2-2:1.
8. the coating composition of claim 1, the surface tension dyne value of the rete that wherein said coating composition is formed on substrate is more than or equal to 38.
9. the coating composition any one of claim 1 to 8, it is for the purposes of base material.
10. a base material, it comprises the rete that the coating composition any one of claim 1 to 8 is formed.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105732889A (en) * | 2016-04-15 | 2016-07-06 | 深圳市容大感光科技股份有限公司 | Photosensitive resin and synthetic method thereof |
| CN105778726A (en) * | 2016-04-15 | 2016-07-20 | 深圳市容大感光科技股份有限公司 | Coating composition and application thereof and substrate including film layer formed by coating composition |
| CN106189725A (en) * | 2016-07-28 | 2016-12-07 | 上海维凯光电新材料有限公司 | Photosensitive layout coating composition and its production and use |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1434833A (en) * | 2000-02-14 | 2003-08-06 | 太阳油墨制造株式会社 | Photocurable/thermoseting composition for forming matte film |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1434833A (en) * | 2000-02-14 | 2003-08-06 | 太阳油墨制造株式会社 | Photocurable/thermoseting composition for forming matte film |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105732889A (en) * | 2016-04-15 | 2016-07-06 | 深圳市容大感光科技股份有限公司 | Photosensitive resin and synthetic method thereof |
| CN105778726A (en) * | 2016-04-15 | 2016-07-20 | 深圳市容大感光科技股份有限公司 | Coating composition and application thereof and substrate including film layer formed by coating composition |
| CN105778726B (en) * | 2016-04-15 | 2017-03-08 | 深圳市容大感光科技股份有限公司 | The base material of coating composition, its application and the film layer formed including the coating |
| CN106189725A (en) * | 2016-07-28 | 2016-12-07 | 上海维凯光电新材料有限公司 | Photosensitive layout coating composition and its production and use |
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