CN105446080B - A kind of coating composition, its application and the substrate using it - Google Patents
A kind of coating composition, its application and the substrate using it Download PDFInfo
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- CN105446080B CN105446080B CN201510944437.5A CN201510944437A CN105446080B CN 105446080 B CN105446080 B CN 105446080B CN 201510944437 A CN201510944437 A CN 201510944437A CN 105446080 B CN105446080 B CN 105446080B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Abstract
The present invention relates to a kind of coating composition, its purposes and use its substrate, the coating composition includes A. photosensitive resin I, it is the photoresist for being simultaneously 50-150mgKOH/g containing carboxyl and at least two ethylene type unsaturated bonds and its acid value in molecule, 10-40%；B. photosensitive resin II is made by following methods: a, the monomer A containing a double bond and the acid anhydrides B containing a double bond are copolymerized to obtain resin C；B, appropriate H is added2O carries out open loop to the acid anhydrides in resin C, obtains resin D；C, the monomer F containing a double bond and an epoxy group simultaneously is added in resin D, reaction obtains photosensitive resin II, 10-40%, C. photoinitiator, 0.5-15%, D. diluent, 10-70% and optional auxiliary agent；Wherein each component is based on composition total weight, and the percentage summation of each component is 100%.The coating composition is with excellent mouldability, developability, light sensitivity and its is formed by substrate the performance that film layer has heat-resisting quantity and high surface tension.
Description
Technical field
More specifically it is related to a kind of resin the present invention relates to a kind of coating composition, its application and using its substrate
Coating composition, its application and the substrate using it.
Background technique
In liquid crystal display production process, a function distinguishing is generally required into plurality of layers, every layer function area is pasted by protective layer
It is combined, if the surface tension of the protective layer of lower layer is too small, will affect the adhesive force of upper layer coating, lead to the coating on upper layer
It is easy to fall off.The surface tension of common protective layer is both less than 32, it is therefore desirable to by either physically or chemically handling protection
Layer surface increases surface tension, improves adhesive force.
Traditional method is to increase the surface tension after composition solidifies, but such side by reducing levelling agent dosage
Method effect is limited.
Summary of the invention
The present invention is directed to overcome the deficiencies of existing technologies, a kind of coating composition to solve the above problems is provided, it includes
A. photosensitive resin I is in molecule simultaneously containing carboxyl and at least two ethylene type unsaturated bonds and its acid value is
The photoresist of 50-150mgKOH/g, 10-40%；
B. photosensitive resin II is made by following methods: a, the monomer A containing a double bond and the acid containing a double bond
Acid anhydride B is copolymerized to obtain resin C；B, appropriate H is added2O carries out open loop to the acid anhydrides in resin C, obtains resin D；C, add in resin D
Enter the monomer F containing a double bond and an epoxy group simultaneously, reaction obtains photosensitive resin II, 10-40%；
C. photoinitiator, 0.5-15%；
D. diluent, 10-70%；
Wherein each component is based on composition total weight, and the percentage summation of each component is 100%.
Coating composition of the invention is also optionally containing filler, colorant, epoxy resin curing accelerator, thermal polymerization polymerization inhibitor
The auxiliary agents such as agent, thixotroping tackifier, dispersing agent, levelling agent and defoaming agent.
On the other hand, the present invention also provides the purposes of the coating composition, for coating substrate.
On the other hand, the present invention also provides the substrates that film layer is formed by comprising the coating composition.
The coating composition has excellent mouldability, developability, light sensitivity and its is formed by film on various substrates
Layer has the performance of excellent light transmittance, heat-resisting quantity and high surface tension.
Specific embodiment
In the present invention, as without opposite explanation, then all operations are implemented in room temperature, normal pressure.
In the present invention, as without opposite explanation, then the percentage composition of each composition component or ratio are based on composition
Total weight, the sum of each component percentage composition are 100%.
The present invention provides a kind of coating composition, it includes
A. photosensitive resin I is in molecule simultaneously containing carboxyl and at least two ethylene type unsaturated bonds and its acid value is
The photoresist of 50-150mgKOH/g, 10-40%；
B. photosensitive resin II is made by following methods: a, the monomer A containing a double bond and the acid containing a double bond
Acid anhydride B is copolymerized to obtain resin C；B, appropriate H is added2O carries out open loop to the acid anhydrides in resin C, obtains resin D；C, add in resin D
Entering the monomer F containing a double bond and an epoxy group simultaneously, reaction obtains photosensitive resin II, 10-40%,
C. photoinitiator, 0.5-15%,
D. diluent, 10-70%,
Wherein each component is based on composition total weight, and the percentage summation of each component is 100%.
Coating composition of the invention is also optionally containing filler, colorant, epoxy resin curing accelerator, thermal polymerization polymerization inhibitor
The auxiliary agents such as agent, thixotroping tackifier, dispersing agent, levelling agent and defoaming agent.
Term meaning used herein is as follows:
" (methyl) acrylate " refers to the general name of acrylate, methacrylate and mixture, other similar
Indicate that meaning is similar.
It will be apparent from each component of coating composition of the present invention below.
The photosensitive resin I is the photonasty containing carboxyl and at least two ethylene type unsaturated bonds simultaneously in molecule
Resin, the photosensitive resin I can following any method disclosed in the patent 200810004765.7 by the applicant synthesize:
(1) there is multi-functional epoxide (a) and the unsaturated monocarboxylic (b) of more than two epoxy groups in molecule
Esterification is carried out, obtained carboxylate is reacted with saturated or unsaturated multi-anhydride (c) again；
(2) (methyl) acrylic acid and other comonomer (d) reactions with ethylene type unsaturated bond form copolymer, then
Partly reacted with (methyl) glycidyl acrylate；
(3) copolymerization of (methyl) glycidyl acrylate and other comonomers (d) with ethylene type unsaturated bond
Object is reacted with unsaturated monocarboxylic (b), and obtained product is reacted with saturated or unsaturated multi-anhydride (c) again；
(4) there is multi-functional epoxide (a), the unsaturated monocarboxylic (b) of more than two epoxy groups in molecule
With in molecule at least containing there are two hydroxyl and have can react with the compound (e) of an other groups of epoxy reaction, give birth to
At intermediate (I), the intermediate is reacted with saturated or unsaturated multi-anhydride (c) again；
(5) unsaturated multi-anhydride and the aromatic hydrocarbon with vinyl react to form copolymer, then with hydroxy alkyl (first
Base) acrylate reactions；Or
(6) intermediate (I) described in method (4) is again with saturated or unsaturated multi-anhydride (c) and containing unsaturated
The monoisocyanates (f) of base reacts.
The example of workable epoxide (a) includes: bisphenol A type epoxy resin, hydrogen in the above method (1) and (4)
Changing bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, novolac epoxy resins, cresols can
Molten epoxy resin, the novalac epoxies of bisphenol-A, united phenol-type epoxy resin, union II toluene phenol-type epoxy resin, triphenol
Methylmethane type epoxy resin and N- glycidol type epoxy resin.Above-mentioned epoxide can be used alone can also two kinds with
On be used in mixed way.Wherein, the novolac epoxy resins in these epoxides, the solvable epoxy resin of cresols, bisphenol-A
Novalac epoxies, because its available welding resistance with the performances such as excellent scolding tin heat resistance and reagent resistance is anti-
Lose film and it is preferable to use.
The example of workable unsaturated monocarboxylic (b) includes: acrylic acid, acrylic acid in the above method (1), (3) and (4)
Dimer, 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 or full in saturation or unsaturated dicarboxylic acid anhydride and molecule
And/or half esters of reactant of unsaturated dibasic acid and unsaturated single glycidyl compound.In view of photo-curable, at these
It is preferable to use acrylic or methacrylic acids in unsaturated monocarboxylic.
The example packet of workable saturated or unsaturated multi-anhydride (c) in the above method (1), (3), (4) and (6)
Include: maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride,
Methylhexahydrophthalic anhydride, Jia Qiao-be interior-tetrabydrophthalic anhydride, methyl first bridge-interior-tetrabydrophthalic anhydride, first
The dibasic acid anhydrides such as base tetrabydrophthalic anhydride；The virtues such as trimellitic anhydride, pyromellitic dianhydride, benzophenone tetrabasic carboxylic acid dicarboxylic anhydride
Fragrant race's polybasic acid anhydride；And 5- (2,5- dioxidotetrahydro furyl) -3- methyl -3- cyclohexene -1,2- dicarboxylic anhydride, and
Similar polybasic acid anhydride derivative.These saturated or unsaturated multi-anhydrides can be used in mixed way alone or in any combination.
In view of the characteristic of cured coating film is, it is preferable to use tetrabydrophthalic anhydride, hexahydrophthalic anhydride and succinic anhydride.It is excellent
Multi-anhydride (c) dosage of choosing is to make the dosage of the solid component acid value 50-150mgKOH/g of reaction product.
The example of workable other comonomers (d) with ethylene type unsaturated bond in the above method (2) and (3)
It include: styrene, chlorostyrene, α-methylstyrene；By methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, tertiary fourth
Base, amino, 2- ethylhexyl, octyl, caprinoyl, nonyl, decyl, dodecyl, cetyl, octadecyl, cyclohexyl, different ice
The acrylic acid that chip base, methoxy ethyl, butoxyethyl group, 2- hydroxyethyl, 2- hydroxypropyl and 3- chlorine-2-hydroxyl propyl replace
Ester or methacrylate；The mono acrylic ester or monomethacrylates of polyethylene glycol or single acrylic acid of polypropylene glycol
Ester or monomethacrylates；Vinyl acetate, vinyl butyrate or vinyl benzoate；Acrylamide, Methacrylamide,
N- hydroxymethylacrylamide, N- methoxy acrylamide, N- ethoxymethyl acrylamide, N- butoxymethyl propylene
Amide, acrylonitrile or maleic anhydride etc..These comonomers (d) can be used alone that two or more may be used in combination.
The example of workable compound (e) includes: dihydromethyl propionic acid, dihydroxymethyl second in the above method (4) and (6)
The monocarboxylic acids containing polyhydroxy such as acid, dimethylolpropionic acid, dimethylol pentanoic acid, dihydroxymethyl caproic acid；And diethanol amine, two
The dialkanols amine such as isopropanolamine.These compounds (e) can be used alone that two or more may be used in combination.
In the method (4), with respect to 1 molar equivalent of epoxy group of epoxide (a), unsaturated monocarboxylic (b) and change
The total amount for closing object (e) is preferably from about 0.8-1.3 molar equivalent, particularly preferably about 0.9-1.1 molar equivalent.Wherein compound
(e) molar equivalent accounts for the 5-50% of (b) He (e) total amount, particularly preferably accounts for 10-30%.For the intermediate (I) and polynary
The reaction of acid anhydrides (c), relative to the hydroxyl in intermediate (I), the preferably hydroxyl of 1 molar equivalent and 0.1-0.9 molar equivalent
Multi-anhydride (c) reaction.
The example of workable unsaturation monoisocyanates (f) includes: that methylacryoyloxyethyl is different in the above method (4)
(methyl) acrylic compounds with a hydroxyl in cyanate or organic diisocyanate and molecule, with about equimolar ratio
The product reacted.These unsaturated monoisocyanates (f) can be used alone that two or more may be used in combination.
The photoresist I is not limited to above-described substance, as long as having carboxyl and at least two in molecule
The photosensitive resin that ethylene type unsaturated bond and its acid value are 50-150mgKOH/g, can be used in the present invention.Above-mentioned substance
It can also be used in mixed way.
The photosensitive resin II, is prepared by following methods: a, with the comonomer A of ethylene type unsaturated bond and insatiable hunger
The multi-anhydride B of sum is copolymerized to obtain resin C；B, appropriate H is added2O carries out open loop to the acid anhydrides in resin C, obtains resin D；c,
The monomer F containing a double bond and an epoxy group simultaneously is added in resin D, reaction obtains photosensitive resin II.
The comonomer A has following available: styrene, chlorostyrene, α-methylstyrene；By methyl,
Ethyl, propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, amino, 2- ethylhexyl, octyl, caprinoyl, nonyl, decyl, ten
Dialkyl group, cetyl, octadecyl, cyclohexyl, isobornyl, methoxy ethyl, butoxyethyl group, 2- hydroxyethyl, 2-
The acrylate or methacrylate that hydroxypropyl and 3- chlorine-2-hydroxyl propyl replace；The mono acrylic ester of polyethylene glycol or
The mono acrylic ester or monomethacrylates of monomethacrylates or polypropylene glycol；Vinyl acetate, vinyl butyrate
Or vinyl benzoate；Acrylamide, Methacrylamide, N- hydroxymethylacrylamide, N- methoxy acrylamide,
N- ethoxymethyl acrylamide, N- butoxy methyl acrylamide, acrylonitrile etc., above compound can be used alone or two
Kind or more be used in mixed way.Styrene or methacrylic acid isoborneol rouge are preferentially selected in the unsaturated monomer.
The example of the unsaturation multi-anhydride B include: maleic anhydride, methylnadic anhydride, carbic anhydride,
Citraconic anhydride, itaconic anhydride etc., above-mentioned chemical combination can be used alone or two or more is used in mixed way.In the unsaturation polyacid
Preferentially use maleic anhydride or carbic anhydride.
The example of the above-mentioned monomer F simultaneously containing 1 double bond and an epoxy group includes: 1,2- epoxy group -4- ethylene
Butylcyclohexane, (methyl) glycidyl acrylate, 3,4- epoxycyclohexyl-methyl (methyl) acrylate, 1,2- epoxy group-
3- butylene, 1,2- epoxy group -5- hexene, 1,2- epoxy -9- certain herbaceous plants with big flowers alkene etc., above compound can be used alone or two or more mixed
It closes and uses.Resin C in above-mentioned photosensitive resin II can also directly select commercialized product, such as the SMA series of Sartomer
Resin, the E098 of Bao Lilong, the SZ4005 of Dutch POLYSCOPE, SZ23110 etc..
The present invention is not particularly limited the photoinitiator, the example include: benzoin, benzoin methyl ether,
The benzoins such as benzoin ethyl ether, benzoin isopropyl ether and benzoin alkylether；Acetophenone, 2,2- dimethoxy -2- phenyl
The acetophenones such as acetophenone, 2,2- diethoxy -2- phenyl acetophenone, 1,1- dichloroacetophenone；1- (6- o-methyl-benzene formyl
- 3 base of base -9- ethyl -9.H.- carbazole)-acetophenone oxime-O- acetic acid esters, 1- [4- (thiophenyl) phenyl] -1,2- octanedione 2- (O-
Benzoyl oxime) etc. ketoxime esters；2- methyl-1-[4- (methyl thio) phenyl]-2- morpholinopropanone-1,2- benzyl-2- diformazan
Base amido -1- (4- morpholino phenyl)-butane -1- ketone, N, the aminoacetophenones class such as N- dimethyl amine benzoylformaldoxime；2- methyl anthracene
The Anthraquinones such as quinone, 2- ethyl hydrazine, 2- tert-butyl anthraquinone, 1- chloroanthraquinone；2,4- dimethyl thioxanthone, 2,4- diethyl thioxanthene
The thioxanthene ketone class such as ketone, 2-chlorothioxanthone, 2,4- diisopropylthioxanthone；Acetophenone dimethyl ketal, benzyl dimethyl ketal etc.
Ketal class；The organic peroxides such as benzoyl peroxide, dicumyl peroxide base；Tri- aromatic radical imidazoles diploid of 2,4,5-, core
The mercaptan compounds such as four butyl ester of flavine, 2- sulfenyl benzimidazole, 2- sulfenyl benzoxazoles, 2- sulfurio benzo thiazole；2,4,6- tri--
The organohalogen compounds such as s- triazine, 2,2,2- ethobrom, trisbromomethyl phenyl ketone；Benzophenone, 4,4 '-bis- diethyl amido hexichol
The Benzophenones such as ketone or thioxanthene ketone class；2,4,6- trimethylbenzoyldiphenyl oxides etc., above-mentioned ultraviolet light is photosensitive
Initiator can be used alone or two or more be used in mixed way.In addition, also may include selected from N, N- diformazan in the photoinitiator
Base amido benzoic acid ethyl ester, N, N- dimethyl amido benzoic acid isoamyl base ester, amyl -4- dimethyl amine yl benzoic acid
The tertiary amines light-initiated auxiliary agent of ester, triethylamine, triethanolamine etc..Wherein, the dosage of the photoinitiator is of the present invention group
Close the 0.5-15%, preferably 1-10% of object total weight.
Diluent in the present invention can be organic solvent, such as: glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol list
Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether,
The ethers such as propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Dipropylene glycol mono-n-butyl Ether；Ethyl acetate, acetic acid
Butyl ester, ethylene glycol monoethylether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol list second
Ether acetic acid ester, butyl carbitol acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol list
The esters such as butyl ether acetic acid esters, dipropylene glycol monomethyl ether acetic acid esters, dipropylene glycol monoethyl ether acetic acid esters, Dipropylene glycol mono-n-butyl Ether acetic acid esters
Class；And common ketones solvent, such as butanone, cyclohexanone, isophorone；Aromatic solvent, such as toluene, dimethylbenzene, durene；With
And petroleum series solvent, such as naphtha, oxidation naphtha, solvent naphtha, above-mentioned solvent can be used alone or two or more mixed
It closes and uses.
In addition, the diluent in the present invention can also be photopolymerization monomer, and such as: (methyl) hydroxy-ethyl acrylate, season penta
(methyl) acrylate containing hydroxyl of tetrol three (methyl) acrylate, dipentaerythritol five (methyl) acrylate etc.
Class；(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) lauryl acrylate etc. are single
Function (methyl) esters of acrylic acid；Bis- (methyl) acrylate of 1,6- hexylene glycol, bis- (methyl) acrylic acid of two contractings/tripropylene glycol
Bis- (methyl) acrylate of ester, two contractings/triethylene Glycol, bis- (methyl) acrylate of ethoxylated bisphenol A, neopentyl glycol diethoxy
Difunctionalities (methyl) esters of acrylic acid such as bis- (methyl) acrylate of base/propoxyl group；Trimethylolpropane tris (methyl) acrylic acid
The multifunctional (methyl) acrylates such as ester, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate
Class；And ethoxylation polyfunctional acrylic ester and propoxylation polyfunctional acrylic ester etc., above compound can be used alone
Or it two or more is used in mixed way.
In the compositions of the present invention, the diluent can be used alone photopolymerization monomer or organic solvent, can also be with
Photopolymerization monomer or organic solvent are used simultaneously.The dosage of the diluent is the 10-70% of present composition total weight,
It is preferred that 20-60%.
Coating composition of the invention also may include customary filler, especially inorganic filler, such as: barium sulfate, barium titanate,
Calcium dioxide, talcum powder, gas-phase silica, silica, clay, magnesium carbonate, calcium carbonate, aluminium oxide, mica powder, kaolin
Deng.The dosage of the filler is the 0-40% of present composition total weight, and the partial size of filler is < 15 μm, preferably < 5 μm.
Coating composition of the invention also may include common colorant, and the example includes: phthalocyanine green, phthalocyanine blue, crystallization
Purple, titanium dioxide, carbon black etc., above-mentioned substance can be used alone or two or more be used in mixed way.Wherein, the dosage of the colorant
For the 0-20% of present composition total weight, preferably 0-10%.
The present invention is coating composition also optionally including epoxy resin curing accelerator, heat polymerization inhibitors, thixotroping
One of tackifier, dispersing agent, levelling agent and defoaming agent etc. or multiple additives.The total weight of the various additives is
The 0-40% of present composition total weight, preferably 0-10%.
Coating composition of the invention can be obtained by each component mixing.If not being to use immediately after preparing, preferably
It is kept in dark place, to avoid solidification.It is of course also possible to photoinitiator is individually placed, Shi Zaiyu other components mixing to be used.
In addition, the present invention also provides aforementioned coating compositions to pass through the use that conventional coating techniques form film layer on substrate
On the way.The coating composition has excellent mouldability, developability and light sensitivity on substrate.The substrate of the substrate can be
Metal, plastics or other materials, such as tin indium oxide (ITO) film, chromium material, copper material, aluminium, glass, poly terephthalic acid second two
Alcohol ester (PET), polypropylene (PP) etc..In use, coating composition is applied directly to substrate surface, shot away into illumination solid
Change.
The present invention also provides the substrate comprising being formed by film layer by conventional coating techniques by the coating composition, institutes
State performance of the film layer with excellent light transmittance, heat-resisting quantity and high surface tension.
Combined with specific embodiments below to further illustrate the present invention, however, the present invention is not limited thereto.
In the present invention, the acid value of polymer resin is measured according to GB/T2895-1989.
In the present invention, the solid content of polymer resin is measured according to GB/T7193-1987.
The synthesis of photosensitive resin I
Synthetic example 1
200g phenol aldehyde type epoxy resin CNE-202 (Taiwan Changchun life insurance resin processing plant, epoxide equivalent are added in the reactor
210), 250g propylene glycol methyl ether acetate (PMA), 69g acrylic acid, heating melt, and add 0.5g hydroquinone, 1.5g triphen
Base phosphine reacts 12 hours at 110 DEG C, obtains product of the acid value less than 5.85g tetrabydrophthalic anhydride is added, is heated to
It 100 DEG C, reacts 6 hours, obtains light yellow resin liquid A1 (photosensitive resin I), acid value 52mgKOH/g, solid content 59%.
Synthetic example 2
In the reactor according to molar ratio be 1:1:2 ratio be added methyl methacrylate, butyl methacrylate and
Acrylic acid, solvent use carbitol acetate, and catalyst uses azodiisobutyronitrile (AIBN), stirs 4 under conditions of 80 DEG C
Hour, obtain resin solution.
The cooling resin solution, uses methylnaphthohydroquinone as polymerization inhibitor and tetrabutyl phosphonium bromide phosphorus as catalyst, in 90-
Addition reaction is carried out with (methyl) glycidyl acrylate under conditions of 105 DEG C, wherein the resin carboxyl and (methyl) third
The molar ratio of olefin(e) acid ethylene oxidic ester is 5:1, and reaction carries out 16 hours, takes out product resin liquid A2 after cooling.
In obtained resin solution A2 (photosensitive resin I), the acid value of nonvolatile component 65%, solid component is
120mgKOH/g, MwIt is about 15000.
The synthesis of photosensitive resin II
Synthetic example 3
1mol styrene, 1mol maleic anhydride and 2mol propylene glycol methyl ether acetate, 2g azo two are added in the reactor
Isobutyronitrile (AIBN) is used as catalyst, stir 4 hours at 80 DEG C~90 DEG C, then addition 1mol distilled water, and it is 2 small that the reaction was continued
When, it adds 1mol glycidyl methacrylate (GMA), successive reaction 14 hours, it is (photosensitive to obtain light yellow resin liquid B1
Resin II), acid value 89mgKOH/g, solid content 58%.
Synthetic example 4
1mol isobornyl methacrylate, 1mol maleic anhydride, 2mol propylene glycol monomethyl ether acetic acid are added in the reactor
Ester, 2g azodiisobutyronitrile (AIBN) are used as catalyst, stir 4 hours at 80 DEG C~90 DEG C, 1mol distilled water is then added,
The reaction was continued 2 hours, adds 1mol 3, and 4- epoxycyclohexyl-methyl methacrylate successive reaction 14 hours, obtains shallow
Yellow coloured resin liquid B2 (photosensitive resin II), acid value 72mgKOH/g, solid content 66%.
Above-mentioned synthesized resin is mixed with other reagents by the weight proportion in table 1, is dispersed using dispersion machine
Uniformly, the coating composition of embodiment 1-6 and comparative example 1-4 are obtained.
The comparison of the transparent material of the transparency and surface tension will be hereinafter carried out while require, if only to surface
Power requires, then filler and pigment can be added in formula.
Application Example
To 10 kinds of coating compositions in the embodiment and comparative example of above-mentioned acquisition, following performance test and assessment are carried out,
The results are shown in table 1.
(1) mouldability
Coating composition obtained is respectively coated on to the glass plate (10cm*10cm*0.1cm) of dry cleansing with rolling method
On to form 2 microns of thick film layers, altogether apply 6.Visually observe whether coating surface has the defects of bubble, pin hole, white point.
Evaluation method: any of above defect is not excellent, and it is poor for having any drawbacks described above then.
(2) developability
The glass plate for being coated with coating composition in step (1) is put into 75 ± 5 DEG C of baking oven preliminary drying 5 minutes, is taken out certainly
It is so cooling, then take wherein a piece of carry out development operation, development conditions are as follows: KOH (potassium hydroxide) water of 0.05% (mass ratio)
Solution, temperature are 30 DEG C, spray pressure 1-3kg/cm2。
Evaluation method: development is clean, otherwise it is difference that it is excellent for, which remaining on substrate without coating composition,.
(3) light sensitivity
It will take and a piece of be placed on coating composition film with 21 rank exposure guide rules in remaining 5 sheet in addition to plate in step (2)
It is exposed, develops by the condition in developability (2), coated with glass plate and expose energy needed for composition film 6 lattice of residual
Amount is standard, is then judged.
Evaluation method: light energy needed for 6 lattice of residual is less than or equal to 80mJ/cm2It is excellent；Light energy needed for remaining 6 lattice is big
In 80mJ/cm2And it is less than or equal to 150mJcm2It is good；Light energy needed for remaining 6 lattice is greater than 150mJ/cm2It is less than or equal to
300mJ/cm2For in, light energy needed for remaining 6 lattice is greater than 300mJ/cm2For difference.
(4) light transmittance
Remaining 4 sheet in addition to plate in step (2), (3) are respectively put into 230 DEG C, 250 DEG C, 270 DEG C, 280 DEG C of baking ovens
Then middle baking 30min surveys light transmittance with ultraviolet specrophotometer, observe the light transmittance at 400nm, records data in table 1.
(5) surface tension
The plate dyne test surfaces tension for 4 pieces in step (4) being surveyed light transmittance, is recorded in table 1 for the data obtained
In.
Photoinitiator 907:2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinyl-1- acetone is purchased from Ciba；
Photoinitiator ITX: isopropyl thioxanthone is purchased from Tianjin Jiuri Chemical Co., Ltd.；
DPHA: dipentaerythritol hexaacrylate is purchased from Sartomer, the U.S.；
Levelling agent BYK-333: purchased from chemical (BYK) company of Bi Ke；
PMA: propylene glycol methyl ether acetate is purchased from Dow solvent company；
The material that other in patent are not particularly illustrated is chosen from commercially available technical grade reagent.
From table 1 it follows that the coating composition is when as transparent material, due to simultaneously in the embodiment of the present invention
Used photosensitive resin I and photosensitive resin II, when obtained coating composition is coated on glass substrate with excellent mouldability,
Developability, light sensitivity and its it is formed by film layer on a glass with excellent light transmittance, heat-resisting quantity and a dyne value it is
38 or more high surface tension；With photosensitive resin I ratio is only used in comparative example, obviously change in terms of light transmittance and surface tension
It is kind, when with only using photosensitive resin II in comparative example, it is obviously improved in terms of light transmittance.In addition, coating group under the same conditions
It closes in object and photosensitive resin I or photosensitive resin is used alone using two kinds of photosensitive resin I and II ratios of molar ratio 1:2~2:1 simultaneously
As the reduction amplitude of light transmittance when temperature, which increases, to be used in mixed way than being used alone may be significantly smaller when II, in terms of heat-resisting quantity
It is obviously improved.
Claims (19)
1. a kind of coating composition, it includes
A. photosensitive resin I is in molecule simultaneously containing carboxyl and at least two ethylene type unsaturated bonds and its acid value is 50-
The photoresist of 150mgKOH/g, 10-18.9%；
B. photosensitive resin II is made by following methods: a, the monomer A containing a double bond and the acid anhydrides B containing a double bond are total
It is poly- to obtain resin C；B, appropriate H is added2O carries out open loop to the acid anhydrides in resin C, obtains resin D；C, it is added in resin D same
The monomer F of Shi Hanyou mono- double bond and an epoxy group, reaction obtain photosensitive resin II, 28.3-40%；
C. photoinitiator, 0.5-15%；
D. diluent, 10-70%；
And optional filler, colorant, epoxy resin curing accelerator, heat polymerization inhibitors, thixotroping tackifier, dispersing agent,
Levelling agent and defoaming agent；
Wherein each component is based on composition total weight, and the percentage summation of each component is 100%,
Wherein the monomer F is selected from 1,2- epoxy group -4- vinyl cyclohexane, (methyl) glycidyl acrylate, 3,4- ring
Oxygen cyclohexyl methyl (methyl) acrylate, 1,2- epoxy group -3- butylene, 1,2- epoxy group -5- hexene, 1,2- epoxy -9- certain herbaceous plants with big flowers
At least one of alkene.
2. coating composition according to claim 1, wherein the monomer A is the comonomer with ethylene type unsaturated bond,
It is selected from styrene, chlorostyrene, α-methylstyrene；By methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, tertiary fourth
Base, amino, 2- ethylhexyl, octyl, caprinoyl, nonyl, decyl, dodecyl, cetyl, octadecyl, cyclohexyl, different ice
The acrylic acid that chip base, methoxy ethyl, butoxyethyl group, 2- hydroxyethyl, 2- hydroxypropyl and 3- chlorine-2-hydroxyl propyl replace
Ester or methacrylate；The mono acrylic ester or monomethacrylates of polyethylene glycol or single acrylic acid of polypropylene glycol
Ester or monomethacrylates；Vinyl acetate, vinyl butyrate or vinyl benzoate；Acrylamide, Methacrylamide,
N- hydroxymethylacrylamide, N- methoxy acrylamide, N- ethoxymethyl acrylamide, N- butoxymethyl propylene
At least one of amide, acrylonitrile.
3. coating composition according to claim 1, wherein the acid anhydrides B is unsaturated multi-anhydride, selected from maleic anhydride,
At least one of methylnadic anhydride, carbic anhydride, citraconic anhydride, itaconic anhydride.
4. coating composition according to claim 1, wherein the photoinitiator is benzoin and benzoin alkylether；Benzene second
Ketone；Ketoxime ester；Anthraquinones；Thioxanthene ketone class；Ketal class；Organic peroxide；Mercaptan compound；Organohalogen compounds；Hexichol
Ketone or thioxanthene ketone class；At least one of 2,4,6- trimethylbenzoyldiphenyl oxide.
5. coating composition according to claim 4, wherein the benzoin alkylether is selected from benzoin methyl ether, benzoin second
At least one of base ether and benzoin isopropyl ether.
6. coating composition according to claim 4, wherein the acetophenones are selected from acetophenone, 2,2- dimethoxy -2- benzene
Benzoylformaldoxime, 2,2- diethoxy-2- phenyl acetophenone, 1,1- dichloroacetophenone, 2- methyl-1-[4- (methyl thio) benzene
Base] -2- morpholinopropanone -1,2- benzyl -2- dimethyl amido -1- (4- morpholino phenyl)-butane -1- ketone and N, N- dimethyl
At least one of aminoacetophenone.
7. coating composition according to claim 4, wherein the ketoxime ester is selected from 1- (6- o-methyl-benzene formoxyl -9- second
- 3 base of base -9.H.- carbazole)-acetophenone oxime-O- acetic acid esters and 1- [4- (thiophenyl) phenyl] -1,2- octanedione 2- (O- benzoyl
At least one of oxime).
8. coating composition according to claim 4, wherein the Anthraquinones are selected from 2-methylanthraquinone, 2- ethyl hydrazine, uncle 2-
At least one of butyl anthraquinone and 1- chloroanthraquinone.
9. coating composition according to claim 4, wherein the thioxanthene ketone class is selected from 2,4- dimethyl thioxanthone, 2,4- diethyl
At least one of base thioxanthones, 2-chlorothioxanthone and 2,4- diisopropylthioxanthone.
10. coating composition according to claim 4, wherein the ketal class is selected from acetophenone dimethyl ketal and benzyl diformazan
At least one of base ketal.
11. coating composition according to claim 4, wherein the organic peroxide is selected from benzoyl peroxide and peroxidating
At least one of cumenyl.
12. coating composition according to claim 4, wherein the mercaptan compound is selected from 2,4,5- tri- aromatic radical imidazoles binary
At least one of body, hibon, 2- sulfenyl benzimidazole, 2- sulfenyl benzoxazoles and 2- sulfurio benzo thiazole.
13. coating composition according to claim 4, wherein the organohalogen compounds are selected from 2,4,6- tri--s- triazines, 2,2,2-
At least one of ethobrom and trisbromomethyl phenyl ketone.
14. coating composition according to claim 4, wherein the Benzophenones are selected from benzophenone and 4,4 '-bis- diethylamides
At least one of base benzophenone.
15. coating composition according to claim 1, wherein the filler is selected from barium sulfate, barium titanate, calcium dioxide, cunning
At least one of mountain flour, silica, clay, magnesium carbonate, calcium carbonate, aluminium oxide, mica powder, kaolin.
16. coating composition according to claim 15, wherein the silica is gas-phase silica.
17. coating composition according to claim 1, wherein the coating composition is formed by the surface of film layer on substrate
Tension dyne value is greater than 38.
18. according to claim 1 to any one of 17 coating composition, be used for the purposes of substrate.
19. a kind of substrate, it includes the coating compositions of any one of claims 1 to 17 to be formed by film layer.
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| CN105732889B (en) * | 2016-04-15 | 2017-09-15 | 深圳市容大感光科技股份有限公司 | A kind of photoresist and its synthetic method |
| 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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