An alkali-soluble resin, an alkali-soluble resin composition, a photocurable composition, and a photocured product

Abstract

The present invention provides an alkali-soluble resin, an alkali-soluble resin composition, a photocurable composition, and a photocured product. The alkali-soluble resin includes any one or more of the repeating units shown in Formula I below and Formula II below; wherein R1 represents a C1-C 20 hydroxyl-containing alkylene group, a C3-C 30 hydroxyl-containing cycloalkylene group, a C6-C 30 hydroxyl-containing aryl group; R2 represents H, a C1-C 20 alkyl group, or a C3-C 20 cycloalkyl group; R3 represents a substituted or unsubstituted alkylene group, a C3-C7 cycloalkylene group, a C6-C 30 aryl group, a C3-C 30 heterocycloalkylene group; R4 represents H, a C1-C 20 alkyl group, or a C3-C 20 cycloalkyl group, and R5 represents nothing, a C1-C 10 straight-chain alkylene group, a C3-C7 cycloalkylene group, a C6-C 30 arylene group. The dispersibility and stability of the photocurable composition are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of light-cured display, in particular, to an alkali-soluble resin, an alkali-soluble resin composition, a light-cured composition and a light-cured product. BACKGROUND

[0002] In recent years, with the progress of photolithography technology, the micropatterning of patterns has been developed. The requirements for the performance of display devices, such as brightness, pattern color, contrast, and the like, are becoming higher and higher; in order to obtain high development precision and contrast, it is necessary to improve the application performance of the photosensitive resin composition and its raw materials: resin, initiator, polymerizable compound and the like, to meet the ever-developing needs. In particular, the photoresist resin has a significant impact on the performance of the photoresist because it accounts for a large proportion in the light-cured composition. The alkali-soluble resin plays a supporting role in the light-cured composition and can provide protection for pigment dispersion and film formation. In particular, the stability of the solution after pigment dispersion has a decisive effect on the color brightness, surface smoothness and development effect of the film material after the composition is cured.

[0003] A siloxane-modified acrylate composition is disclosed in Chinese Patent Application No. CN109343308A, which has significantly improved resistance to acidity and certain improvement in resolution, but the storage stability of the formed light-cured composition is not outstanding. Chinese Patent Application No. CN103718107A discloses a composition containing a silane-modified resin, which has certain improvement in adhesion to developed patterns, but the appearance smoothness of the developed patterns is not high. Chinese Patent Application No. CN112596338A proposes an adhesive resin containing a polycycloalkyl acrylate copolymer, which produces a light-cured composition with good dispersibility, but its storage stability is relatively low and the storage and transportation conditions are relatively high. SUMMARY

[0004] The main purpose of the present application is to provide an alkali-soluble resin, an alkali-soluble resin composition, a light-cured composition and a light-cured product, to solve the problem of poor dispersibility and stability of the light-cured composition in the prior art.

[0005] In order to achieve the above-mentioned purpose, according to one aspect of the present application, an alkali-soluble resin is provided, which comprises any one or more of the following formula I repeat units and any one or more of the following formula II repeat units:

[0006]

[0007] wherein R1 represents C1-C 20 alkyl group containing a hydroxyl group, C3-C 30hydroxyl-containing cycloalkylene compounds, C6-C 30 R2 represents any one or more aromatic groups containing a hydroxyl group; R2 represents H, C1-C1. 20 Alkyl or C3-C 20 R3 represents any one or more of the cycloalkyl groups; R3 represents C1 to C2. 20 Alkylene, C1-C 20 Alkylenes with some carbon atoms replaced by other heteroatoms, C3-C7 cycloalkylenes, C6-C 30 Aromatic group, C3~C 30 Any one or more of heterocyclic alkylene groups; R4 represents H, C1-C1. 20 Alkyl or C3-C 20 Any one or more of the cycloalkyl groups, R5 denotes empty, C1 to C5. 10 Straight-chain alkylene, C3-C7 cycloalkylene, C6-C 30 It can be any one or more of the aromatic groups, where m represents an integer between 1 and 30, and n represents an integer between 1 and 40.

[0008] Furthermore, R1 represents C1~C 20 Alkylenes containing hydroxyl groups, C3-C 30 hydroxyl-containing cycloalkylene compounds, C6-C 30 R2 represents any one or more of the aromatic groups containing hydroxyl groups; R3 represents any one or more of the alkylene groups from C1 to C5; R4 represents any one or more of the alkylene groups from C1 to C5; R5 represents empty, straight-chain alkylene groups from C1 to C5, cycloalkylene groups from C3 to C6, and C6 to C5. 10 It can be any one or more of the aromatic groups, where m represents an integer between 1 and 30, and n represents an integer between 1 and 40.

[0009] Further, R1 represents an ethylene containing a hydroxyl group; R2 represents H, methyl, or ethyl; R3 represents a C1-C3 alkylene; R4 represents any one or more of H, methyl, or ethyl; R5 represents any one or more of empty, -CH2-, -(CH2)2-, cyclohexylene, or phenylene; m represents an integer between 1 and 30; n represents an integer between 1 and 40.

[0010] Furthermore, the alkali-soluble resin also includes structural segments formed by the polymerization of olefinic unsaturated monomers; preferably, the olefinic unsaturated monomers are selected from one or more of vinyl compounds, aromatic vinyl esters, vinyl cyano compounds, maleic anhydride compounds, maleimide compounds, (meth)acrylic acid compounds, and (meth)acrylate compounds.

[0011] Further, the ethylenically unsaturated monomer is one or more of a-p or aromatic ring substituted polymerizable styrene derivative, (meth)acrylic acid, a-bromo(meth)acrylic acid, a-chloro(meth)acrylic acid, b-furyl(meth)acrylic acid, b-styryl(meth)acrylic acid, alkyl(meth)acrylate, benzyl(meth)acrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl(meth)acrylate, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, glycidyl(meth)acrylate, 2,2,2-trifluoroethyl(meth)acrylate, 2,2,3,3-tetrafluoropropyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, glycidyl(meth)acrylate, dicyclopentyl methacrylate, ether derivatives of vinyl alcohol, acrylonitrile vinyl n-butyl ether, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, a-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, N-vinyl caprolactam, N-vinyl pyrrolidone; preferably the ethylenically unsaturated monomer is selected from one or more of styrene, vinyltoluene, a-methylstyrene, p-methylstyrene, p-ethylstyrene, p-chlorostyrene; preferably the ether derivatives of vinyl alcohol are selected from one or more of acrylamide, diacetone acrylamide.

[0012] Further, the ethylenically unsaturated monomer is one or more of benzyl(meth)acrylate, (meth)acrylic acid, dicyclopentyl methacrylate.

[0013] Further, the molecular weight of the alkali-soluble resin is in the range of 5000 to 20000, preferably in the range of 8000 to 15000, more preferably in the range of 10000 to 15000; preferably the acid value of the alkali-soluble resin is in the range of 80 to 200 mgKOH / g, more preferably in the range of 100 to 180 mgKOH / g, further preferably in the range of 100 to 130 mgKOH / g.

[0014] To achieve the above object, according to one aspect of the present application, there is provided an alkali-soluble resin composition, the alkali-soluble resin composition comprising the alkali-soluble resin of any one of the above and a fluorenyl polymer, the structure of the fluorenyl polymer being shown in Formula III;

[0015]

[0016] wherein A, B independently represent a substituent group, n is any one integer in the range of 1 to 20; preferably A is selected from any one of aromatic residues comprising four substitution positions, preferably A is selected from B is selected from any one of an alkyl residue or an aromatic residue comprising 2 substitution positions; preferably B is selected from any one of an alkyl residue or an aromatic residue comprising 2 substitution positions, preferably B is selected from B is selected from any one of an alkyl residue or an aromatic residue comprising 2 substitution positions; preferably B is selected from any one of an alkyl residue or an aromatic residue comprising 2 substitution positions, preferably B is selected from

[0017] Further, the fluorene-based polymer has a molecular weight of 5000-10000, preferably in the range of 6000-8000, further preferably in the range of 6500-7500; preferably the fluorene-based polymer has an acid value of 50-200 mgKOH / g, more preferably in the range of 70-150 mgKOH / g, further preferably in the range of 90-120 mgKOH / g.

[0018] Further, the alkali-soluble resin composition comprises 5-20 parts by weight of the alkali-soluble resin and 5-20 parts by weight of the fluorene-based polymer, preferably the alkali-soluble resin composition comprises 5-15 parts by weight of the alkali-soluble resin and 5-15 parts by weight of the fluorene-based polymer.

[0019] According to another aspect of the present application, the present application also provides a photocuring composition, the photocuring composition comprising the alkali-soluble resin composition of any one of the above.

[0020] Further, the photocuring composition further comprises a photoinitiator and a photopolymerizable monomer, preferably the photoinitiator is in the range of 0.1-5 parts by weight, further preferably in the range of 1-3 parts by weight, preferably the photopolymerizable monomer is in the range of 10-20 parts by weight.

[0021] Further, the photocuring composition further comprises a colorant, an additive and a solvent, preferably the colorant is in the range of 20-30 parts by weight, preferably the additive comprises one or more of a curing agent and a leveling agent, preferably the additive is in the range of 0.1-1.0 parts by weight, preferably the photocuring composition has a solid content in the range of 10%-30%.

[0022] According to still another aspect of the present application, the present application also provides a photocured product, the photocured product being prepared from the photocuring composition of any one of the above, the photocured product being an ink, a paint or a photoresist.

[0023] By applying the technical solution of the present application, the alkali-soluble resin has good alkali solubility due to the fact that the alkali-soluble resin comprises both the structure of Formula I and Formula II, and the structure Formula II has a carboxylic acid hanging group which can well interact with the surface of the pigment to form a uniform dispersion liquid; therefore, the above alkali-soluble resin of the present application is used to prepare a corresponding photocuring composition together with other conventional additives in the photocuring composition, the photocuring composition has good dispersion stability, and the pattern prepared by using the photocuring composition has good fineness and surface smoothness. DETAILED DESCRIPTION

[0024] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to the embodiments.

[0025] As analyzed in the background section of this application, the existing photocurable compositions have poor dispersibility and stability. In order to solve this problem, this application provides an alkali-soluble resin, an alkali-soluble resin composition, a photocurable composition, and a photocurable product.

[0026] In one typical embodiment of this application, an alkali-soluble resin is provided, the alkali-soluble resin comprising any one or more repeating units of Formula I and any one or more repeating units of Formula II.

[0027]

[0028] Where R1 represents C1~C 20 Alkylenes containing hydroxyl groups, C3-C 30 hydroxyl-containing cycloalkylene compounds, C6-C 30 R2 represents any one or more aromatic groups containing a hydroxyl group; R2 represents H, C1-C1. 20 Alkyl or C3-C 20 R3 represents any one or more of the cycloalkyl groups; R3 represents C1 to C2. 20 Alkylene, C1-C 20 Alkylenes with some carbon atoms replaced by other heteroatoms, C3-C7 cycloalkylenes, C6-C 30 Aromatic group, C3~C 30 Any one or more of heterocyclic alkylene groups; R4 represents H, C1-C1. 20 Alkyl or C3-C 20 R5 represents any one or more of the cycloalkyl groups, where R5 represents empty, C1 to C5. 10 Branched alkylene, C3-C7 cycloalkylene, C6-C 30 It can be any one or more of the aromatic groups, where m represents an integer between 1 and 30, and n represents an integer between 1 and 40.

[0029] The alkali-soluble resin of this application contains both Formula I and Formula II structures, which gives it good alkali solubility. Furthermore, Formula II has a carboxylic acid suspension group, which can interact well with the pigment surface to form a uniform dispersion. Therefore, by using the alkali-soluble resin of this application and combining it with other conventional additives in the photocurable composition, a corresponding photocurable composition can be prepared. This photocurable composition has good dispersion stability, and the patterns prepared using this photocurable composition have good fineness and surface smoothness.

[0030] To further enhance the surface interaction between alkali-soluble resin and pigment, in some embodiments, R1 represents C1 to C2. 20 Alkylenes containing hydroxyl groups, C3-C 30 hydroxyl-containing cycloalkylene compounds, C6-C 30 R2 represents any one or more of the aromatic groups containing hydroxyl groups; R3 represents any one or more of H, methyl, and ethyl groups; R4 represents any one or more of H, methyl, and ethyl groups; R5 represents empty, a straight-chain alkylene group from C1 to C5, a cycloalkylene group from C3 to C6, or a C6 to C5 alkylene group. 10 It can be any one or more of the aromatic groups, where m represents an integer between 1 and 30, and n represents an integer between 1 and 40.

[0031] To further improve the surface interaction between alkali-soluble resin and pigment, in some embodiments, R1 represents any one or more of ethylenes containing hydroxyl groups; R2 represents any one or more of H, methyl, and ethyl; R3 represents any one or more of C1-C3 alkylenes; R4 represents H, methyl, and ethyl; R5 represents any one or more of empty, -CH2-, -(CH2)2-, cyclohexylene, and phenylene; m represents an integer between 1 and 30, preferably between 1 and 30; and n represents an integer between 1 and 40.

[0032] In some embodiments, the alkali-soluble resin further includes structural segments formed by polymerization of olefinic unsaturated monomers; preferably, the olefinic unsaturated monomers are selected from one or more of vinyl compounds, aromatic vinyl esters, vinyl cyano compounds, maleic anhydride compounds, maleimide compounds, (meth)acrylic acid compounds, and (meth)acrylate compounds; preferably, (meth)acrylate (ester) compounds include acrylic acid compounds and their esters and / or methacrylic acid compounds and their esters.

[0033] In some embodiments, the ethylenically unsaturated monomer is one or more of a-pi or substituted on the aromatic ring polymerizable styrene derivative, (meth)acrylic acid, a-brominated (meth)acrylic acid, a-chlorinated (meth)acrylic acid, β-furyl (meth)acrylic acid, β-styryl (meth)acrylic acid, alkyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, dicyclopentyl methacrylate, ether derivatives of vinyl alcohol, acrylonitrile vinyl n-butyl ether, maleic anhydride, monomethyl maleate, monoethyl maleate, monoiso-propyl maleate, fumaric acid, cinnamic acid, a-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, N-vinyl caprolactam, N-vinyl pyrrolidone; preferably the ethylenically unsaturated monomer is selected from one or more of styrene, vinyltoluene, a-methylstyrene, p-methylstyrene, p-ethylstyrene, p-chlorostyrene; preferably the ether derivatives of vinyl alcohol are selected from one or more of acrylamide, diacetone acrylamide.

[0034] In some embodiments, the ethylenically unsaturated monomer is one or more of benzyl (meth)acrylate, (meth)acrylic acid, dicyclopentyl methacrylate.

[0035] The structural segments formed by the above-mentioned ethylenically unsaturated monomers, in combination with the repeating units of the above-mentioned Formula I and Formula II, can further adjust the molecular weight, acid value, etc. of the alkali-soluble resin, and affect its properties such as alkali-solubility.

[0036] The weight average molecular weight of the above-mentioned alkali-soluble resin is not particularly limited and should be adapted to the specific application environment. The weight average molecular weight of the polymer is determined by gel permeation chromatography (GPC) and is obtained by conversion using a standard curve of standard polystyrene. In order to obtain good dispersibility and developing effect, in some embodiments, the molecular weight of the above-mentioned alkali-soluble resin is controlled to be 5000-20000, preferably the molecular weight of the above-mentioned alkali-soluble resin is 8000-15000, more preferably the molecular weight of the above-mentioned alkali-soluble resin is 10000-15000; if the molecular weight is less than 5000, the dispersibility decreases, the alkali solubility is too strong, and it is easy to cause insufficient adhesion and developing defects; if the molecular weight is greater than 20000, the alkali solubility decreases significantly, the developing residue increases, and the application effect is affected.

[0037] The acid value of the polymer is tested by acid-base titration. In order to achieve good application results, the acid value of the alkali-soluble resin is preferably in the range of 80-200 mgKOH / g, more preferably in the range of 100-180 mgKOH / g, and further preferably in the range of 100-130 mgKOH / g. If the acid value is less than 80 mgKOH / g, the alkali solubility is poor, and the target pattern cannot be obtained. If the acid value exceeds 200 mgKOH / g, the pattern is easily dissolved rapidly, resulting in overdevelopment and even peeling.

[0038] In another typical embodiment of the present application, an alkali-soluble resin composition is provided, which includes an alkali-soluble resin and a fluorenyl polymer, and the alkali-soluble resin is the alkali-soluble resin described above.

[0039] The use of a fluorenyl polymer containing a fluorene structure in combination with the alkali-soluble resin can make the photocurable composition have good dispersion stability, good heat resistance, good etch resistance, and good development effect. The pattern prepared using the photocurable composition has good fineness and surface smoothness, good adhesion to the substrate, good heat and etch resistance, and high resolution.

[0040] In order to make the alkali-soluble resin composition have high heat resistance and etch resistance, while reducing shrinkage, in some embodiments, the structure of the fluorenyl polymer is shown in Formula III;

[0041]

[0042] wherein A, B independently represent a substituent group, and n is any integer in the range of 1-20; preferably A is selected from any one of the aromatic residues containing four substitution positions, preferably A is selected from preferably B is selected from any one of the alkyl residues or aromatic residues containing two substitution positions, preferably B is selected from any one of the alkyl residues or aromatic residues containing two substitution positions, preferably B is selected from

[0043] From the perspective of good development, heat resistance, and etch resistance, the molecular weight of the fluorenyl polymer is controlled to be in the range of 5000-10000, preferably in the range of 6000-8000, and further preferably in the range of 6500-7500. If the molecular weight is less than 5000, the composition after curing may not have sufficient heat resistance and adhesion to the substrate. If the molecular weight exceeds 10000, the development effect of the obtained composition when forming a pattern is significantly affected, the appearance of the pattern is rough, and jagged edges are easily formed.

[0044] In order to obtain a better developing effect, in some embodiments, the acid value of the fluorene-based polymer is preferably 50 to 200 mgKOH / g, more preferably 70 to 150 mgKOH / g, and further preferably 90 to 120 mgKOH / g. Too low an acid value can easily cause developing residue; and too high an acid value can make it difficult to form a pattern of a certain line width, and can even cause the pattern to fall off.

[0045] In some embodiments, in order to make the alkali-soluble resin and the fluorene-based polymer work together more effectively, the alkali-soluble resin composition includes 5 to 20 parts by weight of the alkali-soluble resin and 5 to 20 parts by weight of the fluorene-based polymer, and preferably the alkali-soluble resin composition includes 5 to 15 parts by weight of the alkali-soluble resin and 5 to 15 parts by weight of the fluorene-based polymer.

[0046] In another typical embodiment of the present application, a photocurable composition is provided, which includes the above-described alkali-soluble resin composition.

[0047] In some embodiments, the photocurable composition further includes a photoinitiator and a photopolymerizable monomer, and preferably the photoinitiator is 0.1 to 5 parts by weight, and further preferably 1 to 3 parts by weight, and preferably the photopolymerizable monomer is 10 to 20 parts by weight.

[0048] The photoinitiator is not particularly limited, and any substance that can initiate the polymerization of a double bond under light can be used. In some embodiments, the photoinitiator is a free radical photoinitiator, such as one or more of a combination of benzophenone-based initiators, triazine-based initiators, dialkoxyphenylacetophenone-based initiators, a-hydroxyalkylphenone-based initiators, a-amine alkylphenone-based initiators, acylphosphine oxide initiators, benzophenone-based initiators, benzoin-based initiators, benzil-based initiators, heterocyclic aromatic ketone-based initiators, and oxime ester-based photoinitiators. An oxime ester-based initiator is particularly preferred.

[0049] Exemplary compounds include one or a mixture of several of the following: benzophenone, 4-phenylbenzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, diethoxyphenylacetophenone, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, benzoin, benzoin methyl ether, benzoin isobutyl ether, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethoxyanthracene, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, o-ethoxycarbonyl-a-oximino-1-phenylpropanone, 1,2-octanedione, 1-(4-phenylthio)phenyl-2(o-benzoyl oxime), 1-(9-ethyl)-6-(2-methylbenzoyl)carbazol-3-yl-1-(O-acetyl oxime), GGI-124, GGI-224, OXE-01, NCI-831, 2,4,5-triarylimidazole dimer, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberenone, trichloroacetophenone, amyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis(9-acridinyl)heptane, 1,3-bis(9-acridinyl)propane, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)vinyl]-4,5-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis(trichloromethyl)-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis(trichloromethyl)-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, 4-benzoyl-4'-methyl dimethyl sulfide, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid methyl ester, benzyl-beta-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2(o-ethoxycarbonyl)oxime, and the like.

[0050] The photopolymerizable monomer in the above-described photocurable composition can improve the photosensitivity, cross-linking property, mechanical strength, drug resistance, and the like of the photocurable composition, and any one or a combination of several of them can be selected as long as it is a compound having one or more than one unsaturated bond in the molecule. The photopolymerizable monomer selected in the present application is exemplified by (meth)acrylic adducts of epoxy compounds such as propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol triglycidyl ether, glycerol triglycidyl ether, and the like; unsaturated organic acids such as maleic acid and anhydride thereof; acrylamides such as N-methyl acrylamide, N-ethyl acrylamide, N-isopropyl acrylamide, N-hydroxymethyl acrylamide, N-methyl acrylamide, N-ethyl methyl acrylamide, N-isopropyl methyl acrylamide, N-hydroxymethyl methyl acrylamide, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, N,N-dimethyl acrylamide, N,N-diethyl methyl acrylamide, and the like; polyethylene glycol di(meth)acrylate (ethylene number: 2 to 14); trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane propoxy tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, polypropylene glycol di(meth)acrylate (propylene number: 2 to 14); dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A polyoxyethylene di(meth)acrylate, bisphenol A dioxyethylene di(meth)acrylate, bisphenol A trioxyethylene di(meth)acrylate, bisphenol A oxyethylene di(meth)acrylate, esterification products of a polybasic acid such as phthalic anhydride and the like with a compound having a hydroxyl group and an ethylenic unsaturated group such as β-hydroxyethyl (meth)acrylate and the like; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and the like; styrene-based compounds such as styrene, hydroxystyrene, and the like; N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinyl imidazole, and the like; and the like. Any one or a combination of several of them can be used alone or in combination.

[0051] The photocurable composition can further optionally contain a colorant, an additive, and a solvent, as needed for the application of the product. The colorant is preferably contained in an amount of 20 to 30 parts by weight, the additive is preferably one or more of a curing agent and a leveling agent, and the additive is preferably contained in an amount of 0.1 to 1.0 parts by weight. The solid content of the photocurable composition is preferably 10% to 30%.

[0052] The above colorants are colorants commonly used in the art, and by adding the colorants, a color filter can be well formed. Any organic pigment, inorganic pigment commonly used in the art can be selectively used as the colorant of the present application. Among them, azo pigments, phthalocyanine pigments, quinacridone pigments, isoindoline pigments, indanthrone pigments, indathrene pigments, perinone pigments, diketopyrrolo pigments, etc. can be used. Each of the above pigments can be used alone or after mixing, depending on the specific requirements of the product.

[0053] Further preferably, organic raw materials, and specific pigments are exemplarily listed below, but are not limited to the following pigments. Specific color index (The Society of Dyers and Colorists (C.I.) number of compounds such as:

[0054] C.I. Pigment Orange 1, 3, 11, 13, 14, 15, 16, 17, 20, 24, 3, 53, 55, 60, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 100, 101, 106, 109, 120, 125, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 167, 175, 180, 183, 185;

[0055] C.I. Pigment Orange 1, 13, 31, 36, 42, 43, 55, 59, 61, 65, 71;

[0056] C.I. Pigment Violet 1, 14, 19, 23, 29, 30, 36, 37, 38, 39, 40;

[0057] C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 18, 19, 21, 23, 30, 31, 37, 38, 40, 42, 48, 53:1, 57, 57:2, 60:1, 83, 97, 105, 122, 144, 166, 176, 180, 192, 202, 206, 207, 208, 215, 224, 242, 254, 255, 264, 265;

[0058] C.I. Pigment Blue 1, 2, 15, 15:3, 15:6, 16, 21, 22, 60, 64, 66;

[0059] C.I. Pigment Green 7, 10, 15, 25, 36, 47, 48;

[0060] C.I. Pigment Brown 23, 25, 26, 28;

[0061] C.I. Pigment Black 1 and 7, etc.

[0062] The above-mentioned photocuring composition can be added with an auxiliary agent to improve partial performance, and the auxiliary agent can be used, for example, a filler, a curing agent, a leveling agent such as BYK307, BYK333, etc., an adhesion promoter, an antioxidant, an ultraviolet absorber, etc., but is not limited thereto.

[0063] Among them, the curing agent is used to improve the deep curing performance and mechanical strength. The curing agent can be specifically selected from an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, etc., but is not limited thereto. The leveling agent can use a commercially available surfactant, and can specifically include a silicone surfactant, an ester surfactant, an ionic surfactant, a nonionic surfactant, an amphoteric surfactant, etc., and these surfactants can be used alone or in combination of two or more. The adhesion promoter can use a silane compound, and can be specifically listed as, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(2-methoxyethoxy)silane, N-(2-aminoethyl)-30 aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, etc. The above-mentioned adhesion promoter can be used alone or in combination of two or more. The antioxidant can be specifically listed as, for example, 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,3'-thiobis(4-methyl-6-tert-butylphenol), p-methoxyphenol, etc. The ultraviolet absorber can be selected from 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone, etc.

[0064] In order to disperse the photocurable composition sufficiently, a solvent is required. In the present application, there is no particular requirement, and any of the solvents commonly used in the industry can be used. Exemplary ones include: (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, and the like; aromatic hydrocarbons such as toluene, xylene, mesitylene, and the like; amide compounds such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and the like; carboxylic acid ester compounds such as 2-oxobutyric acid ethyl ester, acetoacetic acid methyl ester, acetoacetic acid ethyl ester, acetic acid ethyl ester, acetic acid n-propyl ester, acetic acid isopropyl ester, acetic acid butyl ester, acetic acid isobutyl ester, formic acid n-pentyl ester, acetic acid isopentyl ester, propionic acid butyl ester, butyric acid ethyl ester, butyric acid n-propyl ester, butyric acid isopropyl ester, butyric acid butyl ester, pyruvic acid methyl ester, pyruvic acid ethyl ester, pyruvic acid n-propyl ester, 2-hydroxypropionic acid methyl ester, 2-hydroxypropionic acid ethyl ester, 2-hydroxy-2-methylpropionic acid ethyl ester, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, ethoxyacetic acid ethyl ester, hydroxyacetic acid ethyl ester, 2-hydroxy-3-methylbutyric acid methyl ester, 3-methyl-3-methoxybutyl acetic acid ester, 3-methyl-3-methoxybutyl propionic acid ester, and the like; homologous solvents such as methyl ethyl ketone, cyclohexanone, heptanone, 3-heptanone, and the like; cyclic ether compounds such as tetrahydrofuran and tetrahydropyran, and the like; and cyclic ester compounds such as γ-butyrolactone, and the like.

[0065] The above-mentioned organic solvents can be used alone or in a mixture of two or more, and among them, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, and the like are preferable in terms of solubility of the photocurable composition of the present application, and further, propylene glycol monomethyl ether acetate and diethylene glycol methyl ethyl ether are more preferable.

[0066] The present application will be further described in detail by the following specific examples, which should not be construed as limiting the scope of the present application.

[0067] The alkali-soluble resin was prepared by accurately weighing the (meth) acrylate monomers: methacrylic acid (MAA), methyl methacrylate (MMA), benzyl methacrylate (BZMA), dicyclopentyl methacrylate (DCPMA), hydroxyethyl methacrylate (HEMA), and monoethyl acryloyloxy succinate (HOAMS) according to the weight parts in Table 1, mixing them thoroughly to form a monomer mixture solution, and then placing the solution in a constant-pressure funnel for standby. An appropriate amount of azobisdiisopropyl cyanide was accurately weighed, dissolved in propylene glycol methyl ether acetate (PGMEA), and then placed in a constant-pressure funnel for standby after thorough dissolution. An appropriate amount of propylene glycol methyl ether acetate was placed in a four-necked flask, heated to 70°C under a nitrogen atmosphere, and then the monomer mixture solution and initiator solution were simultaneously added dropwise under thorough stirring, and the dropwise addition was completed in 2 h. The reaction was maintained at 60°C for 4 h, filtered, and the target alkali-soluble resin a was obtained. In the present application, HEMA and HOAMS were used as the main monomers for copolymerization with other (meth) acrylate monomers, and alkali-soluble resins with slightly different Mw were obtained by changing the monomer ratio.

[0068] The specific synthesis samples are shown in Table 1: a1-a9 are synthesis examples, and a10-a12 are comparative examples. The weight average molecular weight Mw is determined by gel permeation chromatography (GPC), and the acid value is determined by acid-base titration.

[0069] Table 1

[0070]

[0071] In addition, in order to further verify the application performance of the products after copolymerization of monomers with different structures, polymers (a13-a21) shown in Table 2 were synthesized by fixing the proportion of methacrylic acid and changing other monomers.

[0072] Table 2

[0073]

[0074] Performance evaluation

[0075] (1) Preparation of the photocuring composition

[0076] The application performance of the photocuring composition composed of the photopolymerization initiator and the alkali-soluble resin given in the examples of the present application was evaluated by preparing exemplary photocuring compositions. According to the following formulations, two kinds of alkali-soluble resins provided in the present application were used to prepare photocuring compositions with different compositions by cooperating with other initiators, additives, etc., to form specific examples and comparative examples. In the present application, the alkali-soluble resin was used in the form of a mixture of the alkali-soluble resin a and the fluorenyl polymer b to form the photocuring composition. The specific examples and comparative examples are shown in Table 3.

[0077] Among them, fluorene-based polymer b is selected as a strong company product with Mw=5000 (code: TR-B20102). The reference results are shown in the following formula IV:

[0078]

[0079] The composition preparation ratio is as follows:

[0080]

[0081] Table 3

[0082]

[0083]

[0084] In addition, the application performance of other resins is verified by using different composition formulations, and the reference formulations are as follows:

[0085]

[0086] Table 4

[0087]

[0088]

[0089] (2) Exposure and development

[0090] The photocuring composition with the above composition is stirred under a yellow light, the composition is added to a glass substrate, and a spin coating method is used for coating, vacuum drying at 90°C for 2 min, to obtain a coating film with a dry film thickness of 1 μm. The substrate with the coating film formed is cooled to room temperature, a mask plate is attached, and a high-pressure mercury lamp 1 PCS light source is used. The coating film is exposed to ultraviolet light with a wavelength of 350-420 nm through a 20-micron line width mask plate, then developed in a 2.5% sodium carbonate solution at 25°C for 20 s, rinsed with ultrapure water, dried, and finally baked at 230°C for 30 min to fix the pattern.

[0091] (3) Performance evaluation

[0092] ①Composition storage stability test: The viscosity of the composition solution is measured by a Brookfield DV2T viscometer at 25°C in the torque range of 40%-60%. A certain amount of the above composition is tested for viscosity, and then a certain amount of the above composition is sealed in a glass container and stored at 40°C for 120 h. The viscosity of the composition is measured by the same method. The following formula is used to calculate the viscosity change rate.

[0093] Viscosity change rate = | (η2 - η1) / η1 * 100% |. The storage stability of the composition is judged by the viscosity change rate.

[0094] Composition storage stability judgment criteria:

[0095] O: viscosity change rate ≤ 10%, and no sediment;

[0096] Δ: 10% < viscosity change rate ≤ 30%, and no sediment;

[0097] ╳: 30% < viscosity change rate, or sediment is generated;

[0098] ②Developing appearance: observing the substrate pattern with a scanning electron microscope (SEM), evaluating the developing pattern integrity, and judging the pigment dispersion based on it. The smoother the developing line, the better the pigment dispersion, and vice versa.

[0099] The developing appearance evaluation criteria are as follows:

[0100] O: smooth surface, neat edges, and no defects;

[0101] Δ: smooth surface, jagged edges

[0102] ╳: rough surface, jagged edges.

[0103] ③Residual film rate: the residual film rate is calculated using the following formula: residual film rate = (film thickness after post-baking treatment) / (film thickness before post-baking) * 100%; The higher the residual film rate, the smaller the shrinkage deformation of the film after post-baking, and the better the heat resistance of the product.

[0104] The residual film rate is evaluated according to the following criteria:

[0105] O: residual film rate ≥ 95%;

[0106] Δ: 95% > residual film rate ≥ 90%;

[0107] ╳: residual film rate < 90%.

[0108] ④Adhesion: after 1.5 times over-exposure treatment of the full-exposed coating film, drying, and cutting horizontally and vertically ten times on each 1 mm of the substrate with a knife, a standard 3M 600 tape is used for peeling test, and the residual amount of the pattern on the substrate is observed with a scanning electron microscope (SEM). The more the residual amount, the higher the adhesion.

[0109] Pattern and substrate adhesion:

[0110] O: not peeled off from the substrate, and the pattern is complete;

[0111] Δ: 1-5 squares peeled off from the substrate;

[0112] ╳: More than 5 squares peeled off from the substrate.

[0113] (5) Sensitivity: The minimum exposure amount after which the residual film rate after developing the light irradiated area in the exposure step is 90% or more is evaluated as the exposure requirement amount. The smaller the exposure requirement amount, the higher the sensitivity.

[0114] The evaluation results are shown in Tables 5 and 6.

[0115] Table 5

[0116]

[0117]

[0118] Table 6

[0119]

[0120] From the above evaluation results, it can be seen that the photocuring composition prepared by using the base-soluble resin a having the specific repeating unit (Structural Formula I and Structural Formula II) provided by the present application and the fluorene-based polymer b containing a fluorene structure has good storage stability, good dispersion effect of insoluble materials such as pigments; after exposure and development, the obtained pattern has good integrity, high surface smoothness, and high adhesion to the substrate.

[0121] In the exposure process, the exposure energy required for forming a pattern by using the photocuring composition provided by the present application is low, all less than 60 mJ / cm 2 , indicating that the photocuring composition has high sensitivity; in the comparative examples, the required exposure energy is generally higher than 60 mJ, and the sensitivity is not high.

[0122] It can be seen from the development result test that the composition prepared by using the base-soluble resin a and the fluorene-based polymer b as the base resin has good development, pattern integrity, adhesion, film residual rate, etc.; in the comparative examples, the development effect, residual film rate, and adhesion, etc. of the polymer not containing the repeating units I and II deviate obviously, and the storage stability of the product is also poor; the comparative examples 5 and 6 not using the base-soluble resin a also have poor storage stability and adhesion, etc.

[0123] In summary, the base-soluble resin composition containing the repeating units I and II of the base-soluble resin a and the fluorene-based polymer b containing a fluorene structure has high sensitivity, good development effect, good adhesion to the substrate, small film yield variation in the baking process, good storage stability, and good application prospect.

[0124] From the above description, it can be seen that the above-mentioned embodiments of the present application achieve the following technical effects: the alkali-soluble resin of the present application contains both formula I and formula II, so that the alkali-soluble resin has good alkali solubility, and formula II has a carboxylic acid hanging group, which can well interact with the surface of the pigment to form a uniformly dispersed liquid; therefore, the above-mentioned alkali-soluble resin of the present application is used to prepare a corresponding photocuring composition together with conventional other additives in the photocuring composition, the photocuring composition has good dispersion stability, the pattern prepared by using the photocuring composition has good fineness and surface smoothness, has good adhesion to the substrate, and has high resolution.

[0125] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Those skilled in the art can make various modifications and changes to the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. An alkali-soluble resin, characterized in that, The alkali-soluble resin comprises any one or more of the following Formula I repeating units and any one or more of the following Formula II repeating units; Formula I Formula II wherein R1 represents any one or more of a C1-C4 alkylene group, a C3-C7 cycloalkylene group, a C6-C10 arylene group, a C3-C7 heterocycloalkylene group, a C1-C4 alkyl group, a C3-C7 cycloalkyl group, a C6-C10 aryl group, a C3-C7 heterocycloalkyl group, a C1-C4 hydroxyl-containing alkylene group, a C3-C7 hydroxyl-containing cycloalkylene group, a C6-C10 hydroxyl-containing arylene group, a C3-C7 hydroxyl-containing heterocycloalkylene group, a C1-C4 hydroxyl-containing alkyl group, a C3-C7 hydroxyl-containing cycloalkyl group, a C6-C10 hydroxyl-containing aryl group, a C3-C7 hydroxyl-containing heterocycloalkyl group, R2 represents any one or more of H, a C1-C4 alkyl group, a C3-C7 cycloalkyl group, R3 represents any one or more of a C1-C4 alkylene group, a C1-C4 alkyl group partially substituted with other heteroatoms, a C3-C7 cycloalkylene group, a C6-C10 arylene group, a C3-C7 heterocycloalkylene group, R4 represents any one or more of H, a C1-C4 alkyl group, a C3-C7 cycloalkyl group, R5 represents any one or more of nothing, a C1-C4 straight-chain alkylene group, a C3-C7 cycloalkylene group, a C6-C10 arylene group, m represents an integer between 1 and 30, and n represents an integer between 1 and 40, and the base-soluble resin has a molecular weight of 5000-20000 and an acid value in the range of 80-200 mg KOH / g. 20 30 30 20 20 20 20 30 30 20 20 10 30 ​​​​​​​​​​​​​ The alkali-soluble resin further comprises a structural segment formed by polymerization of an olefinically unsaturated monomer; the olefinically unsaturated monomer is a combination of methacrylic acid, benzyl methacrylate and dicyclopentyl methacrylate; Alternatively, the olefinically unsaturated monomer is a combination of methacrylic acid, benzyl methacrylate and styrene.

2. The alkali-soluble resin according to claim 1, wherein, R1 represents C1~C 20 Alkylenes containing hydroxyl groups, C3~C 30 hydroxyl-containing cycloalkylene compounds, C6~C 30 R2 represents any one or more of the aromatic groups containing hydroxyl groups; R3 represents any one or more of H, methyl, and ethyl groups; R4 represents any one or more of H, methyl, and ethyl groups; R5 represents empty, C1-C5 straight-chain alkylene groups, C3-C6 cycloalkylene groups, and C6-C5 alkylene groups. 10 It can be any one or more of the aromatic groups, where m represents an integer between 1 and 30, and n represents an integer between 1 and 40.

3. The alkali-soluble resin of claim 1, wherein R1 represents a hydroxyl-containing ethylene group; R2 represents any one or more of H, methyl, ethyl; R3 represents any one or more of C1-C3 alkylene groups; R4 represents any one or more of H, methyl, ethyl, R5 represents any one or more of null, -CH2-, -(CH2)2-, cyclohexylidene, phenylene, m represents an integer between 1 and 30, and n represents an integer between 1 and 40.

4. The alkali-soluble resin according to any one of claims 1 to 3, characterized in that, The alkali-soluble resin has a molecular weight of 8000-15000; and / or, the alkali-soluble resin has an acid value in the range of 100-180 mgKOH / g.

5. The alkali-soluble resin of claim 4, wherein The alkali-soluble resin has a molecular weight of 10000-15000; and / or, the alkali-soluble resin has an acid value in the range of 100-130 mgKOH / g.

6. An alkali-soluble resin composition characterized by comprising: The alkali-soluble resin composition comprises the alkali-soluble resin of any one of claims 1-5 and a fluorenyl polymer having a structure as shown in Formula III; Formula III wherein A, B independently represent a substituent group, and n is any one integer between 1 and 20; the A is selected from any one of aromatic residues comprising four substitution positions; the B is selected from any one of alkyl residues or aromatic residues comprising two substitution positions.

7. The alkali-soluble resin composition according to claim 6, wherein The A is selected from any one of , , , , , , and ; and / or, the B is selected from any one of , , , , , , , , , , , , , , , , , , , , , , , , , , , , , .

8. The alkali-soluble resin composition according to claim 6, wherein The fluorenyl polymer has a molecular weight of 5000-10000; and / or, the fluorenyl polymer has an acid value of 50-200 mgKOH / g.

9. The alkali-soluble resin composition according to claim 8, wherein, The fluorenyl polymer has a molecular weight of 6000-8000; and / or, the fluorenyl polymer has an acid value of 70-150 mgKOH / g.

10. The alkali-soluble resin composition according to claim 9, wherein, The fluorenyl polymer has a molecular weight of 6500-7500; and / or, the fluorenyl polymer has an acid value of 90-120 mgKOH / g.

11. The alkali-soluble resin composition according to any one of claims 6 to 10, characterized in that, The alkali-soluble resin composition comprises 5-20 parts by weight of the alkali-soluble resin and 5-20 parts by weight of the fluorenyl polymer.

12. The alkali-soluble resin composition according to claim 11, wherein, The alkali-soluble resin composition comprises 5-15 parts by weight of the alkali-soluble resin and 5-15 parts by weight of the fluorenyl polymer.

13. A photocurable composition, characterized by, The photocurable composition comprises the alkali-soluble resin composition of any one of claims 6-12.

14. The photocurable composition according to claim 13, characterized in that, The photocurable composition further comprises a photoinitiator and a photopolymerizable monomer.

15. The photocurable composition according to claim 14, wherein The photoinitiator is in a weight fraction of 0.1-5 parts; and / or, the photopolymerizable monomer is in a weight fraction of 10-20 parts.

16. The photocurable composition according to claim 15, characterized in that, The photoinitiator is in a weight fraction of 1-3 parts.

17. The photocurable composition according to any one of claims 13 to 16, characterized in that, The photocurable composition further comprises a colorant, an auxiliary agent and a solvent.

18. The photocurable composition according to claim 17, wherein The colorant is 20-30 parts by weight; and / or, the auxiliary agent comprises one or more of a curing agent, a leveling agent; and / or, the auxiliary agent is 0.1-1.0 parts by weight; and / or, the light-curing composition has a solid content of 10%-30%.

19. A photocured product, characterized by, The light-cured product is prepared from the light-curing composition of any one of claims 13-18, and is an ink, a paint, or a photoresist.

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