Resin polymer, photosensitive resin composition and application thereof

Abstract

The invention provides a resin polymer, a photosensitive resin composition and application thereof. Monomers forming the resin polymer include an ethylenically unsaturated bond type monomer compound, and the ethylenically unsaturated bond type monomer compound includes an acrylic acid silyl ester type monomer compound, a phenol oxygen type monomer compound with an ethylenically unsaturated group, and an oxa-naphthene type monomer compound with an ethylenically unsaturated group. A structural unit formed after polymerization of the monomer shown in the formula I can effectively improve the adhesive force and heat resistance of the polymer resin and a related base material. The monomer as shown in the formula II is acidic after being acted by the photoacid generator, and the monomer as shown in the formula II and the monomer as shown in the formula III have epoxy groups, so that the polymer is fully cured, and the solvent resistance and the like are relatively good; the above photosensitive resin composition has good adhesion to materials, the line size after development is finer, the pattern retention performance after bending is better, and the photosensitive resin composition has good application value.

Description

Technical Field

[0001] The present invention relates to the technical field of photocurable materials, and in particular to a resin polymer, a photosensitive resin composition and applications thereof. Background Art

[0002] With the continuous advancement of display technology, people have higher and higher requirements for the use of display devices, not only high definition, brighter colors, etc., but also the use environment is becoming more and more complex. People hope to use related equipment under more demanding conditions. This requires related display materials to have properties such as water resistance, solvent resistance, scratch resistance, and corrosion resistance. In addition, with the development of flexible display devices such as wearable devices, people's requirements for display materials are further improved, which requires corresponding expansion of these related materials.

[0003] In the preparation process of display elements such as filters, in order to make the filters have better adhesion and solvent resistance, it is often necessary to perform a post-baking procedure at high temperature to fully cure the film material. However, the substrate used in flexible display devices generally cannot withstand high-temperature baking, and the material is required to have good adhesion and certain mechanical strength. In order to be used in flexible display devices that are not resistant to high temperatures, the photocurable composition needs to be fully cured under low baking temperature conditions and show good adhesion, good curing, solvent resistance and good pattern retention performance.

[0004] The photocurable resin plays a decisive role in the performance of the photocurable composition. Therefore, in order to improve the low-temperature curing performance of the photosensitive resin composition, people often modify the structure of the photocurable resin or adjust the composition formula in the hope of obtaining a photocurable composition suitable for low-temperature curing.

[0005] A Chinese patent application with patent application publication number CN105837798A discloses a method for synthesizing and using a latent polythiol curing agent, which has the structural characteristics of β-hydroxythiocarboxylate, can effectively reduce the curing temperature of epoxy resin and promote the ring-opening reaction of epoxy groups, but the process of releasing thiol groups is heat-driven rather than light-driven, and the curing temperature is relatively high.

[0006] A Korean patent application with patent application publication number KR1020200019239A discloses a black photosensitive resin composition, which includes a thermal curing agent, such as a multifunctional thiol compound, so that the composition can exhibit good curing degree and solvent resistance when post-baked at below 80°C, but the thiol input amount in the formula is 2.0-4.5%, and the odor is relatively large.

[0007] The Chinese patent application with patent application publication number CN103809375A uses an alkali-soluble resin with silicone side groups to replace part of the silane coupling agent, which can reduce the amount of auxiliary agent used to a certain extent and can improve the adhesion of the product pattern to the substrate, but its tolerance to solvents is poor. Summary of the invention

[0008] The main purpose of the present invention is to provide a resin polymer, a photosensitive resin composition and its application, so as to solve the problems of poor adhesion, poor flexibility, strong odor, poor high temperature curing resistance, poor solvent resistance and poor developing effect of the flexible photocurable film in the prior art. The photocurable combination provided by the present invention can achieve rapid curing at a relatively low baking temperature (below 100°C), and the obtained cured film has the advantages of high crosslinking density and good adhesion.

[0009] In order to achieve the above-mentioned purpose, according to one aspect of the present invention, a resin polymer is provided, and the monomers forming the resin polymer include ethylenically unsaturated bond monomer compounds, and the ethylenically unsaturated bond monomer compounds include acrylic silicon ester monomer compounds, phenol oxygen monomer compounds with ethylenically unsaturated groups, and oxacycloalkane monomer compounds with ethylenically unsaturated groups.

[0010] Furthermore, in parts by weight, the above-mentioned ethylenically unsaturated bond monomer compound includes: 10 to 20 parts of an acrylic silicone monomer compound, 20 to 30 parts of a phenol oxygen monomer compound with an ethylenically unsaturated group, and 20 to 30 parts of an oxacycloalkane monomer compound with an ethylenically unsaturated group.

[0011] Furthermore, the above-mentioned acrylic silicon ester monomer compound has a structure shown in general formula I,

[0012]

[0013] R1 is selected from hydrogen and C1~C 10 Any one of the alkyl groups; R2, R3, and R4 are each independently selected from C1 to C 10 Straight chain alkyl, C3~C 10 Branched alkyl and C3~C 20 Preferably, R1 is selected from any one of hydrogen and C1-C6 alkyl; Preferably, R2, R3, and R4 are each independently selected from C1-C6 straight-chain alkyl, C3-C6 branched-chain alkyl, and C3-C 10any one of the cycloalkyl groups; further, preferably R1 is selected from hydrogen, methyl, ethyl, propyl or butyl; preferably R2, R3, R4 are each independently selected from methyl, ethyl, propyl, butyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; further, preferably the acrylic acid silicone ester monomer compound is selected from the formula (I-1)

[0014]

[0015] Any one or more of .

[0016] Furthermore, the phenoloxy monomer compound having an ethylenically unsaturated group has a structure shown in general formula II,

[0017]

[0018] R5 is selected from C2~C 20 A hydrocarbon group containing an olefinically unsaturated bond; R6 is selected from C1 to C 10 Acyl, C1~C 10 Preferably R5 is selected from C2~C 10 A hydrocarbon group containing an ethylenically unsaturated bond; preferably R6 is selected from C1-C5 acyl, C1-C5 alkoxy acyl; preferably R5 is selected from vinyl, propenyl, butenyl, pentenyl or hexenyl; preferably R6 is selected from formyl, acetyl, propionyl, butyryl, valeryl, methoxyformyl, methoxyacetyl or methoxypropionyl; further, preferably the phenolic oxygen monomer compound with an ethylenically unsaturated group is of formula (II-1) And / or formula (II-2)

[0019] Furthermore, the above-mentioned oxacycloalkane monomer compound having an ethylenically unsaturated group has a structure shown in the general formula III,

[0020]

[0021] R7 and R8 are each independently selected from C1 to C 20 Alkylene, C3~C 20 Cycloalkylene or C6~C 20 A is selected from C4~C 20 Cyclic alkenylene or C2~C 20 R9 is a three-membered epoxy group or a four-membered epoxy group; preferably, R7 and R8 are each independently selected from C1 to C 10 Alkylene, C3~C 10 Cycloalkylene or C6~C 18 A is preferably selected from C4 to C10 Cyclic alkenylene or C3~C 10 Preferably, R7 and R8 are each independently selected from C1 to C6 alkylene, C3 to C6 cycloalkylene or C6 to C 12 A is preferably selected from a C4-C6 cyclic alkenylene or a C3-C6 chain alkenylene; further, preferably R7 and R8 are each independently selected from any one of methylene, ethylene, propylene, butylene, isopropylene, isobutylene, isopentylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, phenylene, biphenylene, and naphthylene; preferably A is selected from cyclobutenylene, cyclopentenylene, cyclohexenylene, propenylene, butenylene, pentenylene, hexenylene, isopropenylene, isobutenylene or isopentenylene; further, preferably the oxacycloalkane monomer compound with an ethylenically unsaturated group is selected from the formula (III-1):

[0022]

[0023]

[0024] Any one or more of .

[0025] Furthermore, the weight average molecular weight of the resin polymer is 8,000 to 30,000, preferably 10,000 to 20,000.

[0026] Furthermore, the acid value of the resin polymer is ≤10 mgKOH / g, and preferably the acid value of the resin polymer is ≤5 mgKOH / g.

[0027] Furthermore, the above-mentioned ethylenically unsaturated bond monomer compound also includes any one or more of acrylate monomers, (meth)acrylic acid derivative monomers, and styrene derivative monomers. Preferably, the acrylate monomer is selected from alkyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl methacrylate, 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, methyl methacrylate, Any one or more of ester, ethyl methacrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, isooctyl methacrylate, cyclohexyl methacrylate, dicyclopentyl methacrylate, and isobornyl methacrylate; preferably, the (meth)acrylic acid derivative monomer is selected from any one or more of (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furanyl(meth)acrylic acid, and β-styryl(meth)acrylic acid; preferably, the styrene derivative monomer is selected from any one or more of styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, and p-chlorostyrene.

[0028] According to another aspect of the present invention, a photosensitive resin composition is provided, which comprises, by weight, 20 to 50 parts of a resin polymer, 0.1 to 10 parts of a photoinitiator and 1 to 25 parts of a photopolymerizable monomer, wherein the photoinitiator comprises a free radical photoinitiator and a photoacid generator, and the resin polymer is the above-mentioned resin polymer.

[0029] Further, the amount of the free radical photoinitiator is 0.01-1.0wt% of the total amount of the photosensitive resin composition, preferably 0.1-0.5wt%; the free radical photoinitiator is preferably selected from any one or more of benzophenone initiators, triazine initiators, dialkoxyacetophenone initiators, α-hydroxyalkyl phenone initiators, α-aminoalkyl phenone initiators, acylphosphine oxide initiators, benzophenone initiators, benzoin initiators, benzyl initiators, heterocyclic aromatic ketone initiators, and oxime ester photoinitiators; further, the free radical photoinitiator is preferably selected from benzophenone, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfonate. ether, diethoxyacetophenone, 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-oxyimino-1-phenylpropanone, 1,2-octanedione, 1-(4-phenylthio)phenyl-2(o-benzoyl oxime), 1-(9-ethyl)-6-(2-methylbenzoyl)carbazole-3-yl-1-(O-acetyl oxime ), GGI-124, GGI-224, OXE-01, NCI-831, 2,4,5-triarylimidazole dimer, 4,4'-bis(diethylamino)benzophenone, 4,4'-dichlorobenzophenone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, trichloroacetophenone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-di(9-acridinyl)heptane, 1,3-di(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-methyl any one or more of]-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)phenylphenyl-s-triazine, 2,4-bis(trichloromethyl)-6-(2-bromo-4-methoxy)phenylphenyl-s-triazine, 4-benzoyl-4'-methyldimethyl sulfide, ethyl 4-dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2(o-ethoxycarbonyl)oxime;

[0030] The amount of the photoacid generator is preferably 0.1 to 10 wt %, preferably 1 to 5 wt % of the total amount of the photosensitive resin composition; the photoacid generator is preferably selected from any one or more of iodonium salts, sulfonium salts, imidosulfonate derivatives, dicarboximidosulfonates, oximesulfonates, diazo(sulfonic acid methyl) compounds, disulfonylmethylenehydrazine compounds, nitrobenzylsulfonates, biimidazole compounds, diazomethane derivatives, oxadioxime derivatives, β-ketosulfone derivatives, and triazine derivatives; the photoacid generator is preferably selected from any one or more of triphenylsulfonium, trifluoromethanesulfonic acid salts, perfluorobutylsulfonic acid triphenylsulfonium salt, D(L)-camphor-10-sulfonic acid triphenylsulfonium salt, N-hydroxyphthalimide p-toluenesulfonate, N-trifluoromethane yellow yloxy-1,8-naphthalene imine, and (Z)-4-methoxy-N-(toluenesulfonyloxy)iminophenylacetonitrile.

[0031] Furthermore, the photopolymerizable monomer is selected from any one or more of (meth)acrylic acid alkyl ester monomers, styrene monomers, unsaturated organic acids, unsaturated organic anhydrides, acrylamide monomers, and vinyl monomers; preferably, the (meth)acrylic acid alkyl ester monomer is selected from any one or more of (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; preferably, the styrene monomer is styrene and / or hydroxystyrene; preferably, the unsaturated organic acid is maleic acid; preferably, the unsaturated organic anhydride is maleic anhydride; preferably, The acrylamide monomer is selected from any one or more of N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-hydroxymethylacrylamide, N-methylacrylamide, N-ethylmethacrylamide, N-isopropylmethacrylamide, N-hydroxymethylmethacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-dimethylmethacrylamide, and N,N-diethylmethacrylamide; the vinyl monomer is selected from any one or more of N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, and N-vinylimidazole.

[0032] According to another aspect of the present invention, there is provided an application of the above-mentioned photosensitive resin composition, which includes applying the above-mentioned photosensitive resin composition to the preparation of protective films, interlayer insulating materials, and pattern transfer materials of electronic components.

[0033] By applying the technical scheme of the present invention, the resin polymer of the present application is obtained by copolymerization of acrylic silicon ester monomer compounds, phenol oxygen monomer compounds with olefinic unsaturated groups and oxacycloalkane monomer compounds with olefinic unsaturated groups. The structural unit formed by the monomer shown in formula I after polymerization can effectively improve the adhesion and heat resistance of the polymer resin to the relevant substrate. The monomer shown in formula II is acidic after being acted on by a photoacid generator, and reacts with the epoxy group of the monomer shown in formula III, so that the polymer is fully cured and has good solvent resistance and other properties; in the photocuring process, its reaction activity is higher, so that the photosensitive resin composition can achieve good curing at a lower temperature, and the density of the cured film is higher, and the solvent resistance is further improved. Therefore, the photosensitive resin composition including the above polymer resin can achieve cross-linking curing at a lower curing temperature; and the cured film has good heat resistance, solvent resistance and weather resistance. It has good adhesion to the material, and the line size is finer after development, and the pattern retention performance is better after bending. It has good application value in the field of high-resolution dry film and LCD photoresist application field. DETAILED DESCRIPTION

[0034] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0035] As analyzed in the background technology of this application, due to material limitations, the flexible photocurable film in the prior art has the problems of poor adhesion, poor flexibility, strong odor, high curing temperature, poor solvent resistance and poor development effect. In order to solve this problem, this application provides a resin polymer, a photosensitive resin composition and its application.

[0036] In a typical embodiment of the present application, a resin polymer is provided, and the monomers forming the resin polymer include ethylenically unsaturated bond monomer compounds, and the ethylenically unsaturated bond monomer compounds include acrylic silicon ester monomer compounds, phenol oxygen monomer compounds with ethylenically unsaturated groups, and oxyheterocycloalkane monomer compounds with ethylenically unsaturated groups.

[0037] The resin polymer of the present application is obtained by copolymerization of acrylic silicon ester monomer compounds, phenol oxygen monomer compounds with olefinic unsaturated groups and oxacycloalkane monomer compounds with olefinic unsaturated groups. The structural unit formed by the monomer shown in formula I after polymerization can effectively improve the adhesion and heat resistance of the polymer resin to the relevant substrate. The monomer shown in formula II is acidic after being acted on by a photoacid generator, and reacts with the epoxy group of the monomer shown in formula III, so that the polymer is fully cured and has good solvent resistance and other properties; in the photocuring process, its reaction activity is higher, so that the photosensitive resin composition can achieve better curing at a lower temperature, and the density of the cured film is higher, and the solvent resistance is further improved. Therefore, the photosensitive resin composition including the above polymer resin can achieve cross-linking curing at a lower curing temperature; and the cured film has good heat resistance, solvent resistance and weather resistance. It has good adhesion to the material, and the line size is finer after development, and the pattern retention performance is better after bending. It has good application value in the field of high-resolution dry film and LCD photoresist application field.

[0038] In order to improve the synergistic effect between the ethylenically unsaturated bond monomer compounds, so that the obtained resin polymer has better adhesion, flexibility, lighter odor, lower curing temperature, solvent resistance and good development effect, the above-mentioned ethylenically unsaturated bond monomer compounds preferably include, by weight: 10 to 20 parts of acrylic silicon ester monomer compounds; 20 to 30 parts of phenol oxygen monomer compounds with ethylenically unsaturated groups and 20 to 30 parts of oxacycloalkane monomer compounds with ethylenically unsaturated groups.

[0039] In one embodiment of the present application, the above-mentioned acrylic silicon ester monomer compound has a structure shown in Formula I,

[0040]

[0041] R1 is selected from hydrogen and C1~C 10 Any one of the alkyl groups; R2, R3, and R4 are each independently selected from C1 to C 10 Straight chain alkyl, C3~C 10 Branched alkyl and C3~C 20 Preferably, R1 is selected from any one of hydrogen and C1-C6 alkyl; Preferably, R2, R3, and R4 are each independently selected from C1-C6 straight-chain alkyl, C3-C6 branched-chain alkyl, and C3-C 10any one of the cycloalkyl groups; further, preferably R1 is selected from hydrogen, methyl, ethyl, propyl or butyl; preferably R2, R3, R4 are each independently selected from methyl, ethyl, propyl, butyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; further, preferably the acrylic acid silicone ester monomer compound is selected from the formula (I-1)

[0042]

[0043] Any one or more of .

[0044] The present application utilizes acrylic silicon ester monomer compounds mainly to provide silicon ester groups to the resin polymer to improve the adhesion of the formed cured product. The preferred acrylic silicon ester monomer compounds help to improve the synergistic effect between them and other ethylenically unsaturated bond monomer compounds.

[0045] In one embodiment of the present application, the phenol-oxygen monomer compound having an ethylenically unsaturated group has a structure shown in Formula II,

[0046]

[0047] R5 is selected from C2~C 20 A hydrocarbon group containing an olefinically unsaturated bond; R6 is selected from C1 to C 10 Acyl, C1~C 10 Preferably R5 is selected from C2~C 10 A hydrocarbon group containing an ethylenically unsaturated bond; preferably R6 is selected from C1-C5 acyl, C1-C5 alkoxy acyl; preferably R5 is selected from vinyl, propenyl, butenyl, pentenyl or hexenyl; preferably R6 is selected from formyl, acetyl, propionyl, butyryl, valeryl, methoxyformyl, methoxyacetyl or methoxypropionyl; further, preferably the phenolic oxygen monomer compound with an ethylenically unsaturated group is of formula (II-1) and / or formula (II-2)

[0048] The above preferred phenoloxy monomer compounds with ethylenically unsaturated groups are more likely to dissociate into acidic phenolic hydroxyl groups after being acted upon by a photoacid generator, thereby effectively promoting their participation in the crosslinking reaction and increasing the crosslinking density of the photosensitive resin composition.

[0049] In one embodiment of the present application, the above-mentioned oxacycloalkane monomer compound having an ethylenically unsaturated group has a structure shown in Formula III,

[0050]

[0051] R7 and R8 are each independently selected from C1 to C 20 Alkylene, C3~C 20 Cycloalkylene or C6~C 20 A is selected from C4~C 20 Cyclic alkenylene or C2~C 20 R9 is a three-membered epoxy group or a four-membered epoxy group; preferably, R7 and R8 are each independently selected from C1 to C 10 Alkylene, C3~C 10 Cycloalkylene or C6~C 18 A is preferably selected from C4 to C 10 Cyclic alkenylene or C3~C 10 Preferably, R7 and R8 are each independently selected from C1 to C6 alkylene, C3 to C6 cycloalkylene or C6 to C 12 A is preferably selected from a C4-C6 cyclic alkenylene or a C3-C6 chain alkenylene; further, preferably R7 and R8 are each independently selected from a methylene, ethylene, propylene, butylene, isopropylene, isobutylene, isopentylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, phenylene, biphenylene or naphthylene; preferably A is selected from a cyclobutenylene, cyclopentenylene, cyclohexenylene, propenylene, butenylene, pentenylene, hexenylene, isopropenylene, isobutenylene or isopentenylene;

[0052] Furthermore, it is preferred that the oxacycloalkane monomer compound having an ethylenically unsaturated group is selected from the formula (III-1):

[0053]

[0054] Any one or more of .

[0055] The oxacycloalkane monomer compound with an ethylenically unsaturated group in the present application is mainly used to provide an oxacyclopropane group to the resin polymer, thereby improving the crosslinking density and solvent resistance of the corresponding cured film. Furthermore, in order to take into account the cost of the oxacycloalkane monomer compound with an ethylenically unsaturated group and the synergistic effect with other ethylenically unsaturated bond monomer compounds, the above-mentioned oxacycloalkane monomer compound with an ethylenically unsaturated group is preferred.

[0056] The present application has no particular restriction on the weight average molecular weight of the above-mentioned resin polymer, which should be adapted to the specific application environment. If the weight average molecular weight of the resin polymer is too large, the dispersibility of the resin polymer in the photosensitive resin composition is limited, affecting the uniformity of the system and the development effect; if the weight average molecular weight of the resin polymer is too small, the adhesion is reduced, resulting in a decrease in pattern integrity. In some embodiments of the present application, the weight average molecular weight of the above-mentioned resin polymer is preferably 8000 to 30000, preferably 10000 to 20000. The weight average molecular weight of the polymer is measured by gel permeation chromatography (GPC) and obtained by conversion using the standard curve of standard polystyrene.

[0057] In some embodiments of the present application, the acid value of the resin polymer is preferably ≤10 mgKOH / g, and the acid value of the resin polymer is preferably ≤5 mgKOH / g.

[0058] Controlling the acidity of the resin polymer within the above range is beneficial to taking into account both the development effect and the storage stability, and preventing the ring-opening crosslinking of the oxacycloalkane monomer compound with ethylenically unsaturated groups during storage, thereby affecting the quality of the resin polymer.

[0059] In one embodiment of the present application, the above-mentioned ethylenically unsaturated bond monomer compound further includes any one or more of an acrylate monomer, a (meth) acrylic acid derivative monomer, and a styrene derivative monomer. Preferably, the acrylate monomer is selected from alkyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl methacrylate, 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, methyl acrylate Any one or more of methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, isooctyl methacrylate, cyclohexyl methacrylate, dicyclopentyl methacrylate, and isobornyl methacrylate; preferably, the (meth)acrylic acid derivative monomer is selected from any one or more of (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furanyl(meth)acrylic acid, and β-styryl(meth)acrylic acid; preferably, the styrene derivative monomer is selected from any one or more of styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, and p-chlorostyrene.

[0060] In another typical embodiment of the present application, a photosensitive resin composition is provided, which comprises, by weight, 20 to 50 parts of a resin polymer, 0.1 to 10 parts of a photoinitiator and 1 to 25 parts of a photopolymerizable monomer, wherein the photoinitiator comprises a free radical photoinitiator and a photoacid generator, and the resin polymer is the above-mentioned resin polymer.

[0061] The preferred contents of the above components help to exert the synergistic effect of the components with each other. On the one hand, it can provide the cured film with higher adhesion, lower shrinkage, more delicate development pattern and excellent development effect; on the other hand, it can provide good photosensitivity, thereby improving the curing efficiency.

[0062] In order to enable the photosensitive resin composition to be cured smoothly, a free radical photoinitiator and a photoacid generator are used in combination, so that the illumination process can smoothly initiate double bond polymerization and epoxy crosslinking. There is no special limitation on the free radical photoinitiator used in the present invention, as long as it can initiate double bond polymerization under illumination conditions. In some embodiments of the present application, the amount of the free radical photoinitiator is preferably 0.01 to 1.0 wt % of the total amount of the photosensitive resin composition, preferably 0.1 to 0.5wt%; preferably, the free radical photoinitiator is selected from any one or more of benzophenone initiators, triazine initiators, dialkoxyacetophenone initiators, α-hydroxyalkyl phenone initiators, α-aminoalkyl phenone initiators, acylphosphine oxide initiators, benzophenone initiators, benzoin initiators, benzyl initiators, heterocyclic aromatic ketone initiators, and oxime ester photoinitiators; further, preferably, the free radical photoinitiator is selected from benzophenone, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, diethoxyacetophenone, 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-oxyimino-1-phenylpropanone, 1,2-octanedione, 1-(4-phenylthio)phenyl-2(o-benzoyl oxime), 1-(9-ethyl)-6-(2-methylbenzoyl)carbazole-3-yl-1-(O-acetyl oxime), GGI-124, GGI-224, OXE-01, NCI-831, 2,4, 5-triarylimidazole dimer, 4,4'-bis(diethylamino)benzophenone, 4,4'-dichlorobenzophenone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, trichloroacetophenone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-di(9-acridinyl)heptane, 1,3-di(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- Any one or more of bis(trichloromethyl)-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis(trichloromethyl)-6-(3-bromo-4-methoxy)phenylphenyl-s-triazine, 2,4-bis(trichloromethyl)-6-(2-bromo-4-methoxy)phenylphenyl-s-triazine, 4-benzoyl-4'-methyldimethyl sulfide, ethyl 4-dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2(o-ethoxycarbonyl)oxime; preferably, the amount of the photoacid generator is 0.1 to 10 wt %, preferably 1 to 5 wt %; preferably, the photoacid generator is selected from any one or more of iodonium salts, sulfonium salts, imidosulfonate derivatives, dicarboxylic imidosulfonates, oximesulfonates, diazo (sulfonic acid methyl) compounds, disulfonyl methylenehydrazine compounds, nitrobenzyl sulfonates, biimidazole compounds, diazomethane derivatives, oxadioxime derivatives, β-ketosulfone derivatives, and triazine derivatives; preferably, the photoacid generator is selected from triphenylsulfonium, salts of trifluoromethanesulfonic acid, triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium ... Any one or more of salt, D(L)-camphor-10-sulfonic acid triphenylsulfonate, N-hydroxyphthalimide p-toluenesulfonate, N-trifluoromethane yellow acyloxy-1,8-naphthalene imine, (Z)-4-methoxy-N-(toluenesulfonyloxy) iminophenylacetonitrile can be used to obtain excellent epoxy ring-opening crosslinking effect, and to promote the dissociation of acidic phenolic hydroxyl groups from phenolic oxygen monomer compounds with ethylenically unsaturated groups, thereby effectively promoting their participation in the crosslinking reaction and improving the crosslinking density of the composition. .

[0063] The polymerizable monomer is used to improve the photosensitivity and other properties of the photosensitive resin composition. The polymerizable monomer provided in the present invention is not particularly limited, as long as there is at least one unsaturated bond in the molecule. In some embodiments of the present application, the photopolymerizable monomer is preferably selected from any one or more of (meth)acrylic acid alkyl ester monomers, styrene monomers, unsaturated organic acids, unsaturated organic acid anhydrides, acrylamide monomers, and vinyl monomers; the (meth)acrylic acid alkyl ester monomer is preferably selected from any one or more of (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylate-2-ethylhexyl ester; the styrene monomer is preferably styrene and / or Hydroxystyrene; preferably the unsaturated organic acid is maleic acid; preferably the unsaturated organic anhydride is maleic anhydride; preferably the acrylamide monomer is selected from any one or more of N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-hydroxymethylacrylamide, N-methylacrylamide, N-ethylmethacrylamide, N-isopropylmethacrylamide, N-hydroxymethylmethacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-dimethylmethacrylamide, and N,N-diethylmethacrylamide; preferably the vinyl monomer is selected from any one or more of N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, and N-vinylimidazole.

[0064] In some embodiments of the present application, in order to smoothly disperse the photosensitive resin composition provided by the present invention and facilitate its use, a solvent is required. As a common solvent, (poly) alkylene glycol monoalkyl ether solvents, aromatic hydrocarbon solvents, amide solvents, carboxylic acid ester solvents, ketone solvents, cyclic ether solvents, and cyclic ester solvents can be selected, among which (poly) alkylene glycol monoalkyl ether solvents 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, triethylene glycol monopropyl ether, triethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol mono-n-butyl ether, triethylene glycol mono-alkyl ... Ethylene 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, etc.; aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene, etc.; amide solvents such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc.; carboxylic acid esters Solvents such as ethyl 2-oxobutyrate, methyl acetoacetate, ethyl acetoacetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl acetone, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methoxy methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, etc.; ketone solvents such as methyl ethyl ketone, cyclohexanone, heptanone, 3-heptanone, etc.; cyclic ether solvents such as tetrahydrofuran and pyran, etc.; cyclic ester solvents such as γ-butyrolactone, etc.

[0065] The above solvents can be used alone or in combination of two or more. Among the above solvents, preferred are propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, and diethylene glycol methyl ethyl ether; further preferred are propylene glycol methyl ether acetate and diethylene glycol methyl ethyl ether to obtain better solubility and dispersibility.

[0066] In some embodiments of the present invention, in order to achieve the application requirements of light shielding, color development, etc., the photosensitive resin composition can also selectively add a colorant commonly used in the art as needed to better form a color filter. Any organic pigment or inorganic pigment commonly used in the art can be selectively used as the colorant of the present application. These include water-soluble pigments, water-insoluble azo pigments, phthalocyanine pigments, acridone pigments, isoindoline pigments, indole anthrone pigments, indanthrone pigments, pyrrole dione pigments, etc. The above-mentioned pigments can be used alone or in combination, depending on the specific application requirements of the product.

[0067] The pigments used in the present invention are exemplified as follows, but are not limited to the following pigments. Specifically, compounds with color index (The Society of Dyers and Colourists (CI) number are listed as follows:

[0068] CI 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; CI Pigment Yellow 1, 2, 3, 5, 13, 31, 32, 34, 36, 37, 42, 43, 46, 53, 65; CI Pigment Violet 1, 14, 19, 23, 29, 30, 36, 37, 38, 39, 40; CI 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, 2 07, 208, 215, 224, 242, 254, 255, 264, 265; CI Pigment Blue 1, 2, 15, 15:3, 15:6, 16, 21, 22, 60, 64, 66; CI Pigment Green 7, 10, 15, 25, 36, 47, 48; CI Pigment Brown 23, 25, 26, 28; CI Pigment Black 1 and 7, etc.

[0069] According to the needs, one or more of the above pigments are selected for mixed use. In the present invention, it is more preferably one of the pigments such as Pigment Red 8, 10, 11, and 12. The content of the colorant can be selected according to the application requirements of the photosensitive resin composition. In the photosensitive resin composition provided by the present invention, if the total amount of the photosensitive resin composition is 100 parts by weight, the weight of the colorant is 10 to 60 parts, and more preferably 20 to 40 parts.

[0070] In order to evenly disperse the colorant in the photosensitive resin composition, a dispersant may be used. As such a dispersant, preferably used are polyethyleneimine-based, polyurethane resin-based, acrylic resin-based polymer dispersants, particularly oleic acid acrylic resin-based dispersants.

[0071] The photosensitive resin composition may contain additives such as fillers, leveling agents, adhesion promoters, antioxidants, ultraviolet absorbers, etc., but is not limited thereto.

[0072] The leveling agent may be a commercially available surfactant, which may include silicone surfactants, ester surfactants, ionic surfactants, nonionic surfactants, amphoteric surfactants, etc. These surfactants may be used alone or in combination of two or more.

[0073] Adhesion promoters can use silane compounds, such as vinyl trimethoxysilane, vinyl triethoxysilane, N-(2-aminoethyl)-30 aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-chloropropyl methyl dimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, etc. The above adhesion promoters can be used alone or in combination of two or more.

[0074] Specific examples of antioxidants include 4,4'-butylenebis(6-tert-butyl-3-methylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,3'-thiobis(4-methyl-6-tert-butylphenol), p-methoxyphenol, and the like.

[0075] The ultraviolet absorber may be selected from 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone.

[0076] In another typical embodiment of the present application, an application of the aforementioned photosensitive resin composition is provided, and the application includes applying the photosensitive resin composition to the preparation of a protective film, an interlayer insulating material, and a pattern transfer material of an electronic component.

[0077] The photosensitive resin composition including the above polymer resin can achieve crosslinking and curing at a relatively low curing temperature; and the cured film has good heat resistance, solvent resistance and weather resistance. It has good adhesion to the material, and the line size is finer after development, the development resolution is high, and the development appearance is smooth. Therefore, when applied to the preparation of the protective film, interlayer insulation material, and pattern transfer material of the above electronic components, the product quality can be improved and has good application value.

[0078] The beneficial effects of the present application will be further illustrated below in combination with embodiments and comparative examples.

[0079] Resin polymer preparation

[0080] Example 1

[0081] Weigh 150.0g of propylene glycol methyl ether acetate (PGMEA) accurately and put it into a 500L four-necked flask with a reflux condenser, and gradually heat it to 80°C; also weigh 10.0g of methyl methacrylate, 5.0g of isooctyl methacrylate, 20.0g of dicyclopentyl methacrylate, 15.0g of trimethylsilyl methacrylate (Formula I-1), 25.0g of 4-acetoxystyrene (Formula II-1), and 25.0g of diglycidyl tetrahydrophthalate (Formula III-1) accurately to prepare a monomer mixed solution; in addition, weigh 50.0g of PGMEA solvent to dissolve 8.8g of dimethyl azobisisobutyrate to prepare an initiator solution. When the temperature of the solution in the flask reaches 80°C, add the monomer and initiator to the four-necked flask at the same time, keep it at 80°C, react under stirring, and complete the addition for 2h. After the addition was completed, the mixture was kept warm for 2 hours, then heated to 90°C for 1 hour, cooled to room temperature, and filtered to obtain a polymer resin solution A1 (Mw=15123, acid value: 2.3 mgKOH / g).

[0082] Example 2

[0083] Weigh 150.0g of propylene glycol methyl ether acetate (PGMEA) accurately and put it into a 500L four-necked flask with a reflux condenser, and gradually heat it to 80°C; also weigh 10.0g of methyl methacrylate, 5.0g of isooctyl methacrylate, 20.0g of dicyclopentyl methacrylate, 15.0g of triethylsilyl methacrylate (Formula I-1), 25.0g of 4-acetoxyphenylpropene (Formula II-1), and 25.0g of diglycidyl maleate (Formula III-2) accurately to prepare a monomer mixed solution; in addition, weigh 50.0g of PGMEA solvent to dissolve 8.8g of dimethyl azobisisobutyrate to prepare an initiator solution. When the temperature of the solution in the flask reaches 80°C, add the monomer and initiator to the four-necked flask at the same time, keep it at 80°C, react under stirring, and complete the addition for 2h. After the addition was completed, the mixture was kept warm for 2 hours, then heated to 90°C for 1 hour, cooled to room temperature, and filtered to obtain a polymer resin solution A2 (Mw=16225, acid value: 2.0 mgKOH / g).

[0084] Example 3

[0085] Accurately weigh 150.0g of propylene glycol methyl ether acetate (PGMEA) and put it into a 500L four-necked flask with a reflux condenser, and gradually heat it to 80°C; accurately weigh 10.0g of methyl methacrylate, 5.0g of isooctyl methacrylate, 20.0g of dicyclopentyl methacrylate, 15.0g of formula (I-2), 25.0g of formula (II-2), and 25.0g of formula (III-2) to prepare a monomer mixed solution; in addition, weigh 50.0g of PGMEA solvent to dissolve 8.8g of dimethyl azobisisobutyrate to prepare an initiator solution. When the temperature of the solution in the flask reaches 80°C, add the monomer and initiator to the four-necked flask at the same time, keep it at 80°C, react under stirring, and complete the addition for 2h. After the addition is completed, keep it warm for 2h, then heat it to 90°C for 1h, cool it to room temperature, and filter it to obtain polymer resin solution A3. (Mw=15354, acid value: 2.5 mgKOH / g).

[0086] Example 4

[0087] Accurately weigh 150.0g of propylene glycol methyl ether acetate (PGMEA) and put it into a 500L four-necked flask with a reflux condenser, and gradually heat it to 80°C; accurately weigh 10.0g of methyl methacrylate, 5.0g of isooctyl methacrylate, 20.0g of dicyclopentyl methacrylate, 15.0g of formula (I-3), 25.0g of formula (II-1), and 25.0g of formula (III-3) to prepare a monomer mixed solution; in addition, weigh 50.0g of PGMEA solvent to dissolve 8.8g of dimethyl azobisisobutyrate to prepare an initiator solution. When the temperature of the solution in the flask reaches 80°C, add the monomer and initiator to the four-necked flask at the same time, keep it at 80°C, react under stirring, and complete the addition for 2h. After the addition is completed, keep it warm for 2h, then heat it to 90°C for 1h, cool it to room temperature, and filter it to obtain polymer resin solution A4. (Mw = 15493, acid value: 1.4 mgKOH / g)

[0088] Example 5

[0089] Accurately weigh 150.0g of propylene glycol methyl ether acetate (PGMEA) and put it into a 500L four-necked flask with a reflux condenser, and gradually heat it to 80°C; accurately weigh 10.0g of methyl methacrylate, 5.0g of isooctyl methacrylate, 20.0g of dicyclopentyl methacrylate, 15.0g of formula (I-1), 25.0g of formula (II-2), and 25.0g of formula (III-1) to prepare a monomer mixed solution; in addition, weigh 50.0g of PGMEA solvent to dissolve 8.8g of dimethyl azobisisobutyrate to prepare an initiator solution. When the temperature of the solution in the flask reaches 80°C, add the monomer and initiator to the four-necked flask at the same time, keep it at 80°C, react under stirring, and complete the addition for 2h. After the addition is completed, keep it warm for 2h, then heat it to 90°C for 1h, cool it to room temperature, and filter it to obtain polymer resin solution A5. (Mw = 16121, acid value: 2.8 mgKOH / g)

[0090] Example 6

[0091] Accurately weigh 150.0g of propylene glycol methyl ether acetate (PGMEA) and put it into a 500L four-necked flask with a reflux condenser, and gradually heat it to 80°C; accurately weigh 10.0g of methyl methacrylate, 5.0g of isooctyl methacrylate, 20.0g of dicyclopentyl methacrylate, 15.0g of formula (I-1), 25.0g of formula (II-1), and 25.0g of formula (III-3) to prepare a monomer mixed solution; in addition, weigh 50.0g of PGMEA solvent to dissolve 8.8g of dimethyl azobisisobutyrate to prepare an initiator solution. When the temperature of the solution in the flask reaches 80°C, add the monomer and initiator to the four-necked flask at the same time, keep it at 80°C, react under stirring, and complete the addition for 2h. After the addition is completed, keep it warm for 2h, then heat it to 90°C for 1h, cool it to room temperature, and filter it to obtain polymer resin solution A6. (Mw = 14992, acid value: 2.3 mgKOH / g)

[0092] Example 7

[0093] Accurately weigh 150.0g of propylene glycol methyl ether acetate (PGMEA) and put it into a 500L four-necked flask with a reflux condenser, and gradually heat it to 80°C; in addition, accurately weigh 10.0g of methyl methacrylate, 5.0.0g of isooctyl methacrylate, 20.0g of dicyclopentyl methacrylate, 15.0g of formula (I-1), 25.0g of formula (II-2), and 25.0g of formula (III-2) to prepare a monomer mixed solution; in addition, weigh 50.0g of PGMEA solvent to dissolve 8.8g of dimethyl azobisisobutyrate to prepare an initiator solution. When the temperature of the solution in the flask reaches 80°C, add the monomer and initiator to the four-necked flask at the same time, keep it at 80°C, react under stirring, and complete the addition for 2h. After the addition is completed, keep it warm for 2h, then heat it to 90°C for 1h, cool it to room temperature, and filter it to obtain polymer resin solution A7. (Mw = 16102, acid value: 1.9 mgKOH / g)

[0094] Example 8

[0095] Accurately weigh 150.0g of propylene glycol methyl ether acetate (PGMEA) and put it into a 500L four-necked flask with a reflux condenser, and gradually heat it to 80°C; in addition, accurately weigh 10.0g of methyl methacrylate, 5.0g of isooctyl methacrylate, 20.0g of dicyclopentyl methacrylate, 15.0g of formula (I-3), 25.0g of formula (II-2), and 25.0g of formula (III-3) to prepare a monomer mixed solution; in addition, weigh 50.0g of PGMEA solvent to dissolve 8.8g of dimethyl azobisisobutyrate to prepare an initiator solution. When the temperature of the solution in the flask reaches 80°C, add the monomer and initiator to the four-necked flask at the same time, keep it at 80°C, react under stirring, and complete the addition for 2h. After the addition is completed, keep it warm for 2h, then heat it to 90°C for 1h, cool it to room temperature, and filter it to obtain polymer resin solution A8. (Mw = 15338, acid value: 2.1 mgKOH / g)

[0096] Example 9

[0097] Accurately weigh 150.0g of propylene glycol methyl ether acetate (PGMEA) and put it into a 500L four-necked flask with a reflux condenser, and gradually heat it to 80°C; in addition, accurately weigh 10.0g of methyl methacrylate, 5.0g of isooctyl methacrylate, 20.0g of dicyclopentyl methacrylate, 15.0g of formula (I-3), 25.0g of formula (II-2), and 25.0g of formula (III-4) to prepare a monomer mixed solution; in addition, weigh 50.0g of PGMEA solvent to dissolve 8.8g of dimethyl azobisisobutyrate to prepare an initiator solution. When the temperature of the solution in the flask reaches 80°C, add the monomer and initiator to the four-necked flask at the same time, keep it at 80°C, react under stirring, and complete the addition for 2h. After the addition is completed, keep it warm for 2h, then heat it to 90°C for 1h, cool it to room temperature, and filter it to obtain polymer resin solution A8. (Mw = 15035, acid value: 2.2 mgKOH / g)

[0098] Comparative Example 1

[0099] Weigh 150.0g of propylene glycol methyl ether acetate (PGMEA) accurately and put it into a 500L four-necked flask with a reflux condenser, and gradually heat it to 80°C; also weigh 10.0g of methyl methacrylate, 5.0g of isooctyl methacrylate, 20.0g of dicyclopentyl methacrylate, 15.0g of benzyl methacrylate, 25.0g of 4-acetoxystyrene (Formula II-1), and 25.0g of diglycidyl tetrahydrophthalate (Formula III-1) accurately to prepare a monomer mixed solution; also weigh 50.0g of PGMEA solvent to dissolve 8.8g of dimethyl azobisisobutyrate to prepare an initiator solution. When the temperature of the solution in the flask reaches 80°C, add the monomer and initiator to the four-necked flask at the same time, keep it at 80°C, react under stirring, and complete the addition for 2h. After the addition was completed, the mixture was kept warm for 2 hours, then heated to 90°C for 1 hour, cooled to room temperature, and filtered to obtain a polymer resin solution B1 (Mw=15112, acid value: 2.0 mgKOH / g).

[0100] Comparative Example 2

[0101] Weigh 150.0g of propylene glycol methyl ether acetate (PGMEA) accurately and put it into a 500L four-necked flask with a reflux condenser, and gradually heat it to 80°C; also weigh 10.0g of methacrylic acid, 5.0g of isooctyl methacrylate, 20.0g of dicyclopentyl methacrylate, 15.0g of trimethylsilyl methacrylate (Formula I-1), 25.0g of cyclohexyl methacrylate, and 25.0g of tetrahydrophthalic acid diglycidyl ester (Formula III-1) accurately to prepare a monomer mixed solution; in addition, weigh 50.0g of PGMEA solvent to dissolve 8.8g of dimethyl azobisisobutyrate to prepare an initiator solution. When the temperature of the solution in the flask reaches 80°C, add the monomer and initiator to the four-necked flask at the same time, keep it at 80°C, react under stirring, and complete the addition for 2h. After the addition was completed, the mixture was kept warm for 2 hours, then heated to 90°C for 1 hour, cooled to room temperature, and filtered to obtain a polymer resin solution B2 (Mw=15331, acid value: 66.17 mgKOH / g).

[0102] Comparative Example 3

[0103] Weigh 150.0g of propylene glycol methyl ether acetate (PGMEA) accurately and put it into a 500L four-necked flask with a reflux condenser, and gradually heat it to 80°C; also weigh 10.0g of methyl methacrylate, 5.0g of isooctyl methacrylate, 20.0g of dicyclopentyl methacrylate, 15.0g of trimethylsilyl methacrylate (Formula I-1), 25.0g of 4-acetoxystyrene (Formula II-1), and 25.0g of glycidyl methacrylate to prepare a monomer mixed solution; also weigh 50.0g of PGMEA solvent to dissolve 8.8g of dimethyl azobisisobutyrate to prepare an initiator solution. When the temperature of the solution in the flask reaches 80°C, add the monomer and initiator to the four-necked flask at the same time, keep it at 80°C, react under stirring, and complete the addition for 2h. After the addition was completed, the mixture was kept warm for 2 hours, then heated to 90°C for 1 hour, cooled to room temperature, and filtered to obtain a polymer resin solution B3 (Mw=15513, acid value: 3.6 mgKOH / g).

[0104] Comparative Example 4

[0105] Weigh 150.0g of propylene glycol methyl ether acetate (PGMEA) accurately and put it into a 500L four-necked flask with a reflux condenser, and gradually heat it to 80°C; also weigh 10.0g of methacrylic acid, 5.0g of isooctyl methacrylate, 20.0g of dicyclopentyl methacrylate, 15.0g of benzyl methacrylate, 25.0g of cyclohexyl methacrylate, and 25.0g of glycidyl methacrylate accurately to prepare a monomer mixed solution; also weigh 50.0g of PGMEA solvent to dissolve 8.8g of dimethyl azobisisobutyrate to prepare an initiator solution. When the temperature of the solution in the flask reaches 80°C, add the monomer and initiator to the four-necked flask at the same time, keep it at 80°C, react under stirring, and complete the addition for 2h. After the addition was completed, the mixture was kept warm for 2 hours, then heated to 90°C for 1 hour, cooled to room temperature, and filtered to obtain a polymer resin solution B4 (Mw=15531, acid value: 65.35 mgKOH / g).

[0106] Comparative Example 5

[0107] Weigh 150.0g of propylene glycol methyl ether acetate (PGMEA) accurately and put it into a 500L four-necked flask with a reflux condenser, and gradually heat it to 80°C; also weigh 10.0g of methacrylic acid, 5.0g of isooctyl methacrylate, 20.0g of dicyclopentyl methacrylate, 15.0g of benzyl methacrylate, 25.0g of cyclohexyl methacrylate, and 25.0g of isobornyl methacrylate accurately to prepare a monomer mixed solution; in addition, weigh 50.0g of PGMEA solvent and dissolve 8.8g of dimethyl azobisisobutyrate to prepare an initiator solution. When the temperature of the solution in the flask reaches 80°C, add the monomer and initiator to the four-necked flask at the same time, keep it at 80°C, react under stirring, and complete the addition for 2h. After the addition was completed, the mixture was kept warm for 2 hours, then heated to 90°C for 1 hour, cooled to room temperature, and filtered to obtain a polymer resin solution B5 (Mw=14982, acid value: 64.12 mgKOH / g).

[0108] Preparation of photosensitive resin composition

[0109] The polymer resin provided by the present invention is used to prepare a photosensitive resin composition, and the proportions (by weight) of the components in the photosensitive resin composition are as follows:

[0110]

[0111] Specific preparation process: 29 parts by weight of the resin polymers of Examples 1 to 9 and Comparative Examples 1 to 5 are respectively mixed with 15 parts by weight of a photopolymerizable monomer dipentaerythritol hexaacrylate, 0.5 parts by weight of a photopolymerization initiator 1-(4-phenylthio)phenyl-2(o-benzoyl oxime), 3.5 parts by weight of N-hydroxyphthalimide p-toluenesulfonate, 32 parts by weight of a colorant Pigment Red 254, and 25 parts by weight of a solvent propylene glycol methyl ether acetate, and stirred evenly with a shaking stirrer at room temperature to obtain photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 5.

[0112] Photosensitive resin composition comparative example 6

[0113] The difference from the photosensitive resin composition example 1 is that there is no photoacid generator.

[0114] Performance Testing

[0115] Development effect evaluation

[0116] Using a spin coater, the photosensitive resin composition solutions provided in Examples 1 to 9 and Comparative Examples 1 to 6 were coated on a PET substrate (100 mm × 100 mm), and pre-baked at 90°C for 100 seconds to form a coating film with a thickness of 6.0 μm. Then, a mirror projection alignment exposure device was used, and the exposure gap was set to 50 μm, and exposure was performed through a negative mask with a 20 μm linear pattern. The exposure amount was set to 60 mJ / cm 2 The exposed sample coating was developed in a 0.04 mass % tetramethylammonium hydroxide aqueous solution at 26°C for 40 seconds. Post-baking was performed at 90°C for 30 minutes to form a pattern. The adhesion of the pattern to the substrate was tested when the line width was 5μm, and the pattern integrity, solvent resistance, heat resistance and other properties were tested.

[0117] Evaluation criteria:

[0118] 1) Test adhesion: Use the hundred-grid method to test.

[0119] ○: The test result is 4B-3B.

[0120] △: The test result is 3B-2B.

[0121] ×: The test result is 2B or less.

[0122] 2) Pattern integrity: The pattern integrity was observed by scanning electron microscopy. The specific standards are as follows:

[0123] ○: The pattern is complete, and the edges are straight and clear.

[0124] △: The pattern is complete and the edges are jagged.

[0125] ×: The pattern is incomplete and the edges are unclear.

[0126] 3) Development accuracy

[0127] ○: Line width <6 μm.

[0128] △: Line width 6-10μm.

[0129] ×: Line width>10 μm.

[0130] 4) Evaluation of solvent resistance

[0131] The developed substrate was baked at 90°C for 60 min, the pattern thickness was measured using a film thickness meter, and the film thickness was measured. The substrate was immersed in an organic solvent (PGMEA) at 60°C for 2 min, dried again, and the film thickness was measured again. The solvent resistance was evaluated according to the following standards.

[0132] Evaluation Criteria

[0133] ○: Change in film thickness before and after immersion <1%.

[0134] △: The film thickness changes by 1%-3% before and after immersion.

[0135] ×: Change in film thickness before and after immersion > 3%.

[0136] 5) Heat resistance

[0137] The exposed and developed substrate pattern is baked again in an oven at 180°C for 60 minutes, then cooled to room temperature, taken out and checked for changes in the contact angle between the pattern and the substrate to determine whether the heat resistance is good or bad.

[0138] ×Contact angle reduction: 5°C or more.

[0139] △Contact angle reduction: 2-5℃.

[0140] ○Contact angle reduction: <2°C.

[0141] The specific evaluation results are listed in Table 1:

[0142] Table 1

[0143] Composition implementation / comparative example Adhesion Pattern integrity Development accuracy Solvent resistance Heat resistance Photosensitive resin composition Example 1 ○ ○ ○ ○ ○ Photosensitive resin composition Example 2 ○ ○ ○ △ ○ Photosensitive resin composition Example 3 ○ ○ ○ ○ ○ Photosensitive resin composition Example 4 ○ ○ ○ ○ ○ Photosensitive resin composition Example 5 ○ ○ ○ △ ○ Photosensitive resin composition Example 6 ○ ○ ○ ○ ○ Photosensitive resin composition Example 7 ○ ○ ○ ○ ○ Photosensitive resin composition Example 8 △ ○ ○ ○ ○ Photosensitive resin composition Example 9 ○ ○ ○ ○ ○ Photosensitive resin composition comparative example 1 △ △ × × ○ Photosensitive resin composition comparative example 2 × △ △ △ △ Photosensitive resin composition comparative example 3 △ △ × △ △ Photosensitive resin composition comparative example 4 × × × △ × Photosensitive resin composition comparative example 5 × × × × × Photosensitive resin composition comparative example 6 × × △ △ ×

[0144] As can be seen from the above table, the photocurable composition prepared by using the resin polymerizable composition provided by the present invention and the related auxiliary agents can show good curing effect even at a lower baking temperature during the illumination process. In addition, the cured film formed after the composition is cured has good solvent resistance and heat resistance. The development accuracy is high and the pattern is complete. As shown in the above table, the photosensitive resin composition embodiments 1, 3, 6 and 7 all show good application effects.

[0145] However, when a resin polymer obtained by copolymerization is used after using two specific monomers, or completely replacing the three monomers proposed in the present invention, and then preparing a composition with a similar formula, its application performance is significantly reduced, as shown in the photosensitive resin composition comparative examples 1 to 6 in the above table.

[0146] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A resin polymer, It is characterized in that The monomers forming the resin polymer include ethylenically unsaturated bond monomer compounds, and the ethylenically unsaturated bond monomer compounds include acrylic silicon ester monomer compounds, phenol oxygen monomer compounds with ethylenically unsaturated groups, and oxacycloalkane monomer compounds with ethylenically unsaturated groups.

2. The resin polymer according to claim 1, It is characterized in that In parts by weight, the ethylenically unsaturated bond monomer compound includes: 10 to 20 parts of acrylic acid silicone ester monomer compound; 20 to 30 parts of a phenolic oxide monomer compound having an ethylenically unsaturated group; and 20 to 30 parts of an oxacycloalkane monomer compound having an ethylenically unsaturated group.

3. The resin polymer according to claim 1 or 2, It is characterized in that The acrylic silicon ester monomer compound has a structure shown in general formula I, R 1 Selected from hydrogen and C 1 ~C 10 Any one of the alkyl groups of 2 , R 3 , R 4 Each independently selected from C 1 ~C 10 Straight chain alkyl, C 3 ~C 10 The branched alkyl and C 3 ~C 20 Any one of the cycloalkyl groups of Preferably, the R 1 Selected from hydrogen, C 1 ~C 6 Any one of the alkyl groups; preferably the R 2 , the R 3 , the R 4 Each independently selected from C 1 ~C 6 Straight chain alkyl, C 3 ~C 6 The branched alkyl and C 3 ~C 10 Any one of the cycloalkyl groups of Furthermore, preferably, the R 1 is selected from hydrogen, methyl, ethyl, propyl or butyl; preferably, R 2 , the R 3 , the R 4 each independently selected from methyl, ethyl, propyl, butyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; Furthermore, it is preferred that the acrylic silicon ester monomer compound is selected from the group consisting of: Any one or more of .

4. The resin polymer according to any one of claims 1 to 3, It is characterized in that The phenolic oxide monomer compound having an ethylenically unsaturated group has a structure shown in general formula II, R 5 Selected from C 2 ~C 20 A hydrocarbon group containing an ethylenically unsaturated bond; R 6 Selected from C 1 ~C 10 Acyl, C 1 ~C 10 Alkoxy acyl; Preferably, the R 5 Selected from C 2 ~C 10 A hydrocarbon group containing an ethylenically unsaturated bond; preferably said R 6 Selected from C 1 ~C 5 Acyl, C 1 ~C 5 Alkoxy acyl; Preferably, the R 5 is selected from vinyl, propenyl, butenyl, pentenyl or hexenyl; preferably, R 6 is selected from formyl, acetyl, propionyl, butyryl, valeryl, methoxyformyl, methoxyacetyl or methoxypropionyl; Furthermore, the phenolic oxide monomer compound having an ethylenically unsaturated group is preferably of formula (II-1): And / or formula (II-2) 5. The resin polymer according to any one of claims 1 to 4, It is characterized in that The oxacycloalkane monomer compound having an ethylenically unsaturated group has a structure shown in the general formula III, R 7 , R 8 Each independently selected from C 1 ~C 20 Alkylene, C 3 ~C 20 Cycloalkylene or C 6 ~C 20 A is selected from C 4 ~C 20 Cyclic alkenylene or C 2 ~C 20 Chain alkenylene; R 9 A three-membered epoxy group or a four-membered epoxy group; Preferably, the R 7 , the R 8 Each independently selected from C 1 ~C 10 Alkylene, C 3 ~C 10 Cycloalkylene or C 6 ~C 18 Preferably, A is selected from C 4 ~C 10 Cyclic alkenylene or C 3 ~C 10 The chain alkenylene; Preferably, the R 7 , the R 8 Each independently selected from C 1 ~C 6 Alkylene, C 3 ~C 6 Cycloalkylene or C 6 ~C 12 Preferably, A is selected from C 4 ~C 6 Cyclic alkenylene or C 3 ~C 6 The chain alkenylene; Furthermore, preferably, the R 7 , the R 8 Each is independently selected from any one of methylene, ethylene, propylene, butylene, isopropylene, isobutylene, isopentylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, phenylene, biphenylene, and naphthylene; preferably, A is selected from cyclobutenylene, cyclopentenylene, cyclohexenylene, propenylene, butenylene, pentenylene, hexenylene, isopropenylene, isobutenylene, or isopentenylene; Furthermore, it is preferred that the oxacycloalkane monomer compound having an ethylenically unsaturated group is selected from the group consisting of: Any one or more of .

6. The resin polymer according to any one of claims 1 to 5, It is characterized in that The weight average molecular weight of the resin polymer is 8,000 to 30,000, preferably 10,000 to 20,000.

7. The resin polymer according to any one of claims 1 to 6, It is characterized in that The acid value of the resin polymer is ≤10 mgKOH / g, and preferably the acid value of the resin polymer is ≤5 mgKOH / g.

8. The resin polymer according to any one of claims 1 to 7, It is characterized in that The ethylenically unsaturated bond monomer compound further includes any one or more of acrylate monomers, (meth) acrylic acid derivative monomers, and styrene derivative monomers. Preferably, the acrylic acid ester monomer is selected from any one or more of alkyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl methacrylate, 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, methyl methacrylate, ethyl methacrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, isooctyl methacrylate, cyclohexyl methacrylate, dicyclopentyl methacrylate, and isobornyl methacrylate; Preferably, the (meth)acrylic acid derivative monomer is selected from any one or more of (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furanyl(meth)acrylic acid, and β-styryl(meth)acrylic acid; Preferably, the styrene derivative monomer is selected from any one or more of styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, p-ethylstyrene and p-chlorostyrene.

9. A photosensitive resin composition, It is characterized in that In parts by weight, the photosensitive resin composition comprises 20 to 50 parts of a resin polymer, 0.1 to 10 parts of a photoinitiator and 1 to 25 parts of a photopolymerizable monomer, wherein the photoinitiator comprises a free radical photoinitiator and a photoacid generator, and the resin polymer is the resin polymer described in any one of claims 1 to 8.

10. The photosensitive resin composition according to claim 9, It is characterized in that The amount of the free radical photoinitiator is 0.01 to 1.0 wt % of the total amount of the photosensitive resin composition, preferably 0.1 to 0.5 wt %; Preferably, the free radical photoinitiator is selected from any one or more of benzophenone initiators, triazine initiators, dialkoxyacetophenone initiators, α-hydroxyalkyl phenone initiators, α-aminoalkyl phenone initiators, acylphosphine oxide initiators, benzophenone initiators, benzoin initiators, benzil initiators, heterocyclic aromatic ketone initiators, and oxime ester photoinitiators; Further, the free radical photoinitiator is preferably selected from benzophenone, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, diethoxyacetophenone, 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-oxyimino-1-phenylpropanone, 1,2-octanedione, 1-(4-phenylthio)phenyl-2(o-benzoyl oxime), 1-(9-ethyl)-6-(2-methylbenzoyl)carbazole-3-yl-1-(O-acetyl oxime), GGI-124, GGI-224, OXE-01, NCI-831, 2,4,5-triarylimidazole dimer, 4,4'-bis(diethylamino)benzophenone, 4,4'-dichlorobenzophenone, 2-methylthioxanthone, 2-isopropylthioxanthone ketone, dibenzosuberone, trichloroacetophenone, amyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-di(9-acridinyl)heptane, 1,3-di(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- any one or more of 2,4-bis(trichloromethyl)-6-(3-bromo-4-methoxy)phenylphenyl-s-triazine, 2,4-bis(trichloromethyl)-6-(2-bromo-4-methoxy)phenylphenyl-s-triazine, 4-benzoyl-4'-methyldimethyl sulfide, ethyl 4-dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2(o-ethoxycarbonyl)oxime; Preferably, the amount of the photoacid generator is 0.1 to 10 wt %, preferably 1 to 5 wt % of the total amount of the photosensitive resin composition; preferably, the photoacid generator is selected from any one or more of iodonium salts, sulfonium salts, imidosulfonate derivatives, dicarboximidosulfonates, oximesulfonates, diazo (sulfonic acid methyl) compounds, disulfonyl methylene hydrazine compounds, nitrobenzyl sulfonates, biimidazole compounds, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, and triazine derivatives; Preferably, the photoacid generator is selected from any one or more of triphenylsulfonium, salts of trifluoromethanesulfonic acid, triphenylsulfonium perfluorobutanesulfonate, D(L)-camphor-10-sulfonic acid triphenylsulfonium, N-hydroxyphthalimide toluenesulfonate, N-trifluoromethane yellow yloxy-1,8-naphthalene imine, and (Z)-4-methoxy-N-(toluenesulfonyloxy)iminophenylacetonitrile.

11. The photosensitive resin composition according to claim 9 or 10, It is characterized in that The photopolymerizable monomer is selected from any one or more of (meth) alkyl acrylate monomers, styrene monomers, unsaturated organic acids, unsaturated organic anhydrides, acrylamide monomers, and vinyl monomers; Preferably, the alkyl (meth)acrylate monomer is selected from any one or more of alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; Preferably, the styrene monomer is styrene and / or hydroxystyrene; Preferably, the unsaturated organic acid is maleic acid; Preferably, the unsaturated organic anhydride is maleic anhydride; Preferably, the acrylamide monomer is selected from any one or more of N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-hydroxymethylacrylamide, N-methylacrylamide, N-ethylmethacrylamide, N-isopropylmethacrylamide, N-hydroxymethylmethacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-dimethylmethacrylamide, and N,N-diethylmethacrylamide; Preferably, the vinyl monomer is selected from any one or more of N-vinyl pyrrolidone, N-vinyl formamide, N-vinylacetamide, and N-vinylimidazole.

12. Use of the photosensitive resin composition according to any one of claims 9 to 11, the use comprising applying the photosensitive resin composition to the preparation of protective films, interlayer insulating materials, and pattern transfer materials of electronic components.

Images