Photocurable resin composition and use thereof

Abstract

The application provides a photocuring resin composition and application thereof. The photocuring resin composition comprises, by weight parts, 45-65 parts of alkali-soluble resin, 35-50 parts of polymerized monomer and 2.7-5.0 parts of photoinitiator; the alkali-soluble resin is selected from one or more of compounds shown in general formula (I)-(IV). The alkali-soluble resin, the polymerized monomer and the photoinitiator are extremely easy to obtain a high solid content, low viscosity resist. Compared with other resists, for the production of the resist with the specific composition, only a small amount of organic solvent needs to be added to obtain a suitable coating glue solution, so that the VOC emission of the production process can be significantly reduced, and the cost of the organic solvent can be significantly reduced. The resist prepared by the above formula can meet the needs of the high-order semiconductor packaging field such as IC packaging board and the high-precision PCB manufacturing field of high frequency and high speed.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of light-cured resin, in particular to a light-cured resin composition and application thereof. BACKGROUND

[0002] Adding (meth)acrylate benzyl, styrene, styrene derivatives with better adhesion and rigidity as copolymer units in the alkali-soluble resin of the resist is conducive to improving the adhesion and resolution of the resist; meanwhile, adding a multifunctional monomer in the photopolymerizable monomer to improve the crosslinking density.

[0003] However, the resist obtained by the above method is hard and brittle, the development time and stripping time are greatly increased, the stripping sheet is too large to cause resist residue, and the dispersion during development is poor to cause more development agglomerates (scum). In addition, if the resist is too brittle, the etching resistance and plating resistance will also decrease, and the etching liquid or plating liquid will penetrate from the bottom of the resist (i.e. penetration plating) during the etching or plating process, thereby causing copper circuit damage, broken holes, short circuits and other problems, which will cause the yield of the resist to decrease when used by downstream PCB manufacturers, and also reduce the production efficiency.

[0004] In order to improve the stripping properties of the resist and the low circuit formation yield, the existing document (publication number CN101971097A) discloses a photosensitive resin composition containing 10-65 parts by mass of styrene and its derivatives, 5-55 parts by mass of (meth)acrylate polymerization units containing an alicyclic or heterocyclic group, and 15-50 parts by mass of a binder polymer copolymerized from (meth)acrylic acid, a photopolymerizable compound and a photopolymerization initiator, wherein the binder polymer is used as the main component of the resist material.

[0005] However, from the experimental results, the stripping properties of the resist have not been significantly improved (the stripping time in the prior art is usually 86-130 s). Moreover, in advanced technical fields such as packaging boards and the like, for example, 25 / 25 μm IC packaging substrates in mass production lines require an independent line adhesion (x: 5x μm) capability of 10-12 μm, and higher-order 10 / 10 μm IC packaging substrates in mass production lines require an independent line adhesion (x: 5x μm) capability of 6-7 μm. By comparison, it can be seen that the adhesion performance of the resist is not enough, and the measured data of the tightness of the equal line width and equal line spacing (x:x μm) is 12-20 μm, and the adhesion performance cannot meet the performance requirements of the resist in advanced technical fields such as the IC packaging substrate field. In addition, the existing document does not involve key parameters such as flexibility and plating resistance, but these performances are very important for improving the production yield.

[0006] For the production of the resist, the components need to be dissolved and diluted in an organic solvent to prepare a suitable glue solution with proper viscosity for coating, and the organic solvent needs to be removed by oven drying after coating, and the collected volatile organic compounds need to be collected and incinerated at high temperature by a regenerative oxidation furnace (RTO furnace) until the indicators are qualified before being discharged.

[0007] To reduce VOC emissions, the common measures taken by resist manufacturers include adjusting the synthesis process of the resin or the molecular weight of the resin while maintaining the chemical structure of the acrylate resin molecules. However, the above methods will affect the performance of the alkali-soluble resin itself.

[0008] In summary, it is of great significance to develop a high-solid, low-viscosity and excellent performance photocuring resin composition to improve precision and yield, reduce VOC emissions and reduce production costs. SUMMARY

[0009] The main purpose of the present application is to provide a photocuring resin composition and its application, to solve the problem of low precision of IC packaging substrate and PCB circuit caused by poor photosensitivity and resolution of existing photocuring resin composition, and large VOC emissions, high production cost in the preparation process of resist, and low yield of IC packaging substrate and PCB circuit caused thereby.

[0010] To achieve the above purpose, the present application provides a photocuring resin composition, which comprises, by weight: 45-65 parts of alkali-soluble resin, 35-50 parts of polymerized monomer, and 2.7-5.0 parts of photoinitiator; the alkali-soluble resin is selected from one or more of the compounds represented by general formula (I)-(IV):

[0011]

[0012]

[0013]

[0014]

[0015] R' is selected from C5-C 14 substituted or unsubstituted monocyclic carbocyclic alkyl, C5-C 14 substituted or unsubstituted bicyclic carbocyclic alkyl, C5-C 14 substituted or unsubstituted polycyclic carbocyclic alkyl, C5-C 14 substituted or unsubstituted monocyclic heterocyclic alkyl, C5-C 14 substituted or unsubstituted bicyclic heterocyclic alkyl, C5-C 14substituted or unsubstituted polycyclic heterocycloalkyl, and the bicyclic carbocycloalkyl and polycyclic carbocycloalkyl each have a fused ring structure or a bridged ring structure; R is selected from C1-C6 alkyl, C1-C3 alkoxy, C1-C3 alkylamino, hydroxyl or carboxyl; M represents C1-C3 alkylene or a heteroatom; R1, R2, R3, R4 and R5 are each independently selected from a hydrogen atom or a methyl group; Q is selected from unsubstituted aryl or heteroaryl, hydroxyl-substituted aryl or heteroaryl, amido-substituted aryl or heteroaryl, fluorine atom-substituted aryl or heteroaryl, cyano-substituted aryl or heteroaryl, amino-substituted aryl or heteroaryl, carbonyl-substituted aryl or heteroaryl, C1-C5 alkyl-substituted aryl or heteroaryl, or C1-C3 alkoxy-substituted aryl or heteroaryl; m represents any integer from 1 to 10; x1 corresponds to a content of the segment of 10-65 wt%, y1 corresponds to a content of the segment of 10-35 wt%, z1 corresponds to a content of the segment of 1-10 wt%, and w1 corresponds to a content of the segment of 0-55 wt%, in terms of a percentage content of the molecular weight of the compound represented by the general formula (I) or (II); and x2 corresponds to a content of the segment of 55-76 wt%, y2 corresponds to a content of the segment of 15-35 wt%, and w2 corresponds to a content of the segment of 2-10 wt%, in terms of a percentage content of the molecular weight of the compound represented by the general formula (III) or (IV).

[0016] To achieve the above object, the application further provides an application of the above-mentioned photo-curable resin composition in the field of photo-curing.

[0017] According to the technical scheme of the application, the x1 and x2 corresponding segments in the above-mentioned alkali-soluble resin have good flexibility, the w1 and w2 corresponding segments have good rigidity and hydrophobicity, the alkali-soluble resin composed of the flexible segment and the rigid segment with the above-mentioned specific structure can improve the flexibility, and thus the adhesion and the plating resistance of the photo-curable resin composition can be improved, so that the production yield of the PCB can be improved, and in particular, in a series of processes such as developing, plating and etching, which have certain pressure spraying, the resist line and the side edge morphology can be kept intact, so that the situation of broken line and short circuit can be significantly reduced; the introduction of the z1 and z2 corresponding segments can significantly improve the stripping performance of the photo-curable resin composition; and the introduction of the z1 corresponding segment and the y1 and y2 corresponding segments into the chemical structure of the alkali-soluble resin can significantly improve the plating resistance of the photo-curable resin composition. Compared with other ranges, the limitation of the weight percentage of each segment in the above-mentioned range is beneficial to improving the comprehensive performance such as the adhesion, the plating resistance and the stripping performance of the photo-curable resin composition.

[0018] In summary, the alkali-soluble resin, the polymerizable monomer and the photoinitiator provided by the present application can be used to easily obtain a resist with high solid content and low viscosity. Compared with other resists, only a small amount of organic solvent needs to be added to obtain a suitable coating glue solution for the production of the resist with the above-mentioned specific composition, thereby significantly reducing the VOC emission during the production process and significantly reducing the cost of organic solvents.

[0019] The resist prepared by using the above-mentioned formula can meet the needs of the high-order semiconductor packaging field such as IC packaging boards and the high-precision PCB manufacturing field of high frequency and high speed. BRIEF DESCRIPTION OF DRAWINGS

[0020] The drawings constituting a part of the specification of the present application are used to provide a further understanding of the present application, the illustrative embodiments of the present application and the description thereof are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings:

[0021] Figure 1 An infrared spectrum of the alkali-soluble resin A-2 is shown;

[0022] Figure 2 An SEM image (magnification of 1000 times) of the sample with a resolution of 8 μm in Example 2 is shown;

[0023] Figure 3 An SEM image (magnification of 1100 times) of the sample with an adhesion test of 8 μm in Example 2 is shown. DETAILED DESCRIPTION

[0024] It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other without conflict. The present application will be described in detail below with reference to the embodiments.

[0025] As described in the background, the existing photocurable resin composition has poor photosensitivity and resolution, which leads to low precision of IC packaging boards and PCB circuits, and the existing resist has a large VOC emission during the preparation process, high production cost and low yield of IC packaging boards and PCB circuits. In order to solve the above technical problems, the present application provides a photocurable resin composition, which comprises, by weight: 45-65 parts of an alkali-soluble resin, 35-50 parts of a polymerizable monomer and 2.7-5.0 parts of a photoinitiator; the alkali-soluble resin includes but is not limited to one or more of the compounds represented by general formulae (I)-(IV):

[0026]

[0027]

[0028]

[0029]

[0030] R' includes, but is not limited to, C5~C 14 Substituted or unsubstituted monocyclic carbocycloalkyl groups, C5-C 14 Substituted or unsubstituted bicyclic carbocycloalkyl groups, C5-C 14 Substituted or unsubstituted polycyclic carbocycloalkyl groups, C5-C 14 Substituted or unsubstituted monocyclic heterocyclic alkyl groups, C5-C 14 Substituted or unsubstituted bicyclic heterocyclic alkyl groups, C5-C 14 The substituted or unsubstituted polycyclic heterocyclic alkyl group, wherein the bicyclic carbocyclic alkyl group and the polycyclic carbocyclic alkyl group have a fused ring structure or a bridged ring structure, respectively; R1, R2, R3, R4 and R5 are independently including but not limited to hydrogen atoms or methyl groups; M represents a C1-C3 alkylene group or heteroatom; Q includes but is not limited to unsubstituted aryl or heteroaryl, hydroxyl-substituted aryl or heteroaryl, amide-substituted aryl or heteroaryl, fluorine-substituted aryl or heteroaryl, cyano-substituted aryl or heteroaryl, amino-substituted aryl or heteroaryl, carbonyl-substituted aryl or heteroaryl, C1-C5 alkyl-substituted aryl or heteroaryl, or C1-C3 alkoxy alkyl-substituted aryl or heteroaryl; m represents any integer from 1 to 10; based on the percentage of the molecular weight of the compound represented by general formula (I) or (II), the content of the segment corresponding to x1 is 10 to 65 wt%, the content of the segment corresponding to y1 is 10 to 35 wt%, the content of the segment corresponding to z1 is 1 to 10 wt%, and the content of the segment corresponding to w1 is 0 to 55 wt%; based on the percentage of the molecular weight of the compound represented by general formula (III) or (IV), the content of the segment corresponding to x2 is 55 to 76 wt%, the content of the segment corresponding to y2 is 15 to 35 wt%, and the content of the segment corresponding to w2 is 2 to 10 wt%.

[0031] The x1 and x2 corresponding segments in the above alkali-soluble resin provided by the present application have good flexibility, and the w1 and w2 corresponding segments have good rigidity and hydrophobicity. The alkali-soluble resin composed of the flexible segments and the rigid segments having the above specific structures can improve the flexibility of the alkali-soluble resin, thereby improving the adhesion and the plating resistance of the photocuring resin composition, so as to improve the production yield of the PCB. In particular, in the processes such as developing, plating and etching, which have certain pressure spraying, the resist lines and the side edge morphology can be kept intact, thereby significantly reducing the situation of broken lines and short circuits. The introduction of the z1 corresponding segment can significantly improve the stripping performance of the photocuring resin composition. Moreover, the introduction of the z1 and z2 corresponding segments and the y1 and y2 corresponding segments into the chemical structure of the alkali-soluble resin can significantly improve the plating resistance of the photocuring resin composition. Compared with other ranges, the limitation of the weight percentage of each segment in the above range is beneficial to improve the comprehensive performance such as the adhesion, the plating resistance and the stripping performance of the photocuring resin composition.

[0032] In summary, the above alkali-soluble resin provided by the present application is extremely easy to obtain a high solid content and low viscosity resist together with a polymerizable monomer and a photoinitiator. Compared with other resists, for the production of the resist having the above specific composition, only a small amount of organic solvent needs to be added to obtain a suitable coating glue solution for coating, thereby significantly reducing the VOC emission during the production process and significantly reducing the cost of the organic solvent. The resist prepared by using the above formula can meet the needs of the high-order semiconductor packaging field such as IC packaging board and the high-precision PCB manufacturing field of high frequency and high speed.

[0033] In a preferred embodiment, the content of the x1 corresponding segment is 15-43 wt% based on the percentage content of the molecular weight of the compound represented by the general formula (I) or (II), the content of the y1 corresponding segment is 22-29 wt%, the content of the z1 corresponding segment is 2-10 wt%, and the content of the w1 corresponding segment is 30-55 wt%. The content of each of x1, y1, z1 and w1 corresponding segment includes but is not limited to the above range, and the limitation of the content of each segment in the above range is beneficial to improve the flexibility of the alkali-soluble resin, thereby being beneficial to improve the adhesion, the plating resistance and the stripping performance of the photocuring resin composition, and simultaneously being beneficial to reduce the VOC emission during the production process of the resist and reduce the production cost.

[0034] In order to further improve the adhesion, plating resistance and stripping performance of the photocuring resin composition, and to further reduce the VOC emission during the production of the resist and to reduce the production cost, preferably, the content of the x1 corresponding segment is 20-43 wt% and the content of the y1 corresponding segment is 25-27 wt% and the content of the z1 corresponding segment is 2-8 wt% and the content of the w1 corresponding segment is 30-45 wt% based on the percentage content of the molecular weight of the compound represented by the general formula (I) or (II).

[0035] In a preferred embodiment, the content of the x2 corresponding segment is 61-73 wt% and the content of the y2 corresponding segment is 27-30 wt% and the content of the w2 corresponding segment is 2-9 wt% based on the percentage content of the molecular weight of the compound represented by the general formula (III) or (IV). The content of each of the x2, y2 and w2 corresponding segments includes but is not limited to the above range, and limiting them in the above range is advantageous to improve the flexibility of the alkali-soluble resin, and further advantageous to improve the adhesion and plating resistance of the photocuring resin composition, and simultaneously advantageous to reduce the VOC emission during the production of the resist and to reduce the production cost.

[0036] In order to further improve the adhesion and plating resistance of the photocuring resin composition, and to further reduce the VOC emission during the production of the resist and to reduce the production cost, preferably, the content of the x2 corresponding segment is 62-73 wt% and the content of the y2 corresponding segment is 28-30 wt% and the content of the w2 corresponding segment is 2-8 wt% based on the percentage content of the molecular weight of the compound represented by the general formula (III) or (IV).

[0037] In a preferred embodiment, the weight ratio of the alkali-soluble resin, the polymerized monomer and the photoinitiator is (50-65):(40-48):(3.0-4.6). When the alkali-soluble resin includes but is not limited to the compound represented by the general formula (I) or (II), the weight ratio of the alkali-soluble resin, the polymerized monomer and the photoinitiator includes but is not limited to the above range, and limiting them in the above range is advantageous to improve the photosensitivity of the photocuring resin composition, and simultaneously advantageous to improve the stripping performance and the dispersibility of the developer, thereby advantageous to improve the resolution of the finally prepared IC packaging board and PCB and the like.

[0038] In a preferred embodiment, in the compound represented by the general formula (I) or (III), R' includes but is not limited to any one of the following structures:

[0039]

[0040] wherein, G represents a carbon atom or a nitrogen atom, M represents a C1-C3 alkylene group or a heteroatom, and n represents an arbitrary integer of 1-10; more preferably, represents

[0041] In general formula (II) or (IV), x1 and x2 correspond to repeating units in the chain segment each independently includes, but is not limited to, any one of the following structures:

[0042]

[0043] Q includes, but is not limited to, any one of the following structures:

[0044]

[0045]

[0046] R' and Q each independently include, but are not limited to, the above ranges, and introduction of the above preferred types of R' groups and Q groups into the chemical structure of the alkali-soluble resin is advantageous for further exerting the flexibility of the x1 and x2 corresponding chain segments, and the rigidity and hydrophobicity of the w1 and w2 corresponding chain segments, and is further advantageous for further improving the adhesion and plating resistance of the photocurable resin composition, thereby being further advantageous for further improving the production yield of the PCB, especially in a series of processes such as development, plating, and etching, which have a certain pressure spray, and is further advantageous for further maintaining the resist line and side edge morphology intact, thereby being further advantageous for further significantly reducing the case of broken lines and short circuits.

[0047] In a preferred embodiment, R1 is a hydrogen atom or a methyl group, R2 is a methyl group, R3 and R4 are each a hydrogen atom, R5 is a hydrogen atom; M is a carbon atom, and n is 1; R' is selected from x2 corresponds to the chain segment is selected from; Q is selected from

[0048] Compared with the alkali-soluble resin of other structures, the limitation of R1, R2, R3, R4, and M in the above ranges and the introduction of the above preferred types of R' groups and Q groups into the chemical structure of the alkali-soluble resin are advantageous for further exerting the flexibility of the x1 and x2 corresponding chain segments, and the rigidity and hydrophobicity of the w1 and w2 corresponding chain segments, and are further advantageous for further improving the adhesion and plating resistance of the photocurable resin composition, thereby being further advantageous for further improving the production yield of the PCB, especially in a series of processes such as development, plating, and etching, which have a certain pressure spray, and are further advantageous for further maintaining the resist line and side edge morphology intact, thereby being further advantageous for further significantly reducing the case of broken lines and short circuits.

[0049] In a preferred embodiment, the acid value of the alkali-soluble resin is 120-250 mgKOH / g; the molecular weight distribution index of the alkali-soluble resin is ≤2.5. The acid value of the alkali-soluble resin includes but is not limited to the above range, and limiting it within the above range is conducive to improving alkali solubility, thereby facilitating the shortening of developing time and stripping time; at the same time, it is also conducive to improving the resolution of the photo-curable resin composition; the molecular weight distribution index of the alkali-soluble resin includes but is not limited to the above range, and limiting it within the above range is conducive to improving the resolution of the subsequently prepared resist, thereby facilitating the improvement of the precision of IC package boards and PCBs and the like. In order to further improve alkali solubility, thereby further shortening developing time and stripping time, the acid value of the alkali-soluble resin is preferably 145-176 mgKOH / g.

[0050] In a preferred embodiment, the polymerized monomer includes but is not limited to one or more of ethoxylated (propoxylated) nonyl phenol acrylate monomers, ethoxylated (propoxylated) bisphenol A di(meth)acrylate monomers, polyethylene glycol (propylene glycol) di(meth)acrylate monomers, and (meth)acrylate monomers containing an ethoxylated (propoxylated) urethane structure. The polymerized monomer includes but is not limited to the above categories, and limiting it within the above category range is conducive to improving the photosensitivity of the photo-curable resin composition, while at the same time being conducive to improving stripping performance and the dispersibility of the developing solution, thereby facilitating the improvement of the resolution of the finally prepared IC package boards and PCBs and the like.

[0051] In order to further improve the photosensitivity of the photo-curable resin composition, thereby further improving the resolution of the IC package boards and PCBs and the like, preferably, the polymerized monomer includes but is not limited to ethoxylated bisphenol A di(meth)acrylate monomers, more preferably 4-ethoxylated bisphenol A di(meth)acrylate and / or 10-ethoxylated bisphenol A di(meth)acrylate.

[0052] In order to further improve stripping performance and the dispersibility of the developing solution, thereby facilitating the further improvement of the resolution of the finally prepared IC package boards and PCBs and the like, preferably, the polymerized monomer includes but is not limited to ethoxylated (propoxylated) nonyl phenol acrylate monomers, more preferably 4-ethoxylated nonyl phenol acrylate and / or 8-ethoxylated nonyl phenol acrylate.

[0053] In order to make circuit patterns and PCB manufacturing ends and the like with higher precision, laser direct imaging (LDI) using digital data to directly irradiate active light images is now commonly used instead of the traditional photomask exposure method, and i-rays (355 nm) or h-rays (405 nm) are used as light sources.

[0054] In order to improve the photosensitivity of the photosensitive resin composition to the laser light source used for exposure, in a preferred embodiment, the photoinitiator includes, but is not limited to, a mixed system of triarylimidazole dimer derivatives and a sensitizer. Compared with using triarylimidazole dimer derivatives alone as the photoinitiating system, using the above-mentioned kind of mixed system is beneficial to simultaneously improving the photosensitivity and resolution of the photocurable resin composition.

[0055] In order to further improve the photosensitivity and resolution of the photocurable resin composition, preferably, the weight ratio of triarylimidazole dimer derivatives to the sensitizer is (2.5-4.2):(0.2-0.8).

[0056] In a preferred embodiment, the photoinitiator includes, but is not limited to, one or more of 2-(o-chlorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl) imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenyl imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenyl imidazole dimer, 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole; and, the sensitizer includes, but is not limited to, one or more of anthracene compounds, pyrazoline compounds, coumarin compounds, benzil derivatives, acridine derivatives, oxazole compounds. The types of photoinitiator and sensitizer include, but are not limited to, the above-mentioned range, and limiting them within the above-mentioned type range is beneficial to further improving the photosensitivity and resolution of the photocurable resin composition.

[0057] In order to further improve the photosensitivity and resolution of the photocurable resin composition, more preferably, the photoinitiator includes, but is not limited to, 2-(o-chlorophenyl)-4,5-diphenyl imidazole dimer; and, the sensitizer includes, but is not limited to, one or more of thioxanthone, isopropyl thioxanthone, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, benzoin phenyl ether, benzophenone, benzoin methyl ether, N,N'-tetramethyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2,3-dimethylanthraquinone, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzil dimethyl ketal, 9-phenylacridine, 1,7-bis(9,9'-acridinyl)heptane, N-phenylglycine.

[0058] In a preferred embodiment, the photocurable resin composition further includes 0.001 to 1 wt% of a polymerization inhibitor, based on the weight percentage of the photocurable resin composition. The amount of the polymerization inhibitor includes but is not limited to the above range, and limiting it within the above range is advantageous for better synergistic effects of the components in the photocurable resin composition, thereby advantageously achieving better levels of photosensitivity, resolution, adhesion, and shape of the subsequently produced resist.

[0059] In order to further simultaneously satisfy the requirements of photosensitivity, resolution, adhesion, and shape of the subsequently produced resist for IC package substrates, PCBs, and the like, preferably, the polymerization inhibitor includes but is not limited to one or more of phenol compounds, quinone compounds, tetramethyl nitroxyl piperidine compounds, and nitrosophenyl hydroxylamine aluminum salt compounds.

[0060] In order to further simultaneously satisfy the requirements of photosensitivity, resolution, adhesion, and shape of the subsequently produced resist for IC package substrates, PCBs, and the like, more preferably, the polymerization inhibitor includes but is not limited to one or more of p-methoxyphenol, 4-ethyl-6-tert-butylphenol, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, catechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, 3,5-di-tert-butylcatechol, resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, 1,4-hydroquinone, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, pyrogallol, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 2,2-methylenebis(4-methyl-6-tert-butylphenol), nitrosophenyl hydroxylamine aluminum salt.

[0061] In a preferred embodiment, the photocurable resin composition further includes 0.5 to 5.0 wt% of an additive, based on the weight percentage of the photocurable resin composition. The amount of the additive includes but is not limited to the above range, and limiting it within the above range is advantageous for better effects of the additive. Preferably, the additive includes but is not limited to one or more of a color former, a color developer, a plasticizer, a photothermal stabilizer, an adhesion promoter, a leveling agent, and a defoaming agent.

[0062] In a preferred embodiment, the photocuring resin composition comprises, by weight parts: 50-65 parts of alkali-soluble resin, 40-48 parts of polymerized monomer, 2.5-4.2 parts of triarylimidazole dimer derivative, 0.2-0.8 parts of sensitizer, 0.001-0.1 parts of polymerization inhibitor, 0.2-1.5 parts of recessive dyeing agent, and 0.01-0.1 parts of dominant dyeing agent.

[0063] The photocuring resin composition provided by the present application has excellent adhesion, plating resistance, and stripping performance, and can be applied to the production of IC package boards and PCBs to achieve high production yield, and in particular, can significantly reduce the occurrence of broken lines and short circuits. The resist prepared by using the above-mentioned formula can meet the needs of the high-level semiconductor packaging field such as IC package boards, and the high-precision PCB manufacturing field of high frequency and high speed.

[0064] The present application also provides the use of the above-mentioned photocuring resin composition in the field of photocuring.

[0065] The photocuring resin composition provided by the present application has excellent adhesion, plating resistance, and stripping performance, and can be applied to the production of IC package boards and PCBs to achieve high production yield, and in particular, can significantly reduce the occurrence of broken lines and short circuits. The resist prepared by using the above-mentioned formula can meet the needs of the high-level semiconductor packaging field such as IC package boards, and the high-precision PCB manufacturing field of high frequency and high speed.

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

[0067] Preparation method of alkali-soluble resin

[0068] The alkali-soluble resins A-1 to A-17 are prepared by using the monomer types and amounts shown in Tables 1 and 2, wherein the weight percentage of each monomer corresponding to the respective chain segment in the molecular weight of the alkali-soluble resin is represented by x, y, z, and w, respectively. The alkali-soluble resins A-18 to A-23 are prepared by using the monomer types and amounts shown in Table 3, wherein the weight percentage of each monomer corresponding to the respective chain segment in the molecular weight of the alkali-soluble resin is represented by x, y, z, and w, respectively, and the chemical structures of the alkali-soluble resins A-18 to A-23 do not satisfy the general formula in the present application.

[0069] The corresponding monomers in Table 1 to Table 3 were mixed uniformly according to the weight ratio (total 100 g) for standby, and mixed with 2.0 g of photoinitiator AIBN, 65 g of butanone, and 10 g of ethanol to obtain a mixed solution, which was dissolved by stirring; part of the mixed solution with a mass fraction of 35% was added to a three-necked flask with nitrogen protection and condensation reflux device through a peristaltic pump, and the oil bath was heated to 80°C. After stirring for 1 h, the remaining mixed solution was added dropwise, and the addition was completed within 3 h. After continuing to heat for 4 h, the temperature was increased to 90°C, and 5 g of butanone solution containing 0.2 g of initiator was added twice with an interval of 1 h. After the dropwise addition was completed, the temperature was maintained for 2 h with stirring, and the reaction was terminated to obtain the alkali-soluble resin A-1 to A-23.

[0070] The infrared spectrum of the alkali-soluble resin A-2 prepared above is shown in Figure 1

[0071] Table 1

[0072]

[0073] Table 2

[0074]

[0075] Table 3

[0076]

[0077] The weight average molecular weight, molecular weight distribution index, and solid content of the alkali-soluble resins A-1 to A-23 prepared above were tested by GPC, and the test results are shown in Tables 4, 5, and 6, respectively.

[0078] Table 4

[0079] Alkali-soluble resin No. A-1 A-2 A-3 A-4 A-5 A-6 A-7 Solid content (%) 55.4 56.1 55.7 55.3 55.2 55.3 55.6 Viscosity (mPa-s) 2076 1344 1436 1377 2135 1209 1221 Molecular weight distribution index 1.7 1.7 1.6 1.5 1.6 1.7 1.5 Weight average molecular weight 35000 38000 37000 34000 37000 36000 35000

[0080] Table 5

[0081]

[0082] Table 6

[0083] Alkali-soluble resin No. A-18 A-19 A-20 A-21 A-22 A-23 Solid content (%) 55.7 55.3 55.4 55.2 55.4 55.5 Viscosity (mPa-s) 1407 1324 1279 4316 1473 10680 Molecular weight distribution index 1.7 1.6 1.6 1.9 1.5 1.6 Weight average molecular weight 36000 34000 33000 31000 37000 35000

[0084] The components were mixed according to the proportions shown in Tables 7, 8, and 9 below, 40 parts by weight of acetone was added, and then stirred until the components were completely dissolved to prepare a resin composition solution with a solid content of 40% for standby. The solution was uniformly coated on the surface of a PET support film with a thickness of 15 μm using a coating machine, placed in an oven at 90°C for 10 min to form a dry film resist layer with a thickness of 25 μm, which appeared blue-green under a yellow light. Then, a polyethylene film protective layer with a thickness of 20 μm was attached to the surface to obtain a 3-layer resist. ​

[0085] The types, sources and corresponding numbers of the polymerization monomers, photoinitiators and additives used in the above all examples and comparative examples of the present application are as follows:

[0086] (1) Polymerization monomers:

[0087] B-1: (4) Ethoxylated bisphenol A diacrylate, molecular weight 512 (Shanghai MerSource) ;

[0088] B-2: (10) Ethoxylated bisphenol A diacrylate, molecular weight 804 (Shanghai MerSource) ;

[0089] B-3: Polyethylene glycol (200) dimethacrylate, molecular weight 336 (Shanghai MerSource) ;

[0090] B-4: (8) Ethoxylated nonyl phenol acrylate, molecular weight 626 (Sartomer) ;

[0091] B-5: (3) Ethoxylated trimethylolpropane triacrylate, molecular weight 428 (Sartomer) ;

[0092] (2) Photoinitiators:

[0093] C-1: 2,2'-bis(2-chlorophenyl)-4,4'-5,5'-tetraphenyl-1,1'-imidazole (Changzhou Qiangli Electronic New Material) ;

[0094] C-2: 9,10-dibutoxyanthracene (DBA) ;

[0095] (3) Additives:

[0096] D-1: 4-tert-butyl catechol;

[0097] D-2: Brilliant green pigment (Shanghai Bailingwei Chemical Technology Co., Ltd.) ;

[0098] D-3: Leuco crystal violet (Shanghai Bailingwei Chemical Technology Co., Ltd.) ;

[0099] D-4: p-methylbenzenesulfonamide (Shanghai Tixi'ai Chemical Industry).

[0100] Table 7

[0101]

[0102] Table 8

[0103]

[0104] Table 9

[0105]

[0106] The following describes the sample preparation method (including film lamination, exposure, development, copper electroplating) of the examples and comparative examples of the present application, the sample evaluation method, and the evaluation results.

[0107] (1) Sample preparation method

[0108]

Film lamination

[0109]

Exposure

[0110]

Development

[0111]

Electroplating

[0112]

Stripping

[0113]

Etching

[0114] (2) Evaluation method

[0115]

Sensitivity Evaluation

[0116]

Resolution Evaluation

[0117]

Adhesion Evaluation

[0118]

Flexibility Evaluation

[0119] Criteria: ○ indicates 2 mm without cracking; Δ indicates 3 to 4 mm without cracking; and × indicates 5 mm or more without cracking.

[0120]

Removal Speed Evaluation

[0121]

Plating resistance evaluation

[0122] (3) Performance evaluation results of photosensitivity, resolution, adhesion, flexibility, stripping speed, and plating resistance (see Tables 10 to 12)

[0123] Table 10

[0124] Example 1 2 3 4 5 6 7 Sensitivity (mJ / cm 2 ) 40 40 40 40 32 50 40 Adhesion force / μm 9 8 8 9 10 10 10 Resolution / μm 7 8 9 9 9 9 10 Flexibility rating ○ ○ ○ ○ ○ ○ ○ Plating resistance Good Good Good Good Good Good Good Good 61 59 58 62 67 56 50

[0125] Table 11

[0126] Good 8 9 10 11 12 13 14 15 16 17 Sensitivity (mJ / cm 2 ) 40 33 40 50 50 40 40 40 40 40 Good 8 10 8 10 9 7 8 9 9 9 Good 7 10 9 9 10 8 8 8 9 9 Good ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Good Good Good Good Good Good Good Good Good Good Good Good 53 67 52 51 56 65 53 52 53 54

[0127] Table 12

[0128] Good 1 2 3 4 5 6 7 Sensitivity (mJ / cm 2 )]]> 40 40 40 40 40 40 33 Good 12 13 7 13 15 15 16 Example 12 10 13 12 13 15 12 Adhesion force / μm ○ ○ △ ○ ○ △ ○ Resolution / μm Flexibility rating Plating resistance Good Good Good Good Good Good 89 121 121 52 51 54 51

[0129] Good and Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good Good respectively show the SEM images of the samples corresponding to the resolution and adhesion tests of the photocuring resin composition prepared in Example 2 at 8 μm.

[0130] From the above description, it can be seen that the above-described embodiments of the present application achieve the following technical effects:

[0131] By comparing Examples 1 to 17 and Comparative Examples 1 and 2, it can be seen that in Examples 1 to 17, a photocuring resin composition with good photosensitivity, excellent resolution and adhesion performance, good flexibility and plating resistance, and fast stripping speed is obtained, and the amount of organic solvent required for preparation of the glue solution and coating process is extremely small. The photocuring resin composition can meet the requirements of high-precision PCB manufacturing, precision, and yield performance in the field of high-order semiconductor packaging such as IC packaging boards, and high frequency and high speed, and if the photocuring resin composition is applied to the preparation of a resist, VOC emissions during the production process can be greatly reduced, and the cost of raw materials related to organic solvents can be greatly reduced.

[0132] Compared with Example 1, the film removal time of Comparative Example 1 is too long, which seriously affects the production efficiency of high-precision PCBs such as IC packaging boards, and the resolution and adhesion of the product do not meet the requirements of the production of high-precision PCBs such as IC packaging boards, that is, the resolution and adhesion test results are not more than 10 μm, which is slightly deviated, and the performance of the photosensitive resist resin composition cannot meet the requirements of the production of high-precision PCBs such as IC packaging boards. In addition, the formula contains a high content of methacrylic acid and styrene, and the glass transition temperature of the polymer corresponding to methacrylic acid and styrene is very high. At the same time, high acid and high benzene can improve the plating resistance.

[0133] Comparing Example 2 and Comparative Example 2, Example 1 and Comparative Example 3, and Example 8 and Comparative Example 4, respectively, and combining the comprehensive performance of the photocuring resin composition given in the table, it can be seen that the x1 corresponding segment in the alkali-soluble resin provided in the present application has good flexibility, the w1 corresponding segment has good rigidity and hydrophobicity, the alkali-soluble resin composed of the flexible segment and the rigid segment with the above specific structure can improve its flexibility, thereby improving the adhesion and plating resistance of the photocuring resin composition, thereby improving the production yield of the PCB, especially in a series of processes with certain pressure spraying such as development, plating and etching, the resist line and side edge morphology can be kept intact, thereby significantly reducing the situation of broken line and short circuit; the introduction of the z1 corresponding segment can significantly improve the film removal performance of the photocuring resin composition; and the introduction of the z1 corresponding segment and the y1 corresponding segment into the chemical structure of the alkali-soluble resin can significantly improve the plating resistance of the photocuring resin composition. Compared with other ranges, limiting the weight percentage content of each segment in the above range is beneficial to improve the comprehensive performance of the photocuring resin composition such as adhesion, plating resistance, film removal performance, etc.

[0134] Comparing Examples 2, 14 and 15, the content of each of x1, y1, z1 and w1 corresponding segment includes but is not limited to the preferred range of the present application, and limiting it in the preferred range of the present application is beneficial to improve the flexibility of the alkali-soluble resin, thereby improving the adhesion, plating resistance and film removal performance of the photocuring resin composition, and also beneficial to reduce the VOC emission amount in the resist production process and reduce the production cost.

[0135] Comparing Examples 8, 16 and 17, the content of each of x2, y2 and w2 corresponding segment includes but is not limited to the preferred range of the present application, and limiting it in the preferred range of the present application is beneficial to improve the adhesion and plating resistance of the photocuring resin composition, and also for further reducing the VOC emission amount in the resist production process and reducing the production cost.

[0136] It should be noted that the terms "first", "second", and the like in the description and in the claims of the present application are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the present application described herein are, for example, capable of orderly execution or performance.

[0137] The preferred embodiments of the application are described above in detail. The application is not limited to the embodiments described above, but can vary and be modified in various ways. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the application should be included in the scope of the protection of the application.

Claims

1. A photocurable resin composition, characterized by, The photocurable resin composition comprises, by weight parts, 45-65 parts of an alkali-soluble resin, 35-50 parts of a polymerized monomer, and 2.7-5.0 parts of a photoinitiator; The alkali-soluble resin is selected from one or more of the compounds represented by general formulas (I)-(IV): （I）， (I), (II), (III), (VI), and (VII). R' is selected from C5~C 14 Substituted or unsubstituted monocyclic carbocycloalkyl groups, C5-C 14 Substituted or unsubstituted bicyclic carbocycloalkyl groups, C5-C 14 Substituted or unsubstituted polycyclic carbocycloalkyl groups, C5-C 14 Substituted or unsubstituted monocyclic heterocyclic alkyl groups, C5-C 14 Substituted or unsubstituted bicyclic heterocyclic alkyl groups, C5-C 14 The substituted or unsubstituted polycyclic heterocyclic alkyl groups, wherein the bicyclic carbocycloalkyl group and the polycyclic carbocycloalkyl group respectively have a fused ring structure or a bridged ring structure; R is selected from C1-C6 alkyl, C1-C3 alkoxy, C1-C3 alkylamino, hydroxyl, or carboxyl; M represents C1-C3 alkylene or a heteroatom; R1, R2, R3, R4, and R5 are each independently selected from a hydrogen atom or a methyl group; Q is selected from an unsubstituted aryl or heteroaryl group, a hydroxyl-substituted aryl or heteroaryl group, an amido-substituted aryl or heteroaryl group, a fluorine atom-substituted aryl or heteroaryl group, a cyano-substituted aryl or heteroaryl group, an amino-substituted aryl or heteroaryl group, a carbonyl-substituted aryl or heteroaryl group, a C1-C5 alkyl-substituted aryl or heteroaryl group, or a C1-C3 alkoxy-substituted aryl or heteroaryl group; m represents any integer from 1-10; x1 corresponds to a content of 10-65 wt% of the segment, y1 corresponds to a content of 10-35 wt% of the segment, z1 corresponds to a content of 1-10 wt% of the segment, and w1 corresponds to a content of 0-55 wt% of the segment, in percentage of the molecular weight of the compound represented by general formula (I) or (II); x2 corresponds to a content of 55-76 wt% of the segment, y2 corresponds to a content of 15-35 wt% of the segment, and w2 corresponds to a content of 2-10 wt% of the segment, in percentage of the molecular weight of the compound represented by general formula (III) or (IV).

2. The photocurable resin composition according to claim 1, characterized by x1 corresponds to a content of 15-43 wt% of the segment, y1 corresponds to a content of 22-29 wt% of the segment, z1 corresponds to a content of 2-10 wt% of the segment, and w1 corresponds to a content of 30-55 wt% of the segment, in percentage of the molecular weight of the compound represented by general formula (I) or (II).

3. The photocurable resin composition according to claim 1, characterized by x1 corresponds to a content of 20-43 wt% of the segment, y1 corresponds to a content of 25-27 wt% of the segment, z1 corresponds to a content of 2-8 wt% of the segment, and w1 corresponds to a content of 30-45 wt% of the segment, in percentage of the molecular weight of the compound represented by general formula (I) or (II).

4. The photocurable resin composition according to claim 1, characterized by x2 corresponds to a content of 61-73 wt% of the segment, y2 corresponds to a content of 27-30 wt% of the segment, and w2 corresponds to a content of 2-9 wt% of the segment, in percentage of the molecular weight of the compound represented by general formula (III) or (IV).

5. The photocurable resin composition according to claim 1, wherein x2 corresponds to a content of 62-73 wt% of the segment, y2 corresponds to a content of 28-30 wt% of the segment, and w2 corresponds to a content of 2-8 wt% of the segment, in percentage of the molecular weight of the compound represented by general formula (III) or (IV).

6. The photocurable resin composition according to claim 2, wherein The weight ratio of the alkali-soluble resin, the polymerized monomer, and the photoinitiator is (50-65):(40-48):(3.0-4.6).

7. The photocurable resin composition according to claim 1, wherein The compound of the general formula (I) or (III) is selected from any one of the following structures: 、 、 、 、 、 、 ； wherein, G represents a carbon atom or a nitrogen atom, M represents a C1-C3 alkylene group or a heteroatom, and n represents an arbitrary integer of 1-10. In the general formula (II) or (IV), x1and x2correspond to the repeating units in the segment each independently is selected from any one of the following structures: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 ； The Q is selected from any one of the following structures: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 。 8. The photocurable resin composition according to claim 7, wherein representative , , , or .

9. The photocurable resin composition according to claim 7, wherein The R1 is a hydrogen atom or a methyl group, the R2 is a methyl group, the R3 and the R4 are both hydrogen atoms, and the R5 is a hydrogen atom. Said R' is selected from , , , or ; The x2 corresponding segment selected from; ; Q is selected from , , , , , , , or .

10. The photocurable resin composition according to claim 1, characterized by The acid value of the alkali-soluble resin is 145-176 mgKOH / g.

11. The photocurable resin composition according to claim 10, characterized in that, The acid value of the alkali-soluble resin is 145-176 mgKOH / g.

12. The photocurable resin composition according to any one of claims 1 to 11, characterized by, The polymerized monomer is selected from one or more of ethoxylated nonyl phenol acrylate monomers, propoxylated nonyl phenol acrylate monomers, ethoxylated propoxylated nonyl phenol acrylate monomers, ethoxylated bisphenol A diacrylate monomers, propoxylated bisphenol A diacrylate monomers, ethoxylated propoxylated bisphenol A diacrylate monomers, ethoxylated bisphenol A dimethacrylate monomers, propoxylated bisphenol A dimethacrylate monomers, ethoxylated propoxylated bisphenol A dimethacrylate monomers, polyethylene glycol diacrylate monomers, polypropylene glycol diacrylate monomers, polyethylene glycol propylene glycol diacrylate monomers, polyethylene glycol dimethacrylate monomers, polypropylene glycol dimethacrylate monomers, polyethylene glycol propylene glycol dimethacrylate monomers, acrylate monomers containing an ethoxylated urethane structure, acrylate monomers containing a propoxylated urethane structure, acrylate monomers containing an ethoxylated propoxylated urethane structure, methacrylate monomers containing an ethoxylated urethane structure, methacrylate monomers containing a propoxylated urethane structure, and methacrylate monomers containing an ethoxylated propoxylated urethane structure.

13. The photocurable resin composition according to claim 12, characterized in that, The photoinitiator is selected from a mixed system of a triarylimidazole dimer derivative and a sensitizer.

14. The photocurable resin composition according to claim 13, characterized by The weight ratio of the triarylimidazole dimer derivative to the sensitizer is (2.5-4.2):(0.2-0.8).

15. The photocurable resin composition according to claim 13, wherein The photoinitiator is selected from one or more of 2-(o-chlorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl) imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenyl imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenyl imidazole dimer, 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole; and the sensitizer is selected from one or more of anthracene compounds, pyrazoline compounds, coumarin compounds, benzil derivatives, acridine derivatives, and oxazole compounds.

16. The photocurable resin composition according to claim 15, characterized by The photoinitiator is selected from one or more of 2-(o-chlorophenyl)-4,5-diphenyl imidazole dimer; and, the sensitizer is selected from one or more of thioxanthone, isopropyl thioxanthone, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2,3-dimethylanthraquinone, benzil dimethyl ketal, 9-phenylacridine, 1,7-bis(9,9'-acridinyl)heptane.

17. The photocurable resin composition according to claim 13, wherein The photopolymerizable resin composition further comprises 0.001-1 wt% of a polymerization inhibitor, based on the weight percentage of the photopolymerizable resin composition.

18. The photocurable resin composition according to claim 17, characterized by The polymerization inhibitor is selected from one or more of phenol compounds, quinone compounds, tetramethyl nitroxyl radical piperidine compounds, and nitroso phenyl hydroxylamine aluminum salt compounds.

19. The photocurable resin composition according to claim 18, characterized by The polymerization inhibitor is selected from one or more of p-methoxyphenol, 4-ethyl-6-tert-butylphenol, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, catechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, 3,5-di-tert-butylcatechol, resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, 1,4-hydroquinone, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, pyrogallol, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 2,2-methylenebis(4-methyl-6-tert-butylphenol), nitroso phenyl hydroxylamine aluminum salt.

20. The photocurable resin composition according to claim 17, wherein The photopolymerizable resin composition further comprises 0.5-5.0 wt% of an additive, based on the weight percentage of the photopolymerizable resin composition.

21. The photocurable resin composition according to claim 20, wherein The additive is selected from one or more of color developers, color formers, plasticizers, photothermal stabilizers, adhesion promoters, leveling agents, defoamers.

22. The photocurable resin composition according to claim 20, wherein The photopolymerizable resin composition comprises, by weight parts: 50-65 parts of the alkali-soluble resin, 40-48 parts of the polymerizable monomer, 2.5-4.2 parts of the triarylimidazole dimer derivative, 0.2-0.8 parts of the sensitizer, 0.001-0.1 parts of the polymerization inhibitor, 0.2-1.5 parts of the recessive color former, and 0.01-0.1 parts of the dominant color former.

23. Use of the photopolymerizable resin composition of any one of claims 1-22 in the field of photopolymerization.

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