Photosensitive resin composition, photosensitive resin film and electronic component

Abstract

The present invention relates to a photosensitive resin composition, a photosensitive resin film and an electronic component, and belongs to the technical field of printed circuit boards. The photosensitive resin composition at least includes: an alkali-soluble resin as component A, a photosensitive polymerizable monomer as component B, an epoxy resin as component C, a curing agent as component D, an inorganic filler as component E and a photoinitiator as component F; wherein the alkali-soluble resin as component A is a rigid epoxy acrylic resin containing a carboxyl group, and the epoxy resin as component C is obtained by compounding, including a rigid epoxy resin Ca component and a flexible epoxy resin Cb component; at the same time, the mass dosage of the AC component satisfies the following relationship: 15>(A+Ca) / Cb>2.5. The present invention obtains good flexibility and thermal properties by rationally proportioning the rigid component and the flexible component; the resolution is improved, and the window refinement performance is significantly improved; at the same time, the sensitivity is significantly improved, the exposure energy threshold is effectively reduced, and the production cost is greatly reduced.

Description

Technical Field

[0001] The invention relates to a photosensitive resin composition, a photosensitive resin film and an electronic component, belonging to the technical field of printed circuit boards. Background Art

[0002] With the demand for higher performance, miniaturization, and lightweight electronic devices, the high integration of semiconductor components is constantly advancing, and the demand for higher density and higher precision of semiconductor elements, semiconductor packages, printed circuit boards, etc. that constitute semiconductor components is constantly improving. As a photosensitive permanent resist, the surface protection film or interlayer insulation film of semiconductor components has also been continuously improved, and its comprehensive performance has been continuously improved: high photosensitivity (improving production efficiency and resolution), high resolution (enabling circuit and window refinement), excellent heat resistance (including low coefficient of thermal expansion (low CTE, reducing stress between the insulating layer and the substrate, improving the stability and reliability of electronic products) and high glass transition temperature (high Tg, improving the thermal stability of electronic products)), good electrical properties (including good insulation (preventing short circuits) and low dielectric properties (ensuring high-speed and efficient communication of electronic products, mainly based on the high-frequency and high-speed communication requirements of 5G and 5G+)), aging resistance (improving product stability and reliability), adhesion (peel strength with the substrate, improving product stability and reliability), and acid, alkali, and solvent resistance.

[0003] During the electronic component manufacturing process, photosensitive materials are required to form the insulating layers required for solder resists, plating resists, etching resists, and interlayer insulating films. Photosensitive materials generally include the following components: alkali-soluble resins (to enable weakly alkaline aqueous solution development, which is more environmentally friendly than organic solvent development), photopolymerizable monomers (to achieve partial exposure and form circuits), and photoinitiator systems (which, under illumination, generate active sites that trigger negative cross-linking reactions or positive decomposition reactions based on the characteristics of the photosensitive material). Based on this, other components are introduced according to different performance requirements and application scenarios: inorganic fillers, thermosetting components (mostly, but not limited to, epoxy polymerization systems), pigments / dyes, various additives, flame retardants, and solvents.

[0004] In recent years, to improve product production efficiency, the sensitivity of permanent resists has been continuously improved and the production exposure intensity has been reduced; to achieve high density and high precision, the resolution of permanent resists has been continuously improved; to meet higher requirements and even be applied to IC packaging substrates, the thermal performance of permanent resists has been continuously optimized. CTE and Tg have become two important indicators of permanent resists. At the same time, under the premise of low CTE and high Tg, permanent resists also need to have good flexibility to pass the bending resistance test.

[0005] Patent 1) Ajinomoto's patent application 2020-144394 and Patent 2) Showa Denko New Materials' patent application 2021-71563 primarily optimize and improve the window opening, but the minimum window aperture remains around 70μm. Patents 3) and 4) Hitachi Chemical's domestic patents CN 110083010A and CN 103748516A report on thermal performance, but do not disclose specific data, simply stating Tg ≥ 120°C. Meanwhile, Patent 5) Hitachi Chemical's patent CN 106687864A reports on the relevant exposure energy, reaching a maximum of 2200mJ / cm 2 The lowest is 1050mJ / cm 2 Obviously, the minimum window aperture and exposure energy threshold of the existing technology need to be further reduced, and the Tg value needs to be further increased. Summary of the Invention

[0006] The present invention aims to solve the above-mentioned problems and thus provides a photosensitive resin composition. The photosensitive resin composition provided by the present invention has good flexibility, can pass the bending resistance test, can pass the acid, alkali and organic solvent resistance test, can be developed in a weak alkaline developer, and is suitable for PCB production and IC substrate production.

[0007] The technical solutions of the present invention for solving the above problems are as follows:

[0008] A photosensitive resin composition comprising at least:

[0009] Component A: alkali soluble resin,

[0010] Component B: photopolymerizable monomer,

[0011] Component C: epoxy resin,

[0012] Component D: curing agent,

[0013] Component E: inorganic filler,

[0014] and component F: photoinitiator;

[0015] Among them, the alkali-soluble resin component A is a rigid epoxy acrylic resin containing carboxyl groups, and the epoxy resin component C includes a Ca component and a Cb component. The Ca component is an epoxy resin with a rigid structure modification, and the Cb component is an epoxy resin with a flexible structure modification. The masses of the A and C components satisfy the following dosage relationship: 15>(A+Ca) / Cb>2.5.

[0016] As a preferred embodiment of the above technical solution, component A is composed of one or more of the following structures:

[0017]

[0018]

[0019]

[0020] Where n = 0 to 10,

[0021] Ra is any one or more of H or C1-C4 alkyl,

[0022] Ra' is H, Any one or more of them, at least a part of Ra' is Any one of them, and at least part of Ra' is Any one of them.

[0023] Ra" is none or CH2,

[0024] Ra'' is any one or more of H, C1-C12 alkyl, and C1-C12 alkoxy.

[0025] As a preferred embodiment of the above technical solution, the rigid structure modified epoxy resin is an epoxy resin containing a comb-like structure of polybisphenol A or bisphenol F, containing multiple condensed ring structures, containing a large π bond conjugated structure, containing multiple dicyclopentadiene, or containing N,N,N,N-tetraglycidyl-4,4′-diaminodiphenylmethane structure; the flexible structure modified epoxy resin is an epoxy resin containing a linear structure of polybisphenol A or bisphenol F, containing a single naphthol structure and a functionality less than or equal to 2, containing a single benzene ring and a functionality less than or equal to 3, or an epoxy-modified phenolic resin.

[0026] As a preferred embodiment of the above technical solution, the rigid structure-modified epoxy resin Ca is composed of one or more of the following structures:

[0027]

[0028]

[0029] Wherein, n=0~20, Rc1 is H or And at least a portion of Rc1 is

[0030] Rc1' is none or CH2,

[0031] Rc1" is any one or more of H or C1-C4 alkyl,

[0032] Rc1″′ is any one or more of H, C1-C4 alkyl, or C1-C4 alkoxy.

[0033] As a preferred embodiment of the above technical solution, the flexible structure-modified epoxy resin Cb is composed of one or more of the following structures:

[0034]

[0035] Wherein, n=0-20;

[0036] Rc2 is H or And at least a portion of Rc2 is

[0037] Rc2" is any one or more of H or C1-C4 alkyl,

[0038] Rc2″′ is any one or more of H, C1-C12 alkyl, and C1-C12 alkoxy.

[0039] As a preferred embodiment of the above technical solution, the photopolymerizable monomer is a multifunctional (meth)acrylate, and preferably the photopolymerizable monomer includes a difunctional photopolymerizable monomer and a hexafunctional photopolymerizable monomer.

[0040] As a preferred embodiment of the above technical solution, the curing agent is selected from any one or more of phenolic resins, dicyandiamide derivatives, organic acid anhydrides, hydrazides or active polyester curing agents.

[0041] As a preferred embodiment of the above technical solution, the photosensitive resin composition is based on the inorganic filler, recorded as 100 parts, wherein the alkali-soluble resin of component A is 30 to 70 parts, the photopolymerizable monomer of component B is 10 to 30 parts, the epoxy resin of component C is 10 to 30 parts, the curing agent of component D is 2.5 to 20 parts, and the photoinitiator of component F is 0.1 to 5 parts.

[0042] As a preferred embodiment of the above technical solution, the inorganic filler is a combination of one or more of silicon dioxide, titanium dioxide, zirconium oxide, calcium carbonate, barium sulfate, etc., and the particle size of the inorganic filler is preferably D50≤1.5um.

[0043] As a preferred embodiment of the above technical solution, the photoinitiator is selected from any one or more of oxime ester photosensitizers, phenyl ketone photosensitizers, bisimidazole photosensitizers, benzophenone photosensitizers, thioxanthone photosensitizers, and phosphine oxide photosensitizers.

[0044] A second object of the present invention is to provide a photosensitive resin film made from the above-mentioned photosensitive resin composition.

[0045] The third object of the present invention is to provide an electronic component made of the above-mentioned photosensitive resin composition.

[0046] As a preferred embodiment of the above technical solution,

[0047] A fourth object of the present invention is to provide a method for preparing a permanent resist layer.

[0048] The method for preparing the permanent resist layer comprises the following steps:

[0049] 1) providing a photosensitive dry film formed of the above-mentioned photosensitive resin composition on a substrate (which can be formed by directly coating the photosensitive resin composition or by attaching a photosensitive resin film prepared from the photosensitive resin composition);

[0050] 2) irradiating the photosensitive dry film with active light in a pattern;

[0051] 3) Developing the photosensitive dry film to form a permanent resist layer.

[0052] In summary, the present invention has the following beneficial effects:

[0053] 1. The photosensitive resin composition provided by the present invention achieves good flexibility and optimized thermal performance by rationally adjusting the ratio between the components of the resin composition and rationally matching the rigid groups and flexible groups, achieving Tg>130°C and CTE<60ppm / °C.

[0054] 2. The present invention improves the resolution by rationally selecting the structure of each component of the resin composition and adjusting the ratio between the components of the resin composition: φVia = 55um; L / S = 40 / 40, which significantly improves the window refinement performance;

[0055] 3. The present invention significantly improves the sensitivity by rationally selecting the structure of each component of the resin composition and adjusting the ratio between the components of the resin composition, effectively reducing the exposure energy threshold. For ST10 / 21 exposure scale, the overall exposure energy is 700-900mJ / cm 2 The lowest can be up to 650mJ / cm 2 , greatly reducing production costs. DETAILED DESCRIPTION

[0056] The present invention is further explained below with reference to specific embodiments.

[0057] This specific embodiment is only an explanation of the present invention and is not intended to limit the present invention. Any changes made by those skilled in the art after reading the description of the present invention will be protected by patent law as long as they are within the scope of the claims.

[0058] The photosensitive resin composition comprises at least component A: alkali-soluble resin, component B: photopolymerizable monomer, component C: epoxy resin, component D: curing agent, component E: inorganic filler, and component F: photoinitiator;

[0059] Among them, the alkali-soluble resin component A is a rigid epoxy acrylic resin containing carboxyl groups, and the epoxy resin component C includes a Ca component and a Cb component. The Ca component is an epoxy resin with a rigid structure modification, and the Cb component is an epoxy resin with a flexible structure modification. The masses of the A and C components satisfy the following dosage relationship: 15>(A+Ca) / Cb>2.5.

[0060] Specifically, the alkali-soluble resin of component A and the component Ca both contain a rigid structure to meet the thermal properties required by the formula, including low CTE and high Tg. During the thermal curing process, the shrinkage rate of the rigid structure is relatively small, which can reduce the tension between the component and the substrate after curing and improve the performance stability of the final product. The Cb component contains a flexible structure to meet the flexibility required by the formula and improve the bending resistance of the final product. When the rigid structure and the flexible structure are in the range of 15>(A+Ca) / Cb>2.5, the thermal performance and flexibility of the product can be effectively balanced; when (A+Ca) / Cb>15, since the proportion of the rigid structure is too large, although the CTE of the formula is reduced and the Tg is increased, due to insufficient flexibility, the brittleness of the product increases and it is easy to bend. During production and use, it is easy to cause damage to the final product, reduce the product yield, and shorten the product life during use. When (A+Ca) / Cb<2.5, the flexibility of the formula is effectively guaranteed due to the excessive proportion of flexible structure. However, due to the insufficient rigid structure, the CTE of the formula increases and the Tg decreases. During the thermal curing process and multiple reflow soldering processes, the large difference in shrinkage rate and substrate shrinkage rate causes increased tension between the insulating layer and the substrate. Creep fatigue of the insulating layer reduces the reliability of the product, affecting the normal use of the product.

[0061] Furthermore, the alkali-soluble resin of component A is a rigid structure containing polybisphenol A or polybisphenol F with a comb-like structure, or containing multiple condensed ring structures or large π-bond conjugated structures, or containing multiple dicyclopentadienes, or N,N,N,N-tetraglycidyl-4,4′-diaminodiphenylmethane structures.

[0062] Furthermore, the rigid structure modified epoxy resin is an epoxy resin containing a comb-like structure of polybisphenol A or bisphenol F, a plurality of condensed ring structures, a large π bond conjugated structure, a plurality of dicyclopentadiene, or an N,N,N,N-tetraglycidyl-4,4′-diaminodiphenylmethane structure;

[0063] The flexible structure modified epoxy resin is an epoxy resin containing linear polybisphenol A or bisphenol F, containing a single naphthol structure with a functionality less than or equal to 2, containing a single benzene ring with a functionality less than or equal to 3, or an epoxy-modified phenolic resin.

[0064] Furthermore, component A is composed of one or more of the following structures:

[0065]

[0066]

[0067] Where n = 0 to 10,

[0068] Ra is any one or more of H or C1-C4 alkyl,

[0069] Ra' is H, Any one or more of them, at least a part of Ra' is Any one of them, and at least part of Ra' is Any one of them.

[0070] Ra" is none or CH2,

[0071] Ra'' is any one or more of H, C1-C12 alkyl, and C1-C12 alkoxy.

[0072] Specifically, the Ra is any of H or C1 to C4 alkyl groups, which means that there are multiple Ra groups, which are the same or different from each other, and each different Ra group is independently selected from H or any of C1 to C4 alkyl groups. The multiple substituent groups described in this application are understood by analogy as above and will not be elaborated here.

[0073] Furthermore, the rigid structure-modified epoxy resin Ca is composed of one or more of the following structures:

[0074]

[0075]

[0076]

[0077] Where n = 0 to 20,

[0078] Rc1 is H or And at least a portion of Rc1 is

[0079] Rc1' is none or CH2,

[0080] Rc1" is any one or more of H or C1-C4 alkyl,

[0081] Rc1″′ is any one or more of H, C1-C4 alkyl, or C1-C4 alkoxy.

[0082] Furthermore, as a preference, the Rc1 are

[0083] Furthermore, the flexible structure-modified epoxy resin Cb is composed of one or more of the following structures:

[0084]

[0085]

[0086] Wherein, n=0-20;

[0087] Rc2 is H or And at least a portion of Rc2 is

[0088] Rc2" is any one or more of H or C1-C4 alkyl,

[0089] Rc2″′ is any one or more of H, C1-C12 alkyl, and C1-C12 alkoxy.

[0090] Furthermore, as a preference, the Rc2 are

[0091] Furthermore, the photopolymerizable monomer is a multifunctional (meth)acrylate.

[0092] As a preferred embodiment of the above technical solution, the photopolymerizable monomer component B is a compound of one or more difunctional, trifunctional, tetrafunctional, pentafunctional, and hexafunctional acrylates or methacrylates, including: ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, tripropylene ...methacrylate, tripropylene glycol diacrylate, ethylene glycol dimethacrylate, Acrylates, tripropylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, oxadiene diacrylate, oxadiene dimethacrylate, hydroxypivalic acid polyglycol diacrylate, hydroxypivalic acid polyglycol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 9,9-(4-phenyl-2-acryloylethoxy)bisfluorene, 9 , 9-(4-phenyl-2-methacryloylethoxy)bisfluorene and other difunctional monomers, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, ethoxylated glycerol triacrylate, ethoxylated glycerol trimethacrylate, tris(2-acryloyloxyethyl isocyanurate), tris(2-methacryloyloxyethyl isocyanurate) and other trifunctional monomers, dimethoxypropane tetraacrylate, dimethoxypropane Tetrafunctional monomers such as tetramethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate; pentafunctional monomers such as dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate; hexafunctional monomers such as phenoxylated dipentaerythritol hexaacrylate, phenoxylated dipentaerythritol hexamethacrylate, ethoxylated dipentaerythritol hexaacrylate, ethoxylated dipentaerythritol hexamethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate.

[0093] The photopolymerizable monomers preferably include at least a difunctional photopolymerizable monomer and a hexafunctional photopolymerizable monomer. Compared to other multifunctional photopolymerizable monomers, difunctional monomers can ensure that the crosslinking density is controlled within a certain range, thereby improving resolution. Hexafunctional monomers, on the other hand, can ensure the integrity of the pattern during development after photocrosslinking and reduce exposure energy. Furthermore, a more preferred photopolymerizable monomer is a combination of a difunctional and a hexafunctional photopolymerizable monomer, which can simultaneously optimize resolution and pattern integrity after development while reducing exposure energy.

[0094] Furthermore, the curing agent is selected from any one or more of phenolic resins, dicyandiamide derivatives, organic acid anhydrides, hydrazides or active polyester curing agents.

[0095] Specifically, phenolic resin curing agents include resol phenolic resin, naphthol phenolic resin with a phenolic resin structure, phenolic resin with a triazine skeleton with a phenolic resin structure, etc. Organic acid anhydride curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, benzophenone tetrahydroxy acid trianhydride, endomethylene tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, etc. Organic hydrazide curing agents include succinic acid hydrazide, adipic acid dihydrazide, sebacic acid hydrazide, isophthalic acid hydrazide and p-hydroxybenzoic acid hydrazide, etc. Active ester curing agents are active ester curing agents obtained by condensation of carboxylic acid compounds and / or acid anhydride compounds with hydroxyl compounds, preferably active ester curing agents obtained by condensation of carboxylic acid compounds and / or acid anhydride compounds with phenol and / or naphthol compounds. Further screening can also be carried out according to the actual curing temperature. Specifically, for photosensitive cover films cured at medium and high temperatures, acid anhydrides and active polyester curing agents are preferred.

[0096] The curing agent can be selected alone or in combination with a curing agent accelerator. Commonly used curing agents and accelerators include imidazole derivatives, quaternary ammonium salt curing accelerators, urea derivatives, and organic guanidine derivatives. Examples of imidazole derivative curing agents and accelerators include, for example, imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, and 2-phenyl-4-methylimidazole, as well as blocked imidazole derivative curing agents and accelerators such as toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate adduct. Quaternary ammonium salt curing agents and accelerators include amino quaternary ammonium salts, imidazole quaternary ammonium salts, and pyridinium quaternary ammonium salts. Furthermore, quaternary ammonium salts containing benzyl groups are preferred, and further, pyridinium quaternary ammonium salts are preferred over imidazole quaternary ammonium salts and amino quaternary ammonium salts. The curing agent and curing agent accelerator can be used in combination, either one-to-one or in a combination of multiple compounds.

[0097] Furthermore, the photosensitive resin composition is based on the inorganic filler, which is recorded as 100 parts, wherein the alkali-soluble resin of component A is 30 to 70 parts, the photopolymerizable monomer of component B is 10 to 30 parts, the epoxy resin of component C is 10 to 30 parts, the curing agent of component D is 2.5 to 20 parts and the curing accelerator is 0 to 5 parts, and the photoinitiator of component F is 0.1 to 5 parts.

[0098] It also includes 0 to 10 parts of additives, including defoaming agents, leveling agents, pigments and other auxiliary agents, which can be increased or decreased according to the formula and application occasions.

[0099] As a preferred embodiment of the above technical solution, the inorganic filler can be one or more inert inorganic fillers such as silica, titanium dioxide, zirconium oxide, calcium carbonate, and barium sulfate. In particular, as a preferred embodiment of the above technical solution, the inorganic filler has a particle size D50 ≤ 1.5 μm. Furthermore, the inorganic filler is preferably silica or titanium dioxide.

[0100] Furthermore, the photoinitiator is selected from any one or more of oxime ester photosensitizers, phenyl ketone photosensitizers, bisimidazole photosensitizers, benzophenone photosensitizers, thioxanthone photosensitizers, and phosphine oxide photosensitizers.

[0101] As a preferred embodiment of the above technical solution, the photoinitiator is selected from one or more of the following photosensitizers:

[0102] 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyl oxime), 1-(6-o-chlorobenzoyl-9-ethylcarbazole)-1-ethanone 1-(O-acetyl oxime), 1-(6-o-methylbenzoyl-9-ethylcarbazole)-1-cyclohexylmethanone 1-(O-acetyl oxime), 1-(6-o-methylbenzoyl-9-ethylcarbazole)-1-cyclohexylmethanone Oxime ester photoinitiators such as oxime ester, 2-methyl-2-(4-morpholino)-1-[4-(methylthio)phenyl]-1-propanone, 2-dimethylamino-2-benzyl-1-[4-(4-morpholino)phenyl]-1-butanone, 2-dimethylamino-2-(4-methyl) ... phenyl]-1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-2-methyl-1-(4-hydroxyethoxy)phenyl-1-propanone, 2-hydroxy-2-methyl-1-(4-methoxy)phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone and other phenyl ketone photosensitizers, 2,2'-di-o-chlorophenyl-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2',5-tri-(o-chlorophenyl)-4- Bisimidazole photosensitizers such as (3,4-dimethoxyphenyl)-4',5'-diphenylbisimidazole, benzophenone photosensitizers such as 3-phenylbenzophenone, 3-methylbenzophenone, and 4,4'-bis(diethylamino)benzophenone, thioxanthone photoinitiators such as isopropylthioxanthone and 2,4-diethylthioxanthone, and phosphine oxide photosensitizers such as (2,4,6-trimethylbenzoyl)diphenylphosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0103] Furthermore, it is more preferred that the photosensitizer is a combination of phenyl ketones, thioxanthones and benzophenones.

[0104] A photosensitive resin film comprises a support and a photosensitive layer arranged on the support, wherein the photosensitive layer is composed of the above-mentioned photosensitive resin composition.

[0105] An electronic component uses a photosensitive insulating material. The photosensitive insulating layer is composed of the photosensitive resin composition or is directly made of the photosensitive resin film.

[0106] Specifically, in each embodiment and comparative example, the material components are as follows:

[0107] Component A, alkali-soluble resin

[0108] A1 AM-8200; (independently modified Jiashengde epoxy resin BPANE8200) (A-1)

[0109] A2 ZXR-1807H; (Nippon Kayaku)(A-4)

[0110] A3 AM-3000; (independently modified Nippon Kayaku epoxy resin NC-3000H) (A-5)

[0111] The preparation method of the alkali-soluble resin prepared by self-modified epoxy is as follows: the alkali-soluble resin is obtained by modifying epoxy resin with acrylic acid and tetrahydrophthalic anhydride or hexahydrophthalic anhydride. The specific operation is as follows:

[0112] A 2L detachable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen gas conduit was added to a mixture of epoxy resin to be modified and dehydrated carbitol acetate (the solvent amount was calculated based on a total solid content of 70%). The mixture was heated to 95°C with continuous stirring. After the epoxy resin was fully dissolved, p-hydroxyanisole (the amount of p-hydroxyanisole required was calculated based on a ratio of p-hydroxyanisole to (epoxy resin + acrylic acid) of 0.5:100) was added. Tetrabutylammonium bromide (the amount of tetrabutylammonium bromide required was calculated based on a ratio of tetrabutylammonium bromide to (epoxy resin + acrylic acid) of 1:100) and acrylic acid (the amount of acrylic acid required was calculated based on a ratio of epoxy to acrylic acid of 1.05:1) were thoroughly mixed and then added dropwise to the epoxy solution over an hour. After the addition is complete, the reaction is stirred for 6 hours. When the acid value is approximately 0.2 mg KOH / g, the temperature is lowered to 85° C., and then tetrahydrophthalic anhydride is added (the required amount of tetrahydrophthalic anhydride is calculated based on the target solid acid value). The reaction is continued for 8 hours. When the acid value substantially reaches the target acid value, most of the solvent is removed by vacuum distillation. Then, butanone is added to adjust the solid content to 70% for later use.

[0113] Component B, photopolymerizable monomer

[0114]

[0115] Component C, epoxy resin

[0116]

[0117] Component D, curing agent and curing accelerator

[0118] D1 2-ethyl-4-methylimidazole; (Aladdin, imidazole curing agent accelerator)

[0119] D2 8000-65T; (DIC) (contains dicyclopentadiene phenolic resin active ester curing agent)

[0120] D3 PF8011; (Shengquan) (phenolic resin curing agent)

[0121] Component E, inorganic filler

[0122] E1 SC2050-MNU; (Yadouma) (Silicon dioxide)

[0123] E2 NFS-200E; (Yishitong) (Silicon dioxide)

[0124] Component F, photoinitiator

[0125]

[0126] G component, additives

[0127] G1 defoamer octamethylcyclotetrasiloxane; (Dow Chemical, trade name SH-193)

[0128] G2 pigment phthalocyanine green G; (BASF, trade name PG7)

[0129] According to the resin composition formulas listed below, mix them in proportion by weight. Add a certain amount of butanone and stir thoroughly until evenly dispersed to prepare a resin composition with a solids content of 65-75wt%. Use a coater to evenly coat the resin composition on the surface of a PET support film. Place the coating in an 85°C oven for 8-12 minutes to form a 25μm thick dry film resist layer that appears green under yellow light. Then, apply a polyethylene protective film to the surface to create a three-layer dry film product. Store in the freezer until ready for use.

[0130] Recipe Sheet

[0131] Table 1

[0132]

[0133]

[0134] Table 2

[0135]

[0136]

[0137] Table 3

[0138]

[0139]

[0140] The following describes the sample preparation methods (including film lamination, exposure, development, etching, electroplating, and film stripping), sample evaluation methods, and evaluation results of the embodiments and comparative examples.

[0141] Test methods and standards:

[0142] 1) Preparation of photosensitive resin composition glue:

[0143] According to the formula table, the components are mixed evenly in proportion according to weight, a certain amount of butanone is added, and then stirred thoroughly until uniformly dispersed to prepare a resin composition glue with a solid content of 65-75wt%.

[0144] 2) Preparation of dry film products of photosensitive resin composition:

[0145] The photosensitive resin composition prepared in step 1) was evenly coated onto the surface of a PET support film using a coater. The film was then pre-baked in an 85°C oven for 8-12 minutes to form a dry film resist layer of predetermined thickness that appeared green under a yellow light. A polyethylene protective film was then applied to the surface to form a three-layer dry film of the photosensitive resin composition. The film was then stored in a freezer until ready for use.

[0146] 3) Lamination, exposure and development of photosensitive resin composition dry film products:

[0147] The photosensitive resin composition dry film product prepared in step 2) above was removed from the freezer and thawed at room temperature for 1 hour. After peeling off the polyethylene protective film, the photosensitive resin composition dry film product was attached to a commercial copper-clad laminate using a vacuum laminator or roller laminator (vacuum laminator: pressure 3.5-4 kgf, vacuum time 30-60 s, pressure time 30-60 s, temperature 85-100°C; roller laminator: pressure 4-4.5 kgf, temperature 100-110°C). After lamination, the film was allowed to stand for 1 hour. Subsequently, the resulting photosensitive resin composition layer was exposed using a high-pressure mercury lamp exposure machine with different masks and different exposure energies. After exposure, the film was allowed to stand for 1 hour, the PET support film was peeled off, and the exposed photosensitive resin composition layer was developed using an alkaline developer (0.8-1.2 wt% sodium carbonate aqueous solution) at 25°C (development time 45-75 s), followed by rinsing with deionized water for 20 seconds.

[0148] Sensitivity: The lowest energy at which ST21 exposure ruler is exposed and developed and ST10 is not developed and fully exposed is recorded as the sensitivity energy of the formula.

[0149] Using the above preparation methods 1), 2), and 3), exposure was performed at different exposure energies using an ST21 exposure ruler mask. After development, the lowest exposure energy at which the ST10 photosensitive resin composition dry film product remained undeveloped and fully exposed was recorded as the sensitivity energy.

[0150] L / S and Via: Through SEM observation, the lines and windows are fully presented.

[0151] Using the above preparation methods 1), 2), and 3), exposures were performed at ST10 / 21 sensitivity using reticles with varying L / S (linewidth / spacing) and vias (windows). After development, the L / S and vias were observed using a SEM. The optimal L / S and via, which showed full linewidth / spacing or window diameter within ±5% of the reticle, was designated as the resolution result.

[0152] Tg and CTE are tested by TMA

[0153] Using the above-mentioned preparation methods 1) and 2), a 50 μm thick photosensitive resin composition dry film product was prepared, and then the entire plate was exposed using ST10 / 21 sensitivity energy. After standing for 1 hour, it was developed, secondary photocured, and heated at 160°C for 2 hours to form a cross-linked resin composition cured product on the PET support film. Then, after being cut into 5 mm wide and 25 mm long pieces with a cutter, the PET support film of the photosensitive resin composition dry film product was peeled off to obtain a photosensitive resin composition cured product for thermal expansion coefficient evaluation. The thermal expansion coefficient in the tensile mode was measured using a TMA device (TMA Q400, Shenzhen Santak Technology). The tensile load was 0.1 N, the span (distance between chucks) was 15 mm, and the heating rate was 10°C / min. First, the sample was mounted on the device, heated from room temperature (25°C) to 160°C, and left for 15 minutes. Then, it was cooled to -60°C and again measured under the conditions of heating from -60°C to 250°C at a heating rate of 10°C / min. The inflection point seen in the range from 25° C. to 200° C. is marked as Tg, and the temperature at that point is recorded. The slope of a tangent line to the curve obtained at a temperature below Tg is used as the CTE.

[0154] ◎: less than 50ppm / ℃;

[0155] ○: 50~60ppm / ℃;

[0156] △: 60~70ppm / ℃;

[0157] ×: more than 70ppm / ℃;

[0158] HAST test

[0159] Using the above preparation methods 1), 2), and 3), a 25μm-thick dry film of the photosensitive resin composition was fully exposed (or exposed using a mask with a small number of lines) using ST10 / 21 sensitivity. After lingering for one hour, the film was developed, post-cured, and heated at 160°C for two hours. The resistivity of the dry film before and after HAST treatment was measured using a resistance meter. The sample was then transferred to a HAST chamber (PC-422R8D, Hirayama Seisakusho) and lingered at 121°C and 100% humidity for 120 hours. The resistivity after HAST treatment was then measured again, and the presence of air bubbles or delamination was observed. The resistivity changes before and after HAST treatment were compared.

[0160] ◎: No bubble peeling or other phenomena occur, or the resistivity changes within ±10%;

[0161] ○: No bubble peeling or other phenomena occur, or the resistivity changes within ±30%;

[0162] △: A small amount of bubbles appear, or the resistivity changes within ±50%;

[0163] ×: There are a lot of bubbles or peeling, or the resistivity changes by more than 50%.

[0164] Acid resistance

[0165] Test samples, prepared using the same method as the HAST test examples, were immersed in a 10 vol% H2SO4 aqueous solution at 30°C for 30 minutes, then rinsed with water and dried. A peel test was then performed using 3M tape. Acid resistance was evaluated according to the following criteria.

[0166] ◎: The dry film has no bubbling, peeling or even falling off;

[0167] ○: The dry film has a small amount of bubbling, no peeling or falling off;

[0168] △: The dry film has a small amount of bubbling, peeling, or even falling off;

[0169] ×: The dry film peeled off in large quantities.

[0170] Alkali resistance

[0171] Test samples, prepared using the same method as the HAST test examples, were immersed in a 10 vol% aqueous NaOH solution at 30°C for 30 minutes, removed, rinsed with water, and dried. A peel test was then performed using 3M tape. Acid resistance was evaluated according to the following criteria.

[0172] ◎: The dry film has no bubbling, peeling or even falling off;

[0173] ○: The dry film has a small amount of bubbling, no peeling or falling off;

[0174] △: The dry film has a small amount of bubbling, peeling, or even falling off;

[0175] ×: The dry film peeled off in large quantities.

[0176] Solvent resistance

[0177] Test samples prepared using the same method as the HAST test examples were immersed in propylene glycol methyl ether acetate at 30°C for 30 minutes, removed, and dried. A peel test was then performed using 3M tape. Acid resistance was evaluated according to the following criteria.

[0178] ◎: The dry film has no bubbling, peeling or even falling off;

[0179] ○: The dry film has a small amount of bubbling, no peeling or falling off;

[0180] △: The dry film has a small amount of bubbling, peeling, or even falling off;

[0181] ×: The dry film peeled off in large quantities.

[0182] Bending resistance

[0183] Evaluation was conducted according to JIS-C-5-016 8.7 and the following criteria. Using the same preparation method as for the HAST test example samples, a dry film of the photosensitive resin composition was attached to a commercial soft copper plate to prepare a flexural resistance test sample. The sample was bent at 180°C with the cured film facing outward, and the following criteria were used to evaluate the performance.

[0184] ◎: There are no obvious creases or cracks on the cured film;

[0185] ○: Creases appeared on the cured film, but no cracks appeared;

[0186] Δ: There are some cracks on the cured film.

[0187] ×: The cured film was broken.

[0188] Test data table

[0189] Table 4

[0190]

[0191] Table 5

[0192]

[0193]

[0194] Table 6

[0195]

[0196] Comparison conclusion:

[0197] The test results of the Examples and Comparative Examples demonstrate that the present invention effectively balances thermal performance (high Tg and low CTE) with various resistances (acid, alkali, solvent, flexure, and HAST resistance) while ensuring good resolution (L / S and windowing), particularly flexure resistance. Comparative Example 1, with increased content of flexible epoxy resin, exhibits good resolution but significantly degrades thermal performance. Comparative Examples 2 and 3, on the other hand, exhibit improved thermal performance with increased content of rigid components, but flexure resistance falls short of the target and resolution is slightly reduced. Comparative Example 4, employing a more flexible aliphatic epoxy resin, achieves results similar to those of Comparative Examples 1 and 2, but exhibits even more pronounced effects, with a sharp decline in thermal performance.

Claims

1. A photosensitive resin composition, characterized in that: At least include Component A: alkali soluble resin, Component B: photopolymerizable monomer, Component C: epoxy resin, Component D: curing agent, Component E: inorganic filler, and component F: photoinitiator; The alkali-soluble resin component A is a rigid epoxy acrylic resin containing a carboxyl group, the epoxy resin component C includes a Ca component and a Cb component, the Ca component is an epoxy resin with a rigid structure modification, and the Cb component is an epoxy resin with a flexible structure modification, and the masses of the A and C components satisfy the following dosage relationship: 15>(A+Ca) / Cb>2.5; The rigid structure modified epoxy resin is an epoxy resin containing a comb-like structure of polybisphenol A or bisphenol F, a plurality of condensed ring structures, a large π bond conjugated structure, a plurality of dicyclopentadiene, or an N,N,N,N-tetraglycidyl-4,4-diaminodiphenylmethane structure; the flexible structure modified epoxy resin is an epoxy resin containing a linear structure of polybisphenol A or bisphenol F, a single naphthol structure with a functionality less than or equal to 2, a single benzene ring with a functionality less than or equal to 3, or an epoxy-modified phenolic resin.

2. The photosensitive resin composition according to claim 1, wherein: Component A consists of one or more of the following structures: Where n = 0 to 10, Ra is any one or more of H or C1-C4 alkyl, Ra' is H, Any one or more of them, at least a part of Ra' is Any one of them, and at least part of Ra' is Any one of Ra" is none or CH2, Ra'' is any one or more of H, C1-C12 alkyl, and C1-C12 alkoxy.

3. The photosensitive resin composition according to claim 1, wherein The rigid structure-modified epoxy resin Ca is composed of one or more of the following structures: Where n = 0 to 20, Rc1 is H or And at least a portion of Rc1 is Rc1' is none or CH2, Rc1" is any one or more of H or C1-C4 alkyl, Rc1″′ is any one or more of H, C1-C4 alkyl, or C1-C4 alkoxy.

4. The photosensitive resin composition according to claim 1, characterized in that: The flexible structure-modified epoxy resin Cb is composed of one or more of the following structures: Wherein, n=0-20; Rc2 is H or And at least a portion of Rc2 is Rc2" is any one or more of H or C1-C4 alkyl, Rc2″′ is any one or more of H, C1-C12 alkyl, and C1-C12 alkoxy.

5. The photosensitive resin composition according to claim 1, wherein: The photopolymerizable monomer is a multifunctional (meth)acrylate.

6. The photosensitive resin composition according to claim 5, wherein: The photopolymerizable monomers include difunctional photopolymerizable monomers and hexafunctional photopolymerizable monomers.

7. The photosensitive resin composition according to claim 1, wherein: The curing agent is selected from any one or more of phenolic resins, dicyandiamide derivatives, organic acid anhydrides, hydrazides or active polyester curing agents.

8. The photosensitive resin composition according to claim 1, wherein: The photosensitive resin composition is based on the inorganic filler and is recorded as 100 parts, wherein the alkali-soluble resin of component A is 30-70 parts, the photopolymerizable monomer of component B is 10-30 parts, the epoxy resin of component C is 10-30 parts, the curing agent of component D is 2.5-20 parts, and the photoinitiator of component F is 0.1-5 parts.

9. The photosensitive resin composition according to claim 1, wherein: The inorganic filler is a combination of one or more of silicon dioxide, titanium dioxide, zirconium oxide, calcium carbonate and barium sulfate.

10. The photosensitive resin composition according to claim 1, wherein: The particle size of the inorganic filler is D50≤1.5um.

11. The photosensitive resin composition according to claim 1, wherein: The photoinitiator is selected from any one or more of oxime ester photosensitizers, phenyl ketone photosensitizers, bisimidazole photosensitizers, benzophenone photosensitizers, thioxanthone photosensitizers, and phosphine oxide photosensitizers. 12 . A photosensitive resin film comprising a support and a photosensitive layer provided on the support, wherein the photosensitive layer is composed of the photosensitive resin composition according to claim 1 . 13 . An electronic component comprising the photosensitive resin composition according to claim 1 .

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