A fluorine-containing diamine and a photosensitive resin composition

Abstract

The present invention discloses a fluorine-containing diamine and a photosensitive resin composition. The photosensitive resin composition comprises 100 parts by mass of an alkali-soluble multifunctional photosensitive epoxy resin, wherein the multifunctional group is a resin containing three or more epoxy groups; 20 to 60 parts by mass of an alkali-soluble polyimide resin; 1 to 40 parts by mass of a photopolymerization initiator; 5 to 50 parts by mass of a photopolymerizable monomer; 10 to 80 parts by mass of a thermosetting component; and 10 to 100 parts by mass of an inorganic filler. Among them, the alkali-soluble polyimide resin is obtained by condensing the above-mentioned fluorine-containing diamine with a carboxyl-containing diamine and a dianhydride monomer. The photosensitive resin composition has good thermal stability, mechanical properties, exposure sensitivity and alkali development characteristics, and has good dimensional stability under temperature changes, and also has excellent dielectric properties.

Description

Technical Field

[0001] The present invention relates to the technical field of synthetic resins, and in particular to a fluorine-containing diamine and a photosensitive resin composition. Background Art

[0002] Printed circuit board (PCB) is the base plate for modern electrical installation and connection components, and is an important basic assembly in the electronics industry. Among them, photosensitive solder resist ink is one of the key materials for printed circuit boards. It is a protective coating covering the copper wires of printed circuits to prevent circuit corrosion and disconnection, prevent short circuits between wires caused by multiple welding points, adjust the amount of solder adhesion, reduce the dissolution contamination of copper in the weld, save solder, reduce the weight of instruments, increase the density of wiring, avoid cold solder joints, and increase inspection speed.

[0003] At present, the most widely used photosensitive solder resist ink is a photosensitive resin composition including a photopolymerization initiator and a carboxyl group. Among them, the photosensitive resin is generally an acrylic modified epoxy resin. Although it has good photocurability, developability and mechanical properties, the heat resistance of the cured film after curing is insufficient, and it is easy to bubble or lose oil during soldering, which cannot meet the stringent requirements of electrical circuit boards. There are two main ways to improve the heat resistance of the photosensitive resin composition: physical modification and chemical modification. Physical modification mainly involves adding organic / inorganic fillers, but the physical blending method is easy to affect the basic properties of the resin-filler composite material through the interface effect. Chemical modification mainly involves the selection of epoxy resins with higher functionality, so that the cured product has a greater degree of crosslinking, thereby having better heat resistance. Although the above methods can effectively improve the heat resistance of the system, there are also some problems. For example, physical modification fails to fundamentally change the heat resistance of the system. During use, the system may be unevenly dispersed, phase separated during long-term storage, and difficult to form a uniform film during coating. The chemical modification method mainly involves introducing some rigid heat-resistant segments into the main chain structure of carboxylated epoxy acrylate. It is difficult to significantly increase the glass transition temperature by modifying the side chain alone.

[0004] With the advent of high-frequency communications, PCB substrates are also developing in the direction of high density and refinement, and the performance requirements for solder mask coatings are becoming higher and higher. Under normal circumstances, high-precision PCB substrates suitable for high-frequency communications must undergo a lead-tin soldering process above 260°C during processing. Correspondingly, photosensitive solder mask inks need to have higher heat-resistant solder processing performance. In addition, high-frequency communications require substrates with low dielectric constants to achieve high-speed information processing. Therefore, photosensitive solder mask inks must not only have high electrical insulation properties, but also have high glass transition temperatures and low dielectric constants. However, traditional photosensitive solder mask inks are not suitable for the production of high-precision circuit boards due to their poor heat resistance and high dielectric constant, which limits their application in high-frequency communications.

[0005] In the prior art, in order to reduce the dielectric constant of the photosensitive solder resist ink, fillers are mainly added to the photocurable solder resist ink. For example, Chinese invention patent CN202010017355.7 discloses a POSS-modified photosensitive solder resist ink with a low dielectric constant and a preparation method thereof, which introduces a dielectric confinement effect produced by modified cage-shaped silsesquioxane (POSS), that is, a strong self-polarization induction effect is produced at the contacting heterogeneous medium, resulting in the limited polarization of the electron cloud of the polymer, thereby reducing the dielectric constant of the polymer material. It should be pointed out that the above technical scheme improves the disadvantage of poor compatibility of low dielectric constant fillers with other components to a certain extent, but still cannot completely solve the interface effect between fillers and resins, and will affect the addition of other fillers in the subsequent ink product production process, and the limitation of the resin matrix is ​​not conducive to the specific implementation of the scheme. In addition, the introduction of a high amount of low dielectric constant fillers in the photosensitive solder resist ink will also cause the solder resist ink components to be complicated, affecting its elongation at break, alkali developability, etc.

[0006] In summary, the photosensitive solder resist ink in the prior art cannot have good heat resistance, low dielectric constant and dielectric loss performance, and cannot meet the application requirements in high-frequency communications. Summary of the invention

[0007] In order to solve the above technical problems, the present invention provides a fluorine-containing diamine and a photosensitive resin composition. The photosensitive resin composition has good thermal stability and mechanical properties and excellent film-forming properties. The dry film prepared therefrom has excellent flexibility and a low dielectric constant.

[0008] To achieve the above object, the technical solution adopted by the present invention is:

[0009] In one aspect, the present invention provides a fluorine-containing diamine having a structure represented by the following formula (i) or the following formula (ii):

[0010]

[0011] In formula (i) and formula (ii):

[0012] L1, L2, L3 are independently selected from any one of -O-, -S-, -Se-, -NH-, -CH2-, -C(CH3)2-, -N(CH3)-, -SiH2-, carbonyl, sulfone, ester, amide, substituted or unsubstituted C2-C6 alkyl chain, substituted or unsubstituted C5-C30 aromatic group; L4 is N;

[0013] Y1 and Y2 are fluorine-containing substituents, which are monosubstituted or polysubstituted; the fluorine-containing substituents are selected from at least one of -F, -CF3 and -OCF3.

[0014] In some specific embodiments, the fluorinated diamine having the structure represented by the above formula (i) or formula (ii) can be listed as follows:

[0015]

[0016]

[0017]

[0018]

[0019] In another aspect, the present invention provides a polyimide resin, which is a product obtained by further imidization after polymerization of any one or more of the above-mentioned fluorine-containing diamines with a carboxyl-containing diamine or a dianhydride.

[0020] In the technical scheme of the present invention, the type of the carboxyl-containing diamine is not particularly limited, and specific examples thereof include 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-bis(3-aminophenoxy)benzoic acid, 3,5-bis(4-aminophenoxy)benzoic acid, 3,3'-diamino-4,4'-dicarboxybiphenyl, 3,3'-diamino-4,4'-dicarboxydiphenylmethane , 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 2,2-bis[4-amino-3-carboxyphenyl]propane, 3,3'-diamino-4,4'dicarboxy diphenyl ether, 3,3'-dicarboxy-4,4'diaminodiphenyl ether, 3,3'-diamino-4,4'dicarboxy diphenyl sulfone and 4,4'-diamino-3,3'dicarboxy diphenyl sulfone, etc. The above diamines can be used alone or in any combination.

[0021] In the technical scheme of the present invention, the type of the dianhydride monomer is not particularly limited, and specific examples include 4,4'-oxydiphthalic anhydride, pyromellitic anhydride, hexafluoro dianhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 3,3,4,4-diphenylsulfone tetracarboxylic anhydride, 3,3',4,4'-benzophenone tetracarboxylic anhydride, bisphenol A type diether dianhydride and p-phenylene-diphthalic acid dianhydride. The above dianhydrides can be used alone or in any combination.

[0022] In the technical solution of the present invention, the diamine monomer may also include other types of diamines, such as p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone. , 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminobenzene 4-(4-aminophenoxy)phenyl] ether, bis[4-(3-aminophenoxy)phenyl] ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2-(4-aminophenyl)benzene, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2-(4-aminophenyl)benzene, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenyl)benzene, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2 ,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfone, 9,9-bis(4-aminophenyl)fluorene, etc., which can be used alone or in any combination.

[0023] In the technical solution of the present invention, the imidization is carried out under the action of a dehydrating agent;

[0024] Preferably, the dehydrating agent is selected from at least one of an acid anhydride-tertiary amine dehydrating agent, thionyl chloride-tertiary amine dehydrating agent and acetyl chloride-tertiary amine dehydrating agent; the acid anhydride is selected from at least one of acetic anhydride, phthalic anhydride and trifluoroacetic anhydride; the tertiary amine is selected from at least one of pyridine and triethylamine;

[0025] In some specific embodiments, the polymerization and imidization are carried out in a solvent. The solvent is not particularly limited, and is preferably a good solvent for the reaction raw materials, and specifically includes N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), toluene, xylene, methanol, ethanol, acetone, tetrahydrofuran, dimethyl sulfoxide, etc., which can be used alone or in any combination.

[0026] Preferably, the polymerization reaction temperature is -10°C to 80°C, and the reaction time is 4 to 24 hours.

[0027] In the technical solution of the present invention, the molar ratio of the diamine monomer to the dianhydride monomer is not particularly limited, and is generally set to 0.9-1.1:1.

[0028] Preferably, the reaction temperature of the imidization is 20 to 120° C., and the reaction time is 1 to 24 hours.

[0029] In another aspect, the present invention provides a photosensitive resin composition, comprising:

[0030] (A) component: 100 parts by mass of an alkali-soluble multifunctional photosensitive epoxy resin; the multifunctional resin contains three or more epoxy groups;

[0031] (B) component: 20 to 60 parts by mass of an alkali-soluble polyimide resin;

[0032] (C) component: 1 to 40 parts by mass of a photopolymerization initiator;

[0033] (D) component: 5 to 50 parts by mass of a photopolymerizable monomer;

[0034] (E) component: 10 to 80 parts by weight of a thermosetting component;

[0035] (F) component: 10 to 100 parts by mass of an inorganic filler;

[0036] Wherein, the alkali-soluble polyimide resin is the above-mentioned polyimide resin.

[0037] As a preferred embodiment, the acid value of the alkali-soluble multifunctional photosensitive epoxy resin is 40 to 200 mgKOH / g, and more preferably 50 to 180 mgKOH / g.

[0038] In the technical solution of the present invention, when the acid value of the alkali-soluble multifunctional photosensitive epoxy resin is less than 40 mgKOH / g, the alkali solubility of the photosensitive resin composition is poor, and the cured film obtained is difficult to develop in a dilute alkali aqueous solution. When the acid value of the alkali-soluble multifunctional photosensitive epoxy resin is greater than 200 mgKOH / g, the anti-development performance of the cured film obtained is poor, and even due to the high solubility in the alkali aqueous solution, an effective cured film cannot be formed.

[0039] In the technical solution of the present invention, the acid value represents the number of milligrams of potassium hydroxide (KOH) required to neutralize 1 gram of chemical substance.

[0040] In the technical solution of the present invention, the alkali-soluble multifunctional photosensitive epoxy resin is a multifunctional epoxy resin containing a photosensitive group and an alkali-soluble group on the molecular chain; the photosensitive group is selected from at least one of a carbonyl group, a carboxyl group, a peroxide group and a carbon-carbon double bond; the alkali-soluble group is selected from at least one of a carboxyl group, an acid anhydride group and an ester group;

[0041] Preferably, the alkali-soluble multifunctional photosensitive epoxy resin is selected from at least one of phenol novolac epoxy resin, bisphenol A novolac epoxy resin, naphthalene epoxy resin, o-cresol novolac epoxy resin, alkylphenol novolac epoxy resin, dicyclopentadiene epoxy resin, glycidylamine epoxy resin, trihydroxybenzene methane epoxy resin, tetraphenol ethane epoxy resin, diglycidyl phthalate resin and epoxy compounds of condensation products of phenols and aromatic aldehydes having phenolic hydroxyl groups.

[0042] In certain specific embodiments, the method for preparing the alkali-soluble multifunctional photosensitive epoxy resin comprises the following steps:

[0043] (a) A polyfunctional epoxy compound and (b) An unsaturated monocarboxylic acid are subjected to an esterification reaction, and then the obtained ester is reacted with (c) A saturated / unsaturated polyacid anhydride.

[0044] Examples of the above-mentioned (b) unsaturated monocarboxylic acid include acrylic acid, acrylic acid dimer, methacrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, reaction products of saturated / unsaturated dibasic acid anhydrides and hydroxyl-containing (meth)acrylates, and reaction products of saturated / unsaturated dibasic acids and unsaturated monoglycidyl compounds. The above-mentioned may be used alone or in any combination.

[0045] As the above-mentioned (c) saturated / unsaturated polybasic acid anhydride, there can be listed: dibasic acid anhydrides, such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and methyltetrahydrophthalic anhydride; polybasic aromatic carboxylic acid anhydrides, such as trimellitic anhydride, pyromellitic anhydride and benzophenonetetracarboxylic anhydride; and other acid anhydride derivatives, such as 5-(2,5-dioxytetrahydrofuranyl)-3-methyl-3-cyclohexenyl-1,2-dicarboxylic anhydride. The above-mentioned can be used alone or in any combination. In view of the characteristics of the resin cured film, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and succinic anhydride are preferred;

[0046] Preferably, the number average molecular weight of the alkali-soluble multifunctional photosensitive epoxy resin is 2,000 to 100,000, and more preferably 5,000 to 30,000.

[0047] In the technical solution of the present invention, the alkali-soluble polyimide resin molecular chain contains alkali-soluble groups such as carboxyl groups, acid anhydride groups and ester groups.

[0048] Preferably, the molecular weight of the alkali-soluble polyimide resin is 3,000 to 150,000.

[0049] In the technical solution of the present invention, the type of the photopolymerization initiator is not particularly limited, and specific examples include oxime ester photopolymerization initiators, such as OXE-1, OXE-2, etc.; acylphosphine oxide photopolymerization initiators, such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc.; acetophenone photopolymerization initiators, such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc.; benzoin and its alkyl ether photopolymerization initiators, such as benzoin, benzoin, anthraquinone photopolymerization initiator, such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, etc.; thioxanthone photopolymerization initiator, such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc.; ketal photopolymerization initiator, such as acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.; benzophenone photopolymerization initiator, such as benzophenone, 4,4'-bis-diethylaminobenzophenone, etc. The above can be used alone or in any combination, and oxime ester photopolymerization initiator is preferred.

[0050] Preferably, the content of the photopolymerization initiator is 5 to 25 parts by mass based on 100 parts by mass of the alkali-soluble multifunctional photosensitive epoxy resin.

[0051] In the technical solution of the present invention, the photopolymerizable monomer is selected from at least one of hydroxyl-containing (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate; monofunctional (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and lauryl (meth)acrylate; and 1,6-hexanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, neopentyl glycol diethoxy / propoxy di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and polydipentaerythritol hexa(meth)acrylate.

[0052] Preferably, the content of the photopolymerizable monomer is 10 to 30 parts by mass based on 100 parts by mass of the alkali-soluble multifunctional photosensitive epoxy resin.

[0053] In the technical solution of the present invention, the thermosetting component is an epoxy resin, selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, hydrogenated bisphenol A epoxy resin, brominated bisphenol A epoxy resin, dimethylbenzene epoxy resin, diphenol epoxy resin, alicyclic epoxy resin, soluble novolac epoxy resin, cresol soluble epoxy resin, trisphenol methane epoxy resin, N-glycidyl epoxy resin, triglycidyl isocyanurate, 2,6-xylenol dimer diglycidyl ether, alicyclic epoxy resin, and xylene epoxy resin.

[0054] Preferably, based on 100 parts by mass of the alkali-soluble multifunctional photosensitive epoxy resin, the content of the heat curing component is 15 to 45 parts by mass.

[0055] In the technical solution of the present invention, the inorganic filler is an inorganic filler having a reactive functional group on the surface after modification and / or an inorganic filler without surface modification treatment; the inorganic filler is selected from at least one of barium sulfate, barium titanate, calcium oxide, talc, fumed silica, silica, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, titanium oxide, mica powder and kaolin, preferably at least one of barium sulfate, silica, aluminum oxide, aluminum hydroxide and calcium carbonate; the reactive functional group is a functional group reactive with the alkali-soluble multifunctional photosensitive epoxy resin, selected from at least one of epoxy, olefinic unsaturated bond, amino, carboxyl, hydroxyl and thiol, preferably at least one of epoxy, olefinic unsaturated bond and hydroxyl, more preferably olefinic unsaturated bond, especially vinyl. These reactive functional groups increase the binding force by forming chemical bonds with the alkali-soluble multifunctional photosensitive epoxy resin.

[0056] In the technical solution of the present invention, in the inorganic filler having reactive functional groups on the surface after modification, the content of the reactive functional groups is 0.001 to 0.5% by weight of the inorganic filler, preferably 0.005 to 0.3% by weight.

[0057] In the technical solution of the present invention, the particle size of the inorganic filler is 0.001-100 μm, preferably 0.05-20 μm, more preferably 0.05-3 μm. In particular, when the photosensitive resin composition needs to be further ground, the particle size of the inorganic filler can also be in other ranges, without special limitation.

[0058] Preferably, based on 100 parts by mass of the alkali-soluble multifunctional photosensitive epoxy resin, the content of the filler is 10 to 80 parts by mass.

[0059] In some specific embodiments, the photosensitive resin composition further comprises a pigment, and the pigment is selected from at least one of phthalocyanine green, phthalocyanine blue, titanium dioxide, carbon black and lithopone, and is preferably a pigment free of free halogen.

[0060] In some specific embodiments, the photosensitive resin composition further includes additives, and the additives include at least one of epoxy resin curing accelerator, photoinitiator auxiliary, thixotropic tackifier, diluent, inhibitor, tackifier, defoamer, leveling agent, coupling agent, antioxidant and rust inhibitor.

[0061] In the technical solution of the present invention, the type of the defoaming agent is not particularly limited, and is preferably a silicone defoaming agent, an acrylate defoaming agent or any mixture thereof, and specifically includes KS-66 of Shin-Etsu Corporation of Japan; defoaming agents of TEGO of Germany: Foamex N, Foamex 815N, Foamex 825, Foamex 840, Foamex 842; Deqian Hemmings defoaming agents: DEUCHEM 3200, DEUCHEM 3500, DEUCHEM 5300, DEUCHEM 5400, DEUCHEM 5600, DEUCHEM 6500, DEUCHEM 6800; DEUCHEM 6600, etc.; acrylate defoaming agents of BYK of Germany: BYK-051, BYK-052, BYK-053, BYK-057, etc. Based on 100 parts by mass of the total mass of the alkali-soluble multifunctional photosensitive epoxy resin and the alkali-soluble polyimide resin, the content of the defoaming agent is 0.05 to 20 parts by mass, preferably 0.1 to 3 parts by mass.

[0062] In the technical solution of the present invention, the type of the leveling agent is not particularly limited, and specific examples thereof include BYK-354, BYK-306, BYK-399 of BYK Chemicals, or any mixture thereof. Based on the total mass of the alkali-soluble multifunctional photosensitive epoxy resin and the alkali-soluble polyimide resin as 100 parts by mass, the content of the leveling agent is 0.05 to 20 parts by weight, preferably 0.1 to 5 parts by weight.

[0063] In the technical solution of the present invention, the diluent is an organic solvent, which is not particularly limited, and includes ethers such as ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, etc.; esters such as ethyl acetate, butyl acetate, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, etc. Methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate, dipropylene glycol butyl ether acetate, etc.; ketones, such as butanone, cyclohexanone, isophorone; aromatic solvents, such as toluene, xylene, tetramethylbenzene; and petroleum solvents, such as naphtha, oxidized naphtha, solvent naphtha, etc., the above-mentioned can be used alone or in any combination.

[0064] In the technical solution of the present invention, the type of the epoxy resin curing accelerator is not particularly limited, and specific examples include imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl- Amine compounds such as N,N-dimethylbenzylamine, guanamine, methylguanamine, benzoguanamine, and melamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphine compounds such as triphenylphosphine; s-triazine derivatives such as 2,4-diamino-6-methacryloyloxyethyl-s-triazine, 2-vinyl-2,4-diamino-s-triazine, 2-vinyl-4,6-diamino-s-triazine·isocyanuric acid adduct, and 2,4-diamino-6-methacryloyloxyethyl-s-triazine·isocyanuric acid adduct, etc. In addition, the blocked isocyanate compounds of dimethylamine 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ produced by Shikoku Chemical Industry Co., Ltd.; U-CAT3503N, U-CAT3502T produced by SAN-APRO Co., Ltd. and bicyclic amidine compounds and their salts DBU, DBN, U-CATSA102, U-CAT5002, etc. can also be cited. Based on 100 parts by mass of the alkali-soluble multifunctional photosensitive epoxy resin, the content of the epoxy resin curing accelerator is 0.05 to 40 parts by mass, preferably 0.1 to 10 parts by mass.

[0065] On the other hand, the present invention provides the use of the above-mentioned fluorine-containing diamine, the above-mentioned polyimide resin, and the above-mentioned photosensitive resin composition in semiconductor packaging, preferably, in the preparation of photosensitive solder resist ink, preferably, in the preparation of photosensitive solder resist ink suitable for high-frequency communication.

[0066] In the technical solution of the present invention, the method for preparing the photosensitive solder resist ink from the photosensitive resin composition is not particularly limited, and specifically comprises mixing the components and then kneading them in a three-roll mill.

[0067] In another aspect, the present invention provides a photosensitive film obtained by curing the above-mentioned photosensitive resin composition; preferably, the thickness of the photosensitive film is 5 to 200 μm, more preferably 15 to 60 μm, and particularly preferably 20 to 50 μm.

[0068] In another aspect, the present invention provides a circuit board, comprising a photosensitive film formed by curing the above-mentioned photosensitive resin composition.

[0069] In the technical solution of the present invention, the method for preparing the circuit board comprises the following steps:

[0070] The photosensitive resin composition is applied to a circuit board with pre-formed circuits by spraying, flow coating, roller coating, wire rod coating, or screen printing, and dried at 50°C to 90°C; selectively exposed; developed in a dilute alkaline aqueous solution, and cured at 130°C to 180°C.

[0071] The above technical solution has the following advantages or beneficial effects:

[0072] The present invention provides a fluorine-containing diamine and a polyimide resin prepared from the fluorine-containing diamine, and the polyimide resin is introduced into a photosensitive resin composition as an alkali-soluble polyimide, which improves the thermal stability and glass transition temperature of the photosensitive resin composition on the one hand; on the other hand, the introduction of the fluorine element with a smaller polarizability makes the polyimide have a lower dielectric constant and loss, which is conducive to meeting the application requirements of high-frequency communication. The photosensitive resin composition can be used to prepare a photosensitive solder resist ink, and the dry film obtained after curing has good flexibility and mechanical strength, and has both excellent thermal stability and a high glass transition temperature, good thermal stability, mechanical properties, exposure sensitivity and alkali development characteristics, and good dimensional stability of temperature changes, and excellent dielectric properties, which can meet the increasingly demanding performance requirements of printed circuit boards, and is suitable for high-frequency communication and more scenes. DETAILED DESCRIPTION

[0073] The following embodiments are only some embodiments of the present invention, rather than all embodiments. Therefore, the detailed description in the embodiments of the present invention provided below is not intended to limit the scope of the present invention claimed for protection, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making creative work belong to the protection scope of the present invention.

[0074] In the present invention, unless otherwise specified, all equipment and raw materials can be purchased from the market or are commonly used in the industry. The methods in the following embodiments are all conventional methods in the art unless otherwise specified.

[0075] In order to solve the problems of poor thermal stability, low glass transition temperature and high dielectric constant of photosensitive solder resist ink in the prior art, the present invention provides a photosensitive solder resist ink and a dry film using the same.

[0076] Synthesis example:

[0077] Synthesis Example 1: Alkali-soluble multifunctional photosensitive epoxy resin A

[0078] 210g of o-cresol epoxy resin (SQPN-704M purchased from Shandong Shengquan New Materials Co., Ltd., with an epoxy equivalent of 210), 0.5g of hydroquinone and 200g of diethylene glycol ethyl ether acetate were added to a four-necked round-bottom flask in a N2 atmosphere, stirred and heated to 105°C and maintained at this temperature for 1 hour to dissolve all the substances; after complete dissolution, the temperature was lowered to 90°C, and then 72g of acrylic acid and 1g of triphenylphosphine were added dropwise, and the temperature was controlled at 95°C during the addition process. After the addition was completed, the temperature was raised to 105°C and reacted at this temperature for 12 hours; during the reaction process, the acid value of the reactant was measured until the acid value was 0.8mgKOH / g, the temperature was lowered to 60°C, and then 75g of tetrahydrophthalic anhydride was added, and the reaction was carried out at 90°C for 4 to 8 hours.

[0079] In this synthesis example, a pale yellow alkali-soluble multifunctional photosensitive resin A having a solid content of 64% and a solid acid value of 92.3 mgKOH / g was finally obtained.

[0080] Synthesis Example 2: Synthesis of 4,4'-((3"-,5"-difluoro-[1,1'-:4'-,1"-triphenyl]-3,5-diyl)bis(oxy)diphenylamine (Diamine 1)

[0081] The diamine preparation process in this synthesis example is as follows:

[0082]

[0083] (1) 1-Bromo-3,5-dichlorobenzene (10 mmol), p-nitrophenol (25 mmol), and potassium carbonate (25 mmol) were added to a 500 mL three-necked flask in sequence. Under a nitrogen atmosphere, 100 mL of ultra-dry N,N-dimethylformamide (DMF) was added, and the mixture was stirred and heated to 150°C for 5 h. After cooling to room temperature naturally, the organic phase and the aqueous phase were separated by extraction with dichloromethane and water, and the solvent was removed by rotary evaporation to obtain a crude product. The product was subjected to column chromatography on a silica gel column using petroleum ether / ethyl acetate (volume ratio 4:1). Finally, a brown-yellow solid was obtained by drying, with a yield of 81%. The mass spectrometry result was 430.88 (m / z).

[0084] (2) 4,4'-((5-bromo-1,3-phenylene)bis(oxy))bis(nitrobenzene) (8 mmol), (3',5'-difluoro-[1,1'-biphenyl]-4-yl)boric acid (8.2 mmol), and potassium carbonate (24 mmol) were added to a 500 mL three-necked flask in sequence, and then 120 mL of tetrahydrofuran and 40 mL of water were added; magnetic stirring and nitrogen flow were performed at room temperature for 10 min, and then Pd(PPh3)4 (0.24 mmol) was added; refluxed at 68°C for 20 hours, and naturally cooled to room temperature; the organic phase and the aqueous phase were separated by extraction with dichloromethane and saturated brine, and the solvent was removed by rotary evaporation to obtain a crude product; column chromatography was performed on a silica gel column with petroleum ether / ethyl acetate (volume ratio 8:1), and the product was obtained after drying, with a yield of 85%. The mass spectrum result was: 541.26 (m / z);

[0085] (3) 3,5-difluoro-3'-,5"-bis(4-nitrophenoxy)-1,1':4'-,1'-triphenyl (10 mmol) and palladium on carbon (0.5 g) were placed in a 500 mL three-necked flask with a nitrogen atmosphere, and 100 mL of ultra-dry tetrahydrofuran (THF) was added. The mixture was stirred and heated to 68°C. 7.4 mL of hydrazine hydrate was slowly added dropwise. After the addition was completed, the mixture was reacted for 5 h and naturally cooled to room temperature. The palladium on carbon was removed by suction, and the solvent was removed by rotary evaporation to obtain a crude product. The product was subjected to column chromatography on a silica gel column using petroleum ether / ethyl acetate (volume ratio 1:1). After drying, a solid product was obtained with a yield of 90%. The mass spectrometry result was 481.31 (m / z).

[0086] Synthesis Example 3: 4,4'-((5-(3,5-difluorophenoxy)-1,3-phenylene)bis(methylene))diphenylamine (diamine 29)

[0087] The diamine preparation process in this synthesis example is as follows:

[0088]

[0089] (1) 4,4'-((5-chloro-1,3-phenylene)bis(methylene))bis(nitrobenzene) (10 mmol), 3,5-difluorophenol (12 mmol), and potassium carbonate (20 mmol) were sequentially added into a 500 mL three-necked flask in a nitrogen atmosphere, and 100 mL of ultra-dry DMF was added. The mixture was stirred and heated to 150° C. and reacted for 5 h. After naturally cooling to room temperature, the organic phase and the aqueous phase were separated by extraction with dichloromethane and water, and the solvent was removed by rotary evaporation to obtain a crude product. The product was subjected to column chromatography on a silica gel column using petroleum ether / ethyl acetate, and the product was obtained after drying. The yield was 78%, and the mass spectrum result was: 478.34 (m / z);

[0090] (2) 4,4'-((5-(3,5-difluorophenoxy)-1,3-phenylene)bis(methylene))bis(nitrobenzene) (10 mmol) and palladium on carbon (0.5 g) were placed in a 500 mL three-necked flask in a nitrogen atmosphere, 100 mL of ultra-dry THF was added, and the mixture was stirred and heated to 68° C. After slowly dropping 7.5 mL of hydrazine hydrate, the mixture was reacted for 5 h and naturally cooled to room temperature. The palladium on carbon was removed by suction filtration, and the solvent was removed by rotary evaporation to obtain a crude product. The product was subjected to column chromatography on a silica gel column using petroleum ether / ethyl acetate (1:1 volume ratio), and a solid product was obtained after drying, with a yield of 83%. The mass spectrometry result was: 417.23 (m / z);

[0091] Synthesis Example 4: 5-(3,4,5-trifluorophenoxy)-1,3-phenylenebis(4-aminobenzoate) (diamine 48)

[0092] The diamine preparation process in this synthesis example is as follows:

[0093]

[0094] (1) 5-Chlorobenzene-1,3-diol (10 mmol) was added to a 500 mL three-necked flask, and 200 mL N,N-dimethylacetamide and 40 mL triethylamine were added. Then, 4-nitrobenzoyl chloride (40 mmol) was slowly added under ice bath conditions. The temperature was raised to 100°C with magnetic stirring under nitrogen atmosphere for 24 h. The reaction solution was poured into a mixture of methanol and water in a volume ratio of 1:1 to precipitate. The solid obtained by filtration was recrystallized in N,N-dimethylformamide, the solid was collected, and dried at 80°C for 24 h to obtain the product with a yield of 84%. The mass spectrometry result was 443.82 (m / z).

[0095] (2) 5-Chloro-1,3-phenylenebis(4-nitrobenzoate) (10 mmol), 3,4,5-trifluorophenol (12 mmol), and potassium carbonate (20 mmol) were sequentially added to a 500 mL three-necked flask in a nitrogen atmosphere, and 100 mL of ultra-dry DMF was added. The mixture was stirred and heated to 150° C. for reaction for 5 h, and then naturally cooled to room temperature. The organic phase and the aqueous phase were separated by extraction with dichloromethane and water, and the solvent was removed by rotary evaporation to obtain a crude product. The product was subjected to column chromatography on a silica gel column using petroleum ether / ethyl acetate and dried to obtain the product with a yield of 84%. The mass spectrum result was: 555.19 (m / z);

[0096] (3) 5-(3,4,5-trifluorophenoxy)-1,3-phenylenebis(4-nitrobenzoate) (10 mmol) and palladium on carbon (0.5 g) were placed in a 500 mL three-necked flask with a nitrogen atmosphere, 100 mL of ultra-dry THF was added, the mixture was stirred and heated to 68°C, 7.5 mL of hydrazine hydrate was slowly added dropwise, and after the addition was completed, the mixture was reacted for 12 h, and then naturally cooled to room temperature. The palladium on carbon was removed by suction, and the solvent was removed by rotary evaporation to obtain a crude product; column chromatography was performed on a silica gel column using petroleum ether / ethyl acetate (1:1 volume ratio), and the product was obtained after drying, with a yield of 83%. The mass spectrometry result was: 495.26 (m / z).

[0097] Synthesis Example 5: N 1 ,N 3 Bis(4-aminophenyl)-N 5 ,N 5 Bis(3,5-bis(trifluoromethyl)phenyl)benzene-1,3,5-triamine (diamine 88)

[0098] The diamine preparation process in this synthesis example is as follows:

[0099]

[0100] (1) 3,5-difluoroaniline (10 mmol), p-aniline (24 mmol), and potassium carbonate (35 mmol) were sequentially added to a 500 mL three-necked flask in a nitrogen atmosphere, and 150 mL of dimethyl sulfoxide was added. The mixture was stirred magnetically and heated to 150° C. for 12 h. The reaction solution was poured into cold water, the precipitate was filtered out, and washed with hydrochloric acid and water to obtain the product with a yield of 71%. The mass spectrum result was: 306.39 (m / z);

[0101] (2) N 1 ,N 3Bis(4-aminophenyl)benzene-1,3,5-triamine (10mmol), 1-fluoro-3,5-bis(trifluoromethyl)benzene (24mmol) and potassium carbonate (35mmol) were added successively into a 500mL three-necked flask in a nitrogen atmosphere, and 150mL of dimethyl sulfoxide was added. The mixture was stirred magnetically and heated to 150°C for 12h. The reaction solution was poured into cold water, the precipitate was filtered out, and the product was obtained by column chromatography with a yield of 76%. The mass spectrometry result was 730.30 (m / z).

[0102] Synthesis Example 6: Alkali-soluble polyimide resin B-1

[0103] A 100 mL three-necked flask equipped with a mechanical stirrer was filled with a nitrogen atmosphere, and then 5 mmol of diamine was added: 2.5 mmol 4,4'-((3"-,5"-difluoro-[1,1'-:4'-,1"-triphenyl]-3,5-diyl)bis(oxy)diphenylamine (diamine 1 prepared in Synthesis Example 2) and 2.5 mmol 3,5-diaminobenzoic acid, and NMP was added at room temperature until the diamine powder was completely dissolved; 5 mmol 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride (a-ODPA) was added twice to the NMP solution of the above diamine; after stirring at room temperature for 12 hours, NMP was added for dilution, and 3.06 g acetic anhydride and 2.52 g triethylamine were added, and the reaction was continued at room temperature for 12 hours to control the molecular weight at 60000; the reaction solution was dropped into deionized water, filtered and washed with anhydrous ethanol to obtain an alkali-soluble polyimide resin B-1 powder.

[0104] Synthesis Example 7: Alkali-soluble polyimide resin B-2

[0105] The preparation process of the alkali-soluble polyimide resin in this synthesis example is the same as that in Synthesis Example 6, except that the diamine is replaced by 4,4'-((5-(3,5-difluorophenoxy)-1,3-phenylene)bis(methylene))diphenylamine (diamine 29) prepared in Synthesis Example 3 to obtain alkali-soluble polyimide resin B-2 powder.

[0106] Synthesis Example 8: Alkali-soluble polyimide resin B-3

[0107] The preparation process of the alkali-soluble polyimide resin in this synthesis example is the same as that in Synthesis Example 6, except that the diamine is replaced by 5-(3,4,5-trifluorophenoxy)-1,3-phenylenebis(4-aminobenzoate) (diamine 48) prepared in Synthesis Example 4 to obtain alkali-soluble polyimide resin B-3 powder.

[0108] Synthesis Example 9: Alkali-soluble polyimide resin B-4

[0109] The preparation process of the alkali-soluble polyimide resin in this synthesis example is the same as that in Synthesis Example 6, except that the diamine is replaced by N prepared in Synthesis Example 5.1 ,N 3 Bis(4-aminophenyl)-N 5 ,N 5 Bis(3,5-bis(trifluoromethyl)phenyl)benzene-1,3,5-triamine (diamine 88) was added to obtain an alkali-soluble polyimide resin B-4 powder.

[0110] Synthesis Example 10: Alkali-soluble polyimide resin B-5:

[0111] The preparation process of the alkali-soluble polyimide resin in this synthesis example is the same as that in Synthesis Example 6, except that the diamine is replaced by diaminodiphenyl ether (ODA) to obtain an alkali-soluble polyimide resin B-5 powder.

[0112] Example: Photosensitive resin composition

[0113] The photosensitive resin composition was prepared according to the mass fractions shown in Table 1:

[0114] Table 1:

[0115]

[0116]

[0117] Note 1: Photopolymerization initiator: OXE-2 purchased from Tianjin Huiren Hengtong Technology Co., Ltd.

[0118] Note 2: Epoxy resin: YSLV-80XY purchased from Nippon Steel, Japan;

[0119] Note 3: Silicon dioxide, particle size is 100nm~3μm;

[0120] Note 4: Barium sulfate: B-34 purchased from Sakai Chemical Co., Ltd., Japan;

[0121] Note 5: Pigment: Phthalocyanine green purchased from BASF;

[0122] Note 6: Leveling agent: purchased from BYK Chemicals, Germany;

[0123] Note 7: Defoaming agent: KS-66 purchased from Shin-Etsu Chemical Co., Ltd., Japan;

[0124] Note 8: Diluent: Carbitol acetate.

[0125] Effect Example: Photosensitive Solder Mask Ink

[0126] The photosensitive resin composition in the embodiment and the comparative example was stirred and mixed with a three-roller machine to prepare a photosensitive solder resist ink, which was coated to maintain a thickness of 25 μm, soft-baked at 80° C. for 10 minutes, exposed, developed with a 1% dilute sodium carbonate solution, and thermally cured at 170° C. for 1 hour, and then tested for relevant properties. The results are shown in Table 2.

[0127] Table 2

[0128]

[0129]

[0130] The above results show that the alkali-soluble polyimide resin prepared from fluorinated diamine monomers can reduce the dielectric constant of photosensitive solder resist ink to below 2.7, and the dielectric loss to about 0.003 (at 1 GHz). At the same time, its glass transition temperature is as high as 180°C, 5% thermal weight loss is above 350°C, and the photolithography performance is excellent, wherein the resolution of the lines or holes of the photolithography pattern reaches 40μm, which is judged as excellent, 40μm<resolution<60μm is judged as good, and 60μm<resolution<80μm is judged as qualified. Compared with comparative example 1, both the thermodynamic and dielectric properties are greatly improved.

[0131] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A fluorinated diamine, characterized in that: The fluorinated diamine has a structure shown in the following formula (i): In formula (i): L1, L2, and L3 are independently selected from any one of -O-, -S-, -Se-, -NH-, -CH2-, -C(CH3)2-, -N(CH3)-, -SiH2-, carbonyl, sulfone, ester, amide, C2-C6 alkyl chain, and C5-C30 aromatic group; Y1 is a fluorine-containing substituent, which is monosubstituted or polysubstituted; the fluorine-containing substituent is selected from at least one of -F, -CF3, and -OCF3.

2. Use of the fluorinated diamine according to claim 1 in semiconductor packaging.

3. The use according to claim 2, characterized in that: Use in preparing photosensitive solder resist ink.

4. The use according to claim 3, characterized in that Use in preparing photosensitive solder resist ink suitable for high-frequency communication.

5. A polyimide resin, characterized in that: The polyimide resin is a product obtained by further imidizing any one or more of the fluorinated diamines described in claim 1 with a carboxyl-containing diamine or dianhydride.

6. The polyimide resin according to claim 5, characterized in that The imidization is carried out under the action of a dehydrating agent.

7. The polyimide resin according to claim 6, characterized in that The dehydrating agent is selected from at least one of anhydride-tertiary amine dehydrating agent, thionyl chloride-tertiary amine dehydrating agent and acetyl chloride-tertiary amine dehydrating agent; the anhydride is selected from at least one of acetic anhydride, phthalic anhydride and trifluoroacetic anhydride; the tertiary amine is selected from at least one of pyridine and triethylamine.

8. The polyimide resin according to claim 5, characterized in that The polymerization reaction temperature is -10°C to 80°C, and the reaction time is 4 to 24 hours.

9. The polyimide resin according to claim 5, characterized in that The reaction temperature of the imidization is 20 to 120° C., and the reaction time is 1 to 24 hours.

10. Use of the polyimide resin according to claim 5 in semiconductor packaging.

11. The use according to claim 10, characterized in that Use in preparing photosensitive solder resist ink.

12. The use according to claim 10, characterized in that Use in preparing photosensitive solder resist ink suitable for high-frequency communication.

13. A photosensitive resin composition, characterized in that: include: (A) component: 100 parts by mass of an alkali-soluble multifunctional photosensitive epoxy resin; The multifunctional group contains three or more epoxy groups; (B) component: 20 to 60 parts by mass of an alkali-soluble polyimide resin; (C) component: 1 to 40 parts by mass of a photopolymerization initiator; (D) component: 5 to 50 parts by mass of a photopolymerizable monomer; (E) component: 10 to 80 parts by weight of a thermosetting component; (F) component: 10 to 100 parts by mass of an inorganic filler; Wherein, the alkali-soluble polyimide resin is the polyimide resin according to claim 2.

14. The photosensitive resin composition according to claim 13, characterized in that: The acid value of the alkali-soluble multifunctional photosensitive epoxy resin is 40 to 200 mg KOH / g.

15. The photosensitive resin composition according to claim 14, characterized in that: The acid value of the alkali-soluble multifunctional photosensitive epoxy resin is 50 to 180 mg KOH / g.

16. The photosensitive resin composition according to claim 13, characterized in that: The alkali-soluble multifunctional photosensitive epoxy resin is a multifunctional epoxy resin containing a photosensitive group and an alkali-soluble group on the molecular chain; the photosensitive group is selected from at least one of a carbonyl group, a carboxyl group, a peroxide group and a carbon-carbon double bond; the alkali-soluble group is selected from at least one of a carboxyl group, an acid anhydride and an ester group.

17. The photosensitive resin composition according to claim 13, characterized in that: The alkali-soluble multifunctional photosensitive epoxy resin is selected from at least one of phenol novolac epoxy resin, bisphenol A novolac epoxy resin, naphthalene epoxy resin, o-cresol novolac epoxy resin, alkylphenol novolac epoxy resin, dicyclopentadiene epoxy resin, glycidylamine epoxy resin, trihydroxybenzene methane epoxy resin, tetraphenol ethane epoxy resin, diglycidyl phthalate resin and epoxy compounds of condensation products of phenols and aromatic aldehydes having phenolic hydroxyl groups.

18. The photosensitive resin composition according to claim 13, characterized in that: The number average molecular weight of the alkali-soluble multifunctional photosensitive epoxy resin is 2,000 to 100,000.

19. The photosensitive resin composition according to claim 18, characterized in that: The number average molecular weight of the alkali-soluble multifunctional photosensitive epoxy resin is 5,000 to 30,000.

20. The photosensitive resin composition according to claim 13, characterized in that: The molecular weight of the alkali-soluble polyimide resin is 3,000 to 150,000.

21. The photosensitive resin composition according to claim 13, characterized in that: The content of the photopolymerization initiator is 5 to 25 parts by mass based on 100 parts by mass of the alkali-soluble multifunctional photosensitive epoxy resin.

22. The photosensitive resin composition according to claim 13, characterized in that: The content of the photopolymerizable monomer is 10 to 30 parts by mass based on 100 parts by mass of the alkali-soluble multifunctional photosensitive epoxy resin.

23. The photosensitive resin composition according to claim 13, characterized in that: The content of the heat curing component is 15 to 45 parts by mass based on 100 parts by mass of the alkali-soluble multifunctional photosensitive epoxy resin.

24. The photosensitive resin composition according to claim 13, characterized in that: Based on 100 parts by mass of the alkali-soluble multifunctional photosensitive epoxy resin, the content of the filler is 10 to 80 parts by mass.

25. Use of the photosensitive resin composition according to claim 13 in semiconductor packaging.

26. The use according to claim 25, characterized in that Use in preparing photosensitive solder resist ink.

27. The use according to claim 26, characterized in that Use in preparing photosensitive solder resist ink suitable for high-frequency communication.

28. A photosensitive film, characterized in that: The photosensitive resin composition is obtained by curing the photosensitive resin composition according to any one of claims 13 to 24.

29. The photosensitive film according to claim 28, characterized in that The thickness of the photosensitive film is 5 to 200 μm.

30. The photosensitive film according to claim 29, characterized in that The thickness of the photosensitive film is 15-60 μm.

31. The photosensitive film according to claim 30, characterized in that The thickness of the photosensitive film is 20-50 μm.

32. A circuit board, characterized in that: It comprises a photosensitive film formed by curing the photosensitive resin composition according to any one of claims 13 to 24.

Images