Photosensitive resin composition and application thereof

Abstract

The invention discloses a photosensitive resin composition and application thereof, the photosensitive resin composition is formed by the following components: component (A): alkali soluble resin; component (B): a compound containing an unsaturated bond; a component (C): a photoinitiator; a component (D): a coupling agent; the photoinitiator has a structure as shown in a formula I, and in the formula I, R1, R2, R3 and R4 are independently selected from one of hydrogen atoms, fluorine atoms, C1-C25 alkyl groups and alkoxy groups; and R5 and R6 are independently selected from bromine or chlorine. The photosensitive resin composition disclosed by the invention can be exposed, is developed through an alkaline developing solution, is good in sensitivity and high in resolution ratio, and has a wide application prospect; # imgabs0 #

Description

Technical Field

[0001] The present application relates to a photosensitive resin composition and application thereof, belonging to the field of polymer compounds. Background Art

[0002] Electronic information technology is changing with each passing day and developing rapidly. The reason is that the design and manufacturing level of integrated circuits in the semiconductor industry is constantly improving and developing, and the core and key technology for manufacturing integrated circuits is the photolithography process. As a key material in the photolithography process, negative photoresist has been widely used in the modern electronics industry. Generally speaking, under light, the photoinitiator system in the negative photoresist initiates the polymerization of monomers to form a cross-linked network structure, and the photoresist that is not photo-cross-linked is easily washed away by an alkaline solution, thereby forming the required pattern. The photoinitiator system plays a vital role in photoresist, and many studies are focused on the development of the photoinitiator system to obtain a high-performance initiator system that meets industrial requirements.

[0003] The most commonly used in industry is the bimolecular photoinitiator system, also known as the hydrogen absorption initiator system, which is a triplet excited state of the photoinitiator under light, which further reacts with another hydrogen donor molecule to produce an activated molecule to initiate a polymerization reaction. The photoinitiator system used in industry for photoresists is basically based on hexaaryl diimidazole compounds and has long been monopolized by DuPont. Due to its special structure and atomic composition, it leads to a series of problems such as poor compatibility and toxicity. Therefore, a new type of photoinitiator system is developed to improve other properties while ensuring the initiation performance. Summary of the invention

[0004] In order to develop a curing material suitable for microelectronic fields such as semiconductor packaging, the present invention provides a photosensitive resin composition, the photoinitiator of the photosensitive resin composition contains a quinoxaline structure, can be exposed, and developed by an alkaline developer, has good sensitivity and high resolution, and has broad application prospects.

[0005] According to a first aspect of the present application, a photosensitive resin composition is provided, which is formed by the components of the following formula, wherein the photosensitive resin composition comprises the following components:

[0006] Component (A): alkali-soluble resin;

[0007] Component (B): a compound containing an unsaturated bond;

[0008] Component (C): photoinitiator;

[0009] Component (D): coupling agent;

[0010] The photoinitiator has a structure shown in Formula I:

[0011]

[0012] In formula I, R1, R2, R3, and R4 are independently selected from a hydrogen atom, a fluorine atom, a C1-C25 alkyl group, and a C1-C25 alkoxy group;

[0013] R5, R6 are independently selected from bromine or chlorine;

[0014] The alkali-soluble resin is selected from at least one of alkali-soluble polyimide and alkali-soluble polyimide precursor.

[0015] Optionally, in Formula I, R1, R2, R3, and R4 are independently selected from a hydrogen atom, a fluorine atom, a C6-C18 alkyl group, and a C6-C18 alkoxy group.

[0016] Optionally, the photoinitiator is selected from one of the structures shown in Formula A-1 to Formula A-5;

[0017]

[0018]

[0019] In order to ensure the solubility of the quinoxaline photoinitiator in the system, enhance its light absorption ability, and electron transfer ability, the structure of the quinoxaline photoinitiator of formula I is preferably A-1 to A-5.

[0020] Quinoxaline derivatives have a similar structure to pigments, and their ultraviolet absorption can be easily changed by changing the substituents, making them potential high-efficiency photoinitiators. The introduction of alkoxy side chains into quinoxaline compounds can improve the solubility of quinoxaline photoinitiators in the system and enhance their light absorption capacity; the introduction of halogen atoms is to increase the electron transfer ability of the molecule.

[0021] Alkali solubility means that the amount of the resin dissolved in 100 g of a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 25°C is 0.1 g or more.

[0022] Optionally, the alkali-soluble polyimide and the alkali-soluble polyimide precursor are both prepared by reacting a tetracarboxylic dianhydride compound with a diamine compound.

[0023] Optionally, the tetracarboxylic dianhydride compound is selected from at least one of pyromellitic dianhydride, 3,4,3',4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,4,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride.

[0024] Optionally, the diamine compound is selected from diamine compound A or a mixture of diamine compound A and diamine compound B, and the molar amount of diamine compound B is less than or equal to 10% of the total molar amount of diamine compounds.

[0025] Optionally, the diamine compound A is selected from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2'-bis(3-amino-4-hydroxyphenyl)propane, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylmethane, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfide, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, p-phenylenediamine, m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4' -diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 4,4'-bis(4-aminophenyl)propane, 4,4'-bis(4-aminophenoxy)diphenyl sulfone, 2,2'-trifluoromethyl-4,4'-diaminodiphenyl ether, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-diaminodiphenyl sulfone, and the diamine compound containing phenolic hydroxyl group in the diamine compound A accounts for 50 to 100% of the total molar amount of the diamine compound.

[0026] Optionally, the diamine compound B is selected from at least one of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 3,3′-(1,4-phenylenebis(dimethylsilanediyl))bis(propyl-1-amine), and 4,4′-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)diphenylamine.

[0027] Optionally, the (A) alkali-soluble resin is at least one selected from polyamic acid, polyamic acid ester, and polyimide. Alkali-soluble means that the amount of the resin dissolved in 100g of 2.38wt% tetramethylammonium hydroxide aqueous solution at 25°C is 0.1g or more.

[0028] Optionally, polyamic acid, polyamic acid ester and polyimide can be obtained by reacting a tetracarboxylic dianhydride compound with a diamine compound. The specific preparation method can refer to the preparation method in the prior art, which is not difficult for those skilled in the art.

[0029] Optionally, a capping agent may be used to cap at least a portion of the ends of the alkali-soluble resin, thereby controlling the molecular weight of the alkali-soluble resin within an appropriate range. The capping agent is preferably 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzenesulfonic acid, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 3-aminosalicylic acid, 4-aminosalicylic acid, etc.

[0030] Alternatively, the alkali-soluble resin can be prepared by the following method:

[0031] (1) Preparation method of polyamic acid

[0032] Polyamic acid can be obtained by reacting a diamine compound with tetracarboxylic dianhydride in an organic solvent. The organic solvent can be used as long as it can dissolve the generated polyamic acid, and specifically can be listed as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, γ-butyrolactone, etc. In addition, when the solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, etc. can be used. The above organic solvents can be used alone or in combination. Since the moisture in the organic solvent inhibits the polymerization reaction, the organic solvent can be used after dehydration and drying.

[0033] As a method for reacting a diamine compound and tetracarboxylic dianhydride in an organic solvent, there are listed: a method of obtaining a solution by dispersing or dissolving the diamine compound in an organic solvent with stirring, directly adding tetracarboxylic dianhydride or adding after dispersing or dissolving the tetracarboxylic dianhydride in an organic solvent; a method of adding a diamine compound to a solution obtained by dispersing or dissolving the tetracarboxylic dianhydride in an organic solvent; a method of adding the tetracarboxylic dianhydride and the diamine compound to the organic solvent alternately or simultaneously, and any of the above methods may be used.

[0034] The temperature for synthesizing polyamic acid can be selected from any temperature of -20 to 150°C, preferably 0 to 80°C. The reaction time is preferably 1 to 72 hours, more preferably 2 to 48 hours. The reaction concentration is preferably 1 to 60%, more preferably 10 to 50%. When the reaction concentration is too low, it is difficult to obtain a polymer with a high molecular weight. When the reaction concentration is too high, the viscosity of the reaction solution is too large, making it difficult to stir evenly. During the reaction, the ratio of the molar amount of tetracarboxylic dianhydride to the molar amount of the diamine compound is 1:0.8 to 1.2. Generally, the closer the molar ratio is to 1:1, the greater the molecular weight of the generated polyamic acid.

[0035] (2) Preparation method of polyamic acid ester

[0036] 1) Prepared from polyamic acid

[0037] The polyamic acid ester can be prepared by esterification reaction of the polyamic acid. Specifically, the polyamic acid and the esterification agent are reacted in an organic solvent at -20 to 150° C., preferably 0 to 50° C., for 0.5 to 24 hours, preferably 1 to 4 hours. As the esterifying agent, an esterifying agent that can be easily removed by purification is preferred, and examples thereof include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide dineopentyl butyl acetal, N,N-dimethylformamide di-tert-butyl acetal, 1-methyl-3-tolyl triazene, 1-ethyl-3-p-tolyl triazene, 1-propyl-3-p-tolyl triazene, 4-(4,6-dimethoxy-1,3,5-triazine-2-yl)-4-methylmorpholinochloride, and the like. The amount of the esterifying agent added is in a molar ratio of 2 to 6:1 to the polyamic acid repeating unit.

[0038] The organic solvent may be any solvent as long as it can dissolve the generated polyamic acid, and specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, γ-butyrolactone, etc. In addition, when the solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, and 4-hydroxy-4-methyl-2-pentanone can be used.

[0039] The above organic solvents can be used alone or in combination. Since the water in the organic solvent inhibits the polymerization reaction, the organic solvent can be used after dehydration and drying. From the perspective of polymer solubility, the organic solvent used in the above reaction is preferably N,N-dimethylformamide, N-methylpyrrolidone or γ-butyrolactone, and one or more of them can be used. From the perspective of polymers that are not easy to precipitate and have high molecular weight, the reaction concentration is preferably 1 to 60wt%, more preferably 10 to 50wt%.

[0040] 2) Prepared by reacting a tetracarboxylic acid diester dichloride compound with a diamine compound: Specifically, the tetracarboxylic acid diester dichloride is reacted with a diamine compound in the presence of a base and an organic solvent at -20 to 150°C, preferably 0 to 50°C for 0.5 to 24 hours, preferably 1 to 4 hours. As the base, pyridine, triethylamine, 4-dimethylaminopyridine, etc. can be used. In order to make the reaction proceed gently, pyridine is preferably used. From the viewpoint of easy removal and easy to obtain high molecular weight, the amount of base added is preferably 2 to 4 times the mole of the tetracarboxylic acid diester dichloride, and more preferably 2 to 3 times the mole. From the viewpoint of solubility of monomers and polymers, the solvent used for the above reaction is preferably N-methylpyrrolidone or γ-butyrolactone, and one or a mixture of two or more of the above solvents can be used. From the viewpoint that the polymer is not easy to precipitate and has a high molecular weight, the reaction concentration is preferably 1 to 60wt%, and more preferably 10 to 50wt%. In order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for producing the polyamic acid ester is preferably a dehydrated solvent, and the production is performed under nitrogen protection to prevent mixing of the air.

[0041] 3) Preparation by polycondensation of tetracarboxylic acid diester and diamine compound: Specifically, it can be prepared by reacting tetracarboxylic acid diester and diamine compound in the presence of condensation agent, base and organic solvent at 0 to 150°C, preferably 0 to 100°C for 30 minutes to 24 hours, preferably 3 to 15 hours. As the condensation agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylpropyl)carbodiimide hydrochloride, N,N'-carbonyldiimidazole, dimethyl-1,3,5-triazinylmethylmorpholine, 0-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, 0-(benzotriazol-1-yl)N,N,N',N'-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thia-3-benzoxazolyl) diphenyl phosphate, etc. can be used. The amount of the condensing agent added is preferably 2 to 3 times the molar amount relative to the tetracarboxylic acid diester. As the base, a tertiary amine such as pyridine and triethylamine can be used. From the viewpoint of easy removal and easy to obtain a high molecular weight, the amount of the base added is preferably 2 to 4 times the molar amount relative to the diamine component.

[0042] In the above reaction, the reaction can be efficiently carried out by adding a Lewis acid as an additive. The Lewis acid is preferably a halogenated lithium such as lithium chloride or lithium bromide. The amount of the Lewis acid added is preferably 0 to 1.0 times the molar amount of the diamine component.

[0043] In order to obtain high molecular weight polyamic acid ester more easily among the above-mentioned 3 methods for producing polyamic acid ester, the production method described in the above 1) or 2) is preferred.

[0044] The polyamic acid ester solution obtained by the above method is injected into a poor solvent while stirring to precipitate the polymer. After precipitation several times and washing with a poor solvent, it is dried at room temperature or heated to obtain a purified polyamic acid ester powder. The poor solvent is not particularly limited, and water, methanol, ethanol, ethane, butyl cellosolve, acetone, toluene, etc. can be listed.

[0045] (3) Preparation method of polyimide

[0046] The polyimide of the present invention can be prepared by imidization of the aforementioned polyimide precursor (polyamic acid or polyamic acid ester). The imidization rate of the polyimide of the present invention may not be 100%, and can be adjusted according to the use requirements. Regarding the imidization method, a thermal imidization method in which a polyimide precursor is heated without using a catalyst and a catalytic imidization method using a catalyst can be listed.

[0047] When the polyimide precursor is thermally imidized, the polyimide precursor solution is preferably heated to 100 to 350° C., preferably 120 to 200° C., and thermal imidization is performed while removing water / alcohol generated by the imidization reaction to the outside of the system.

[0048] The catalytic imidization of the polyimide precursor can be carried out by adding a basic catalyst and anhydride to a solution of polyamic acid and stirring at -20 to 250°C, preferably 0 to 180°C. The amount of the basic catalyst is 0.5 to 30 moles of the amic acid group, preferably 2 to 20 times the molar amount, and the amount of the anhydride is 1 to 50 times the molar amount of the amic acid group, preferably 3 to 30 times the molar amount. As the basic catalyst, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. can be listed, among which pyridine is preferred because it has a basicity suitable for promoting the reaction. As the anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. can be listed, among which, when acetic anhydride is used, it is easy to purify after the reaction is completed, so acetic anhydride is preferred. The imidization rate of the catalytic imidization can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

[0049] When recovering the polymer component from the reaction solution of the polyimide, the reaction solution may be put into a poor solvent to precipitate it. Examples of the poor solvent include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, etc. The polymer obtained by precipitating it by putting into the poor solvent is preferably recovered by filtration and then dried at room temperature under normal pressure or reduced pressure or heated.

[0050] Optionally, the weight average molecular weight of (A) the alkali-soluble resin is preferably 10,000 or more and 100,000 or less. When the weight average molecular weight is less than 10,000, the mechanical strength is reduced and the bonding strength is weakened, and the weight average molecular weight is preferably 12,000 or more. When the weight average molecular weight exceeds 100,000, the developability in the alkaline solution is reduced, and the weight average molecular weight is preferably 50,000 or less. In order to adjust the weight average molecular weight of the alkali-soluble resin to an appropriate range, it is preferred to cap at least a portion of the ends of the alkali-soluble resin with the above-mentioned end-capping agent.

[0051] Optionally, the compound containing an unsaturated bond is selected from diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, styrene, α-methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene, 4-methylstyrene, p-vinylbenzene, 2-vinylnaphthalene, butyl acrylate, Butyl methacrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, tricyclodecanediol Alkane dimethanol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-diacryloxy-2-hydroxypropane, 1,3-dimethacryloxy-2-hydroxypropane, methylenebisacrylamide, N,N-dimethylacrylamide, N-hydroxymethylacrylamide, 2,2,6,6-tetramethylpiperidine At least one of methyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, propoxylated bisphenol A diacrylate, propoxylated bisphenol A methacrylate, propoxylated ethoxylated bisphenol A diacrylate, propoxyethoxylated bisphenol A dimethacrylate, N-vinyl caprolactam, polyethylene glycol diacrylate, and 2-isocyanatoethyl methacrylate.

[0052] Optionally, the coupling agent is selected from at least one of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, bis(γ-aminopropyl)tetramethylsiloxane, bis(γ-aminobutyl)tetramethylsiloxane, bis(γ-aminopropyl)tetraphenylsiloxane, bis(γ-aminopropyl)tetraphenylpolysiloxane, bis(γ-aminopropyl)tetraphenylsiloxane, bis(γ-aminobutyl)tetraphenylpolysiloxane, 3-(2,3-epoxypropoxy)propyltriethoxysilane and vinyltriethoxysilane.

[0053] Optionally, the photoinitiator may be used in combination with other photosensitizers, wherein the other photosensitizers are selected from at least one of 2-mercaptobenzothiazole, N-phenylglycine, and N-methyldiethanolamine.

[0054] Optionally, the components of the photosensitive resin composition also contain a solvent, and the solvent is selected from at least one of N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N-vinylpyrrolidone, N,N-diethylformamide, γ-butyrolactone, ethyl lactate, methyl monoglycol dimethyl ether, methyl diglycol dimethyl ether, methyl triglycol dimethyl ether, ethyl monoglycol dimethyl ether, ethyl diglycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether.

[0055] Optionally, the mass ratio of the (A) alkali-soluble resin to the solvent is 100:(80-5000).

[0056] Optionally, the mass ratio of the unsaturated bond-containing compound to the alkali-soluble resin is 20 to 150:100.

[0057] Optionally, the mass ratio of the photoinitiator to the alkali-soluble resin is 0.1-20:100.

[0058] Optionally, the molar ratio of the (C) photoinitiator to other photosensitizers is 1:(1-5).

[0059] Optionally, the mass ratio of the coupling agent to the alkali-soluble resin is 0.01 to 10:100.

[0060] According to the second aspect of the present application, a method for preparing a photosensitive resin composition is provided. The preparation of the photosensitive resin composition of the present application is preferably completed in a Class 1000 clean room equipped with a yellow light source, especially at room temperature, by adding a formulated amount of (A) alkali-soluble resin, (B) a compound containing an unsaturated bond, (C) a photoinitiator and other photosensitizers, and (D) a coupling agent to a solvent and stirring evenly to obtain the composition.

[0061] In order to ensure the purity of the photosensitive resin composition, the photosensitive resin composition may be filtered using a filtering device such as filter paper, filter membrane, filter, etc. The filtering method is not particularly limited, but preferably, pressure filtration is performed using a filter with a pore size of 0.2 to 5 μm.

[0062] According to a third aspect of the present application, there is provided a photosensitive resin sheet, the photosensitive resin sheet comprising a supporting substrate, the supporting substrate being covered with a cured film formed of a photosensitive resin composition varnish;

[0063] The raw materials of the photosensitive resin composition varnish include the above-mentioned photosensitive resin composition and an organic solvent. The organic solvent is selected according to the coating effect of the photosensitive resin composition varnish on the supporting substrate. It can be the solvent used in the preparation process of the photosensitive resin composition or another organic solvent, and there is no special limitation. The following can be listed: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, butyl lactate, butyl lactate; acetone, methyl ethyl acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, 2-heptanone, butanol, isobutanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, diacetone alcohol, toluene, xylene, N-methylpyrrolidone, N-cyclohexylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, etc.

[0064] In order to ensure the purity of the photosensitive resin composition varnish, the photosensitive resin composition varnish can be filtered using a filtering device such as filter paper, filter membrane, filter, etc. The filtering method is not particularly limited, and pressure filtration using a filter with a pore size of 0.2 to 5 μm is preferred.

[0065] There is no particular limitation on the supporting substrate, and various films on the market such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide can be used. In order to improve the adhesiveness and releasability, the bonding surface between the supporting substrate and the photosensitive resin composition film can be surface treated with silicone, silane coupling agent, aluminum chelating agent, polyurea, etc. There is no particular limitation on the thickness of the supporting substrate, and from the perspective of operability, it is preferably 10 to 100 μm.

[0066] The photosensitive resin sheet of the present invention can be obtained by coating the photosensitive resin composition on a supporting substrate and then drying to obtain a cured film. As a method for coating the photosensitive resin composition on a substrate, spin coating, spray coating, roller coating, screen printing, or coating methods such as a blade coater, a calender coater, a slit coater, a roller coater, a comma roll coater, and a gravure coater can be cited. The coating film thickness varies depending on the coating method, the solid content of the photosensitive resin composition, the viscosity, etc., and the film thickness after drying is preferably in the range of 0.5 to 100 um.

[0067] The drying method can be an oven, a heating plate, an infrared heater, etc. The drying temperature and the drying time can be controlled within the range that allows the organic solvent to volatilize. It is preferred to appropriately set the photosensitive resin composition film to an uncured or semi-cured state. The specific drying temperature is preferably 40 to 120°C, and the drying time is preferably 1 to 60 minutes. Furthermore, staged heating can also be used, for example, heat treatment at 70°C, 80°C, and 90°C for 1 minute each.

[0068] In addition, the photosensitive resin sheet can be protected by a protective film to avoid the influence of pollutants such as dust and dirt in the air. Examples of the protective film include polyethylene film, polypropylene film, polyester film, etc. The protective film is preferably a film with low adhesion to the photosensitive resin composition film.

[0069] According to a fifth aspect of the present application, an electronic component or a semiconductor device is provided, wherein the electronic component or the semiconductor device is obtained by bonding a plurality of substrates or bonding a substrate to other components through a cured film of the photosensitive resin composition described above.

[0070] The photosensitive resin composition and photosensitive resin sheet of the present application are suitable for surface protection films of semiconductor elements, ultra-thin flexible circuit boards, interlayer insulation films, and insulation layers of organic electroluminescent elements. In the present application, a specific electronic component or semiconductor device is provided, wherein the electronic component or semiconductor device is used to bond multiple substrates or to bond a substrate to other components through a cured film of the photosensitive resin composition of the present invention. The cured film of the photosensitive resin composition can be prepared by directly coating the photosensitive resin composition on a substrate, or can be introduced in the form of a photosensitive resin sheet.

[0071] On the other hand, when using a photosensitive resin sheet, the protective film must be peeled off first, so that the photosensitive resin sheet and the substrate are opposite to each other and bonded by thermocompression bonding. Thermocompression bonding can be performed by thermal sub-treatment, thermal lamination treatment, thermal vacuum lamination treatment, etc. Considering the adhesion to the substrate, the thermocompression bonding temperature is preferably above 40°C. In addition, in order to prevent the resolution of the photosensitive resin sheet from being deteriorated during curing, exposure, and pattern formation in the development process during thermocompression bonding, the thermocompression bonding temperature is preferably below 150°C. After thermocompression bonding, the support film is peeled off, and the photosensitive resin composition film is retained on the substrate.

[0072] The obtained photosensitive resin composition film is irradiated with chemical rays through a mask plate for exposure. As chemical rays for exposure, there are ultraviolet rays, visible rays, electron rays, X-rays, etc. In the present application, it is preferred to use i-rays (365nm), h-rays (405nm) or g-rays (436nm) of a mercury lamp. For the photosensitive resin sheet, when the support film is a transparent material, it is also possible to expose without peeling the support film from the photosensitive resin sheet.

[0073] When forming a pattern, the unexposed part is removed with a developer after exposure. As a developer, tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, 1,6-hexanediamine and other alkaline compound aqueous solutions are preferred. Depending on the circumstances, one or more polar solvents selected from N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide and the like; alcohols such as methanol, ethanol, isopropanol; esters such as ethyl lactate and propylene glycol azomethyl ether acetate; compounds such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may also be added to these alkaline aqueous solutions.

[0074] The development can be carried out by spraying the above-mentioned developer on the film-attached surface of the substrate or immersing the film in the developer together with the substrate, or by applying ultrasonic waves while immersing the substrate in the developer. In addition, the developer can be sprayed on the film surface while rotating the substrate. The development time, development steps, and temperature of the developer are not limited, as long as the unexposed portion can be removed. In order to process fine patterns or remove residues between patterns, it is preferred to further develop after removing the unexposed portion.

[0075] After development, the film may be rinsed with water. Alcohol such as ethanol or isopropyl alcohol and ethyl lactate, propylene glycol monomethyl ether acetate, etc. may be added to water for rinsing.

[0076] In order to further improve the resolution and expand the development process range, a baking treatment may be performed before development. The baking treatment temperature is preferably 50 to 180° C., more preferably 60 to 120° C. The baking treatment time is preferably 5 s to 60 min.

[0077] From the viewpoint of reducing the solvent, solid content, water content, etc. of the photosensitive resin composition film remaining after pattern formation, it is preferably heated and dried at 60 to 200° C. The heating and drying time is preferably 1 to 60 minutes.

[0078] The substrate with the patterned photosensitive resin composition film is thermally pressed onto another substrate or other hanging parts. The thermal pressing temperature can be above the glass transition temperature of the resin composition film, preferably 100 to 400°C, and the pressure during pressing is preferably 0.01 to 10 MPa, and the time is preferably 1 second to 10 minutes.

[0079] After the thermal compression bonding, the photosensitive resin composition film is cured by applying 120 to 400° C., preferably 180 to 250° C. The curing temperature can be increased stepwise or continuously within a specified temperature range. The heating treatment time is preferably 5 min to 5 h.

[0080] Optionally, the thickness of the cured film can be set arbitrarily, preferably 0.5 um to 100 um.

[0081] In the present application, C1-C25 and C6-C18 refer to the number of carbon atoms contained in the group.

[0082] In the present application, the term "alkyl" refers to a group formed by losing any hydrogen atom from an alkane compound molecule.

[0083] In the present application, the term "alkoxy" refers to an alkyl group combined with an oxygen atom to form an alkoxy group, wherein the alkyl portion is as defined in the aforementioned "alkyl"; preferred "C1-C3 alkoxy groups" include methoxy, ethoxy, n-propoxy, isopropoxy.

[0084] The beneficial effects of this application include:

[0085] The photosensitive resin composition provided in the present application can be exposed within the visible light wavelength range and developed by an alkaline developer, has good sensitivity and high resolution, and has broad application prospects in the fields of semiconductor packaging and the like. DETAILED DESCRIPTION

[0086] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0087] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0088] In the embodiments of the present application, the structures of the photoinitiators of formula A-1 to A-5 are as follows:

[0089]

[0090] Synthesis Example 1 Preparation of polyimide

[0091] Under a nitrogen atmosphere, 311.32 g (0.85 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF), 12.43 g (0.05 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (SiDA) and 21.83 g (0.20 mol) of 3-aminophenol (MAP) were dissolved in 984 g of γ-butyrolactone (GBL), and 310.21 g (1.0 mol) of 4,4'-oxydiphthalic anhydride (ODPA) was added, stirred at 60°C for 1 hour, then heated to 180°C, stirred for 2 hours, and cooled to room temperature to obtain an alkali-soluble polyimide solution.

[0092] The molecular weight and imidization rate of the obtained polyimide were detected as follows:

[0093] Molecular weight: The alkali-soluble polyimide solution was diluted in NMP (N-methylpyrrolidone) to obtain a solution with a solid content of 0.1 wt%. The molecular weight was measured by gel permeation chromatography (GPC) device LC-20AD (Shimadzu Corporation, Japan), with N-methylpyrrolidone as the mobile phase. The molecular weights obtained were all weight average molecular weights (M w ).

[0094] Imidization rate: Alkaline soluble polyimide solution was spin-coated on a 4-inch silicon wafer to form a film, baked at 100°C for 15 min, and the infrared absorption spectrum of the polyimide film was measured to confirm the absorption peak of the polyimide structure (1780cm -1 、1377cm -1 The silicon wafer coated with polyimide film was then heat treated at 300°C for 1.5 hours, and the infrared absorption spectrum was measured again. The intensity of 1377 cm before and after the heat treatment was compared. -1 The imidization rate of the polymer before the heat treatment was calculated from the peak intensity ratio, with the imidization rate of the polymer after the heat treatment being set as 100%.

[0095] The results show that the weight average molecular weight of the obtained soluble polyimide is 19573, and the imidization rate is 95%.

[0096] Preparation of photosensitive resin composition

[0097] Example 1

[0098] 35 g of ethoxylated bisphenol A dimethacrylate, 2 g of photoinitiator A-1, and 0.5 g of vinyl triethoxysilane were added to 50 g of the alkali-soluble polyimide solution prepared in Synthesis Example 1, and the mixture was evenly mixed. The resulting solution was pressure filtered using a filter with a pore size of 0.2 μm to obtain a photosensitive resin composition.

[0099] Example 2

[0100] Except that the photoinitiator A-1 was changed from 2 g to 1 g, the other steps were the same as in Example 1.

[0101] Example 3

[0102] Except that the photoinitiator A-1 was changed from 2 g to 5 g, the other steps were the same as in Example 1.

[0103] Example 4

[0104] Except that the photoinitiator A-1 is changed to A-2, the other steps are the same as those in Example 1.

[0105] Example 5

[0106] Except that the photoinitiator A-1 is changed to A-3, the other steps are the same as those in Example 1.

[0107] Example 6

[0108] Except that the photoinitiator A-1 is changed to A-4, the other steps are the same as those in Example 1.

[0109] Example 7

[0110] Except that the photoinitiator A-1 is changed to A-5, the other steps are the same as those in Example 1.

[0111] Example 8

[0112] Except for adding 1.27 g of 2-mercaptobenzothiazole into the system, the rest is the same as Example 5.

[0113] Example 9

[0114] The process is the same as in Example 8 except that the photoinitiator 2-mercaptobenzothiazole 1.27 g is replaced by N-phenylglycine 2.21 g.

[0115] Comparative Example 1

[0116] Except that 2g of photoinitiator A-1 is replaced with 1.23g of the compound of formula II, the rest is the same as Example 1.

[0117]

[0118] Comparative Example 2

[0119] Except that 2 g of photoinitiator A-1 is replaced by 0.70 g of benzophenone, the other steps are the same as those in Example 1.

[0120] Comparative Example 3

[0121] Except that photoinitiator A-1 is not added, the other steps are the same as those in Example 1.

[0122] Comparative Example 4

[0123] Except that 2g of photoinitiator A-3 is replaced with 2g of the compound of formula II, the rest is the same as Example 5.

[0124] The photosensitive resin compositions prepared in the above-mentioned embodiments and comparative examples were evaluated by the following method:

[0125] (1) Sensitivity: The photosensitive resin composition in each embodiment and comparative example was coated on a PET support film with a thickness of 38 μm using a comma roll coater, dried at 100°C for 15 minutes, and a PE film with a thickness of 38 μm was attached as a protective film to obtain a photosensitive resin sheet. The protective film was peeled off, and the peeled surface was laminated on a silicon wafer using a lamination device (Takatori, VTM-200M) under the conditions of a processing table temperature of 80°C, a roller temperature of 80°C, a pressure of 150 Pa, an attachment speed of 5 mm / s, and an attachment pressure of 0.2 MPa. After the support film was torn off, the film thickness was tested using a step profiler (KLA Tencor P-7). The film thickness of the photosensitive resin composition film was 15 μm. The film was exposed using an ultraviolet lamp (i and g lines), and sprayed with a 2.38 wt% tetramethylammonium hydroxide aqueous developer to obtain a cured film. The minimum exposure energy for obtaining the cured film was recorded. The smaller the value, the better the sensitivity.

[0126] (2) Resolution: The photosensitive resin sheet obtained in (1) was peeled off from the protective film, and the peeled surface was laminated on a silicon wafer using a laminating device (Takatori, VTM-200M) under the conditions of a processing table temperature of 80°C, a roller temperature of 80°C, a pressure of 150Pa, a pasting speed of 5mm / s, and a pasting pressure of 0.2MPa. After the support film was peeled off, a step profiler (KLA Tencor P-7) was used to test the film thickness. The film thickness of the photosensitive resin composition film was 15um. The ultraviolet lamp (i and g lines) was used with an exposure amount of 400mJ / cm 2 , and expose through a mask. After exposure, spray development was performed using a 2.38wt% tetramethylammonium hydroxide water-based developer for 120s, and the unexposed portion was removed and rinsed with water. The pattern was observed using an optical microscope (MX63-F, Olympus) at a magnification of 20 times, and the minimum size of the through-hole pattern was taken as the resolution. The smaller the resolution, the better the resolution.

[0127] The evaluation results are shown in Table 1 below:

[0128] Table 1

[0129]

[0130] “ / ” indicates that the minimum exposure energy exceeds 400mJ / cm 2 , “-” indicates the resolution is over 100 μm.

[0131] From the data in Table 1, we can see that:

[0132] 1. By comparing Examples 1 to 3 and Comparative Examples 1 to 4, it can be seen that in the photosensitive composition, when the mass ratio of the quinoxaline structure photoinitiator of the present invention to the photopolymerizable compound is between 3% and 14%, the photosensitive composition has good sensitivity and resolution.

[0133] 2. It can be seen from Examples 3 to 7 and Comparative Examples 1 to 4 that the photosensitive composition containing the quinoxaline structure photoinitiator of the present invention has good sensitivity and resolution, and the photosensitive composition containing photoinitiator A-3 has the best sensitivity and resolution.

[0134] 3. By comparing Examples 8 to 9 and Comparative Examples 1 to 4, it can be seen that when photoinitiator A-3 is used in combination with 2-mercaptobenzothiazole, the sensitivity of the photosensitive composition is the same as that of A-3 alone, and the resolution is optimal.

[0135] The data in Table 1 show that the polyimide film prepared from the photosensitive resin composition of the present invention has high sensitivity and resolution, can be used in the field of photosensitive polyimide materials, such as semiconductor packaging, and has broad application prospects.

[0136] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A photosensitive resin composition, characterized in that The photosensitive resin composition is formed by the following components: Component (A): alkali-soluble resin; Component (B): a compound containing an unsaturated bond; Component (C): photoinitiator; Component (D): coupling agent; The photoinitiator has a structure shown in Formula I: In formula I, R1, R2, R3, and R4 are independently selected from a hydrogen atom, a fluorine atom, a C1-C25 alkyl group, and a C1-C25 alkoxy group; R5, R6 are independently selected from bromine or chlorine; The alkali-soluble resin is selected from at least one of alkali-soluble polyimide and alkali-soluble polyimide precursor.

2. The photosensitive resin composition according to claim 1, characterized in that The photoinitiator is selected from one of the structures shown in Formula A-1 to Formula A-5; 3. The photosensitive resin composition according to claim 1, characterized in that The alkali-soluble polyimide and the alkali-soluble polyimide precursor are both prepared by reacting a tetracarboxylic dianhydride compound with a diamine compound; Preferably, the tetracarboxylic dianhydride compound is selected from at least one of pyromellitic dianhydride, 3,4,3',4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,4,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride.

4. The photosensitive resin composition according to claim 3, characterized in that: The diamine compound is selected from diamine compound A or a mixture of diamine compound A and diamine compound B, and the molar amount of diamine compound B is less than or equal to 10% of the total molar amount of diamine compounds; Preferably, the diamine compound A is selected from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2'-bis(3-amino-4-hydroxyphenyl)propane, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylmethane, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfide, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, p-phenylenediamine, m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4' -diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 4,4'-bis(4-aminophenyl)propane, 4,4'-bis(4-aminophenoxy)diphenyl sulfone, 2,2'-trifluoromethyl-4,4'-diaminodiphenyl ether, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-diaminodiphenyl sulfone, and at least one of the following, and the diamine compound containing a phenolic hydroxyl group in the diamine compound A accounts for 50 to 100% of the total molar amount of the diamine compound; Preferably, the diamine compound B is at least one selected from 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 3,3′-(1,4-phenylenebis(dimethylsilanediyl))bis(propyl-1-amine), and 4,4′-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)diphenylamine.

5. The photosensitive resin composition according to claim 1, characterized in that: The unsaturated bond-containing compound is selected from diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, styrene, α-methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene, 4-methylstyrene, p-vinylbenzene, 2-vinylnaphthalene, butyl acrylate, methyl acrylate, Butyl acrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, tricyclodecane dimethacrylate Methanol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-diacryloxy-2-hydroxypropane, 1,3-dimethacryloxy-2-hydroxypropane, methylenebisacrylamide, N,N-dimethylacrylamide, N-hydroxymethylacrylamide, 2,2,6,6-tetramethylpiperidinyl At least one of methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, propoxylated bisphenol A diacrylate, propoxylated bisphenol A methacrylate, propoxylated ethoxylated bisphenol A diacrylate, propoxyethoxylated bisphenol A dimethacrylate, N-vinyl caprolactam, polyethylene glycol diacrylate, and 2-isocyanatoethyl methacrylate.

6. The photosensitive resin composition according to claim 1, characterized in that: The coupling agent is selected from at least one of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, bis(γ-aminopropyl)tetramethylsiloxane, bis(γ-aminobutyl)tetramethylsiloxane, bis(γ-aminopropyl)tetraphenylsiloxane, bis(γ-aminopropyl)tetraphenylpolysiloxane, bis(γ-aminopropyl)tetraphenylsiloxane, bis(γ-aminobutyl)tetraphenylpolysiloxane, 3-(2,3-epoxypropyloxy)propyltriethoxysilane and vinyltriethoxysilane; Preferably, the photoinitiator can be used in combination with other photosensitizers, and the other photosensitizers are selected from at least one of 2-mercaptobenzothiazole, N-phenylglycine, and N-methyldiethanolamine.

7. The photosensitive resin composition according to claim 1, characterized in that: The components of the photosensitive resin composition also contain a solvent, and the solvent is selected from at least one of N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N-vinylpyrrolidone, N,N-diethylformamide, γ-butyrolactone, ethyl lactate, methyl monoglyme, methyl diglyme, methyl triglyme, ethyl monoglyme, ethyl diglyme, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether.

8. The photosensitive resin composition according to claim 1, characterized in that: The mass ratio of the unsaturated bond-containing compound to the alkali-soluble resin is 20 to 150:100; Preferably, the mass ratio of the photoinitiator to the alkali-soluble resin is 0.1 to 20:100; Preferably, the mass ratio of the coupling agent to the alkali-soluble resin is 0.01 to 10:

100.

9. A photosensitive resin sheet, characterized in that: The photosensitive resin sheet comprises a supporting substrate, on which a cured film formed of a photosensitive resin composition varnish is coated; The raw materials of the photosensitive resin composition varnish include the photosensitive resin composition according to any one of claims 1 to 8 and an organic solvent.

10. An electronic component or a semiconductor device, characterized in that: The electronic component or semiconductor device is obtained by bonding a plurality of substrates or bonding a substrate to another member via the cured film of the photosensitive resin composition according to any one of claims 1 to 8.

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