CN111830786B

CN111830786B - Photosensitive resin composition containing silane coupling agent

Info

Publication number: CN111830786B
Application number: CN202010690691.8A
Authority: CN
Inventors: 李铭新; 公聪聪; 王华森; 陈存浩; 王建伟
Original assignee: Bomi Technology Co ltd
Current assignee: Bomi Technology Co ltd
Priority date: 2020-07-17
Filing date: 2020-07-17
Publication date: 2023-05-23
Anticipated expiration: 2040-07-17
Also published as: CN111830786A

Abstract

The invention discloses a photosensitive resin composition containing a silane coupling agent, wherein the silane coupling agent with a double bond and imide structure is introduced into the photosensitive resin composition, and the adhesion between the photosensitive resin composition and a base material after high-temperature thermal curing is improved through the addition of the silane coupling agent with the structure.

Description

Photosensitive resin composition containing silane coupling agent

Technical Field

The present invention relates to a photosensitive resin composition containing a silane coupling agent, and more particularly to a photosensitive resin composition containing a silane coupling agent which is suitable for use in particle shielding, surface protection, interlayer dielectric or insulation of a semiconductor element, an insulating layer of an OLED element, and the like. The photosensitive resin composition comprises a silane coupling agent with double bonds and an imide structure, and can improve the adhesive force of the photosensitive resin and a substrate (silicon wafer, ceramic, aluminum material and other metal substrates).

Background

Since heat-resistant resins such as polyimide and polybenzoxazole have excellent heat resistance and electrical insulation properties, they can be used for surface protective films, interlayer insulating films, and the like of semiconductor elements such as LSIs (Large Scale integration; large-scale integrated circuits). With miniaturization of semiconductor devices, resolution of several micrometers is also required for surface protective films, interlayer insulating films, and the like. Therefore, in the above-mentioned applications, a positive photosensitive polyimide composition or a photosensitive polybenzoxazole composition which can be finely processed can be used. A precondition for using a heat-resistant resin such as polyimide or polybenzoxazole for a surface protective film or an interlayer insulating film is that a polyimide composition film or a polybenzoxazole composition film after heat curing is permanently left in the element. Therefore, adhesion of such films to substrates after heat curing is critical.

In the heat-resistant resins known heretofore, the adhesion to a substrate such as a silicon wafer is not yet sufficiently good. In order to improve the adhesion between the heat-resistant resin film and the substrate, there has been proposed a method of pretreating the substrate with a silane coupling agent or the like, adding the silane coupling agent to the heat-resistant resin precursor composition (hereinafter referred to as a coating paste), or adding an organosilicon compound capable of participating in polymerization during the synthesis of the heat-resistant resin precursor to improve the adhesion between the heat-resistant resin film and the substrate. Among these methods, the method of adding a silane coupling agent to a coating paste is the simplest. The silane coupling agent is suitable for being matched with high heat-resistant organic materials such as polyimide, polybenzoxazole, polyether sulfone and other high molecular polymers, and the structure of the silane coupling agent is generally similar to that of the high molecular polymers so as to promote the adhesion of the heat-resistant materials and the base materials.

In patent documents JP-a 2009-015285, JP-a 2010-152302 and WO2009/096050, silane coupling agents containing imide structural groups are disclosed, which have good compatibility with heat resistant resins having polyimide structures and exhibit good adhesion promoting effects with substrates, but polyimide structures themselves do not have strong chemical bonding ability, and thus have limited promotion effects on adhesion, thus leaving a large adhesion promoting space. In patent document CN102292675a, a silane coupling agent containing an epoxy group is used in combination with a silane coupling agent containing a styrene group, and in the structure of the silane coupling agent containing a styrene group, an alkoxysilane is directly bonded to an aromatic ring, and because of its strong bonding energy, the obtained resin composition can still obtain a resin film excellent in adhesion to a substrate after heat treatment at 350 ℃ or more or heat treatment in air, but the silane coupling agent is expensive to prepare. Liu Feng et al (study on synthesis of phenylacetylene phthalic anhydride modified silane coupling agent [ J ]. Chemical reagent, 2009,31 (07): 538-540.) modified gamma-aminopropyl triethoxysilane (gamma-APS) with 4-phenylacetylene phthalic anhydride (4-PEPA), the adhesion of the phenylacetylene phthalic anhydride modified silane coupling agent on a metal substrate is enhanced, and the principle is that the imidization temperature of a polyimide precursor is similar to the polymerization temperature of an ethynyl group, so that hydrophobic terminal alkynyl is polymerized at high temperature, and hydrophilic terminal silicon group is bonded with the substrate well to achieve the effect of enhancing adhesion. But phenylethynyl phthalic anhydride is expensive and is not suitable for large-scale industrialized use.

Disclosure of Invention

In view of the shortcomings of the prior art, the invention provides a photosensitive resin composition containing a silane coupling agent, wherein the composition contains the silane coupling agent with a double bond and an imide structure, and the photosensitive resin composition still shows excellent adhesion with a substrate after heat treatment in an air atmosphere at 300 ℃ or above by using the silane coupling agent alone or in combination with other silane coupling agents.

According to the invention, the silane coupling agent with double bond and imide structure is added into the photosensitive resin composition, and the introduction of the silane coupling agent greatly improves the adhesiveness between the photosensitive resin film formed by thermally curing the photosensitive resin composition and a substrate (such as silicon, ceramic, metal and other substrates), and the adhesiveness is further improved when the silane coupling agent is matched with other silane coupling agents.

The specific technical scheme of the invention is as follows:

a photosensitive resin composition (hereinafter referred to as photosensitive resin composition) containing a silane coupling agent, the photosensitive resin composition comprising the following components:

component (a): a polymer having a structure represented by the following general formula (1) as a main component and/or a polymer having a structure represented by the following general formula (2) as a main component;

Component (b): quinone diazide compounds;

component (c): at least one silane coupling agent comprising at least a silane coupling agent having a structure represented by the following general formula (3);

component (d): and (3) a solvent.

Further, in the general formula (1), R ₁ And R is ₂ Each independently represents a 2-to 8-valent organic group having 2 or more carbon atoms; r is R ₃ And R is ₄ Each independently represents hydrogen or a 1-valent organic group having 1 to 20 carbon atoms; n represents a range of 5 to 1000; l and m independently represent integers from 0 to 2, and p and q independently represent integers from 0 to 2, wherein p+q>0。

Further, in the general formula (2), R ₅ An organic group having a valence of 4 to 8; r is R ₆ An organic group having a valence of 2 to 10; r is R ₇ And R is ₈ Represents a phenolic hydroxyl group, a sulfonic acid group or a thiol group, R ₇ And R is ₈ Each of the two groups may be a single group, or may be a mixture of different groups; t represents a range of 3 to 1000; r and s are each independently an integer of 0 to 4.

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Further, in the general formula (3), R ₉ Is hydrogen, C ₁ -C ₁₀ Alkyl or C of (2) ₁ -C ₁₀ Alkoxy groups of (a); r is R ₁₀ Is hydrogen, C ₁ -C ₁₀ Alkyl or C of (2) ₁ -C ₁₀ Alkoxy groups of (a); r is R ₁₁ Is hydrogen, C ₁ -C ₁₀ Alkyl or C of (2) ₁ -C ₁₀ Alkoxy groups of (a). R is R ₉ 、R ₁₀ 、R ₁₁ May be the same or different. R is R ₁₂ Is hydrogen or C ₁ ～C ₁₀ Alkyl of (a); r is R ₁₃ Is hydrogen or C ₁ ～C ₁₀ Is a hydrocarbon group. R is R ₁₂ 、R ₁₃ May be the same or different.

Preferably, in formula (3), R ₉ Is C ₁ -C ₁₀ Alkyl or C of (2) ₁ -C ₁₀ More preferably C ₁ -C ₄ Alkyl or C of (2) ₁ -C ₄ Most preferably methoxy or ethoxy.

Preferably, in formula (3), R ₁₀ Is C ₁ -C ₁₀ Alkyl or C of (2) ₁ -C ₁₀ More preferably C ₁ -C ₄ Alkyl or C of (2) ₁ -C ₄ Most preferably methoxy or ethoxy.

Preferably, in formula (3), R ₁₁ Is C ₁ -C ₁₀ Alkyl or C of (2) ₁ -C ₁₀ More preferably C ₁ -C ₄ Alkyl or C of (2) ₁ -C ₄ Most preferably methoxy or ethoxy.

Preferably, in formula (3), R ₁₂ And R is ₁₃ Are all hydrogen atoms.

The silane coupling agent of the general formula (3) of the present invention is obtained by amidation reaction of a furoic acid anhydride compound represented by the formula (4) and a silane compound having an amino group as a terminal group represented by the formula (5), followed by imidization.

In the above formula (4) and formula (5), R ₉ 、R ₁₀ 、R ₁₁ 、R ₁₂ 、R ₁₃ Is defined in accordance with the definition set forth above.

Further, the amidation reaction and the imidization reaction are carried out in an aprotic polar solvent, preferably, the aprotic polar solvent is selected from at least one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide and γ -butyrolactone.

Further, the molar ratio of the furoic acid anhydride compound shown in the formula (4) to the silane compound with the amino end group shown in the formula (5) is 1:0.9-1.1.

Further, after the amidation reaction, a base and an acid anhydride are added to the reaction solution to carry out imidization reaction. The base is pyridine, triethylamine or diisopropylethylamine, and the anhydride is acetic anhydride or trifluoroacetic anhydride. Preferably, the amount of the base is 2 to 10 times the molar amount of the silane compound having an amino group as the terminal group, and the amount of the acid anhydride is 2 to 10 times the molar amount of the silane compound having an amino group as the terminal group.

Further, the temperature of the amidation reaction was room temperature.

Further, in addition to the silane coupling agent described in the above general formula (3), the component (c) may further include other types of silane coupling agents reported in the prior art, that is, the silane coupling agent described in the general formula (3) may be used in combination with silane coupling agents of other structures, which is advantageous for improving the adhesion with a substrate after the heat curing of the inductive resin composition. The silane coupling agent that can be used in combination with the silane coupling agent described by the general formula (3) may be selected from among those disclosed in the art. Experiments prove that when the silane coupling agent shown in the general formula (3) is used in combination with one or two of 3- (triethoxysilylthio) propyl trimethoxy silane and gamma-ureido propyl triethoxy silane, better tackifying effect is shown.

Further, the mass ratio of the component (a) to the component (b) is 100:1 to 50, preferably 100:5 to 30.

Further, the mass ratio of the component (a) to the component (c) is 100:0.1-10, preferably 100:0.25 to 5.0, more preferably 100:0.5 to 3.5.

Further, the mass ratio of the component (a) to the component (d) is 1:0.8 to 50, preferably 1:1.5 to 10.

Further, the component (d) is a solvent which may be one or more of aprotic polar solvents, ketone solvents, ester solvents, aromatic hydrocarbon solvents, and the like. The aprotic polar solvent may be one or more of N-methylpyrrolidone, γ -butyrolactone, tetrahydrofuran, dioxane, N-dimethylformamide, dimethylsulfoxide, and the like. The ketone solvent may be one or more of methyl ethyl ketone, acetone, etc. The ester solvent may be one or more of ethyl acetate, ethyl lactate, etc. The aromatic solvent may be one or more of toluene, xylene, etc.

Further, the viscosity of the photosensitive resin composition is 1 to 5000 mPas, preferably 500 to 3000 mPas, and more preferably 1000 to 2000 mPas.

Further, the above components were uniformly mixed to obtain the photosensitive resin composition of the present invention, which was spin-coated on a 4-inch silicon wafer, and then soft-baked at 120℃for 3 minutes using a heating stage to obtain a photosensitive resin film having a thickness of 8 to 10. Mu.m. The photosensitive resin film was placed in an inert gas oven and subjected to heat treatment under a nitrogen flow (oxygen content of less than 20 ppm), first heat-treated at 170 ℃ for 30 minutes, then heated to 320 ℃ over 1 hour, and treated at 320 ℃ for 1 hour to obtain an imidized (cured) resin cured film exhibiting excellent PCT test adhesion with a substrate. From this, it can be seen that the resin cured film prepared by the present invention has excellent adhesion by the selection of the silane coupling agent. The photosensitive resin composition of the present invention can be used as a particle shielding, surface protection, interlayer dielectric or insulation of a semiconductor element, an insulation layer of an OLED element, etc., and its application as a surface protection film or an interlayer insulation film of a semiconductor element is also within the scope of the present invention.

The photosensitive resin composition contains the silane coupling agent with double bond and imide structure, and the introduction of the silane coupling agent ensures that the photosensitive resin composition has excellent adhesion with a base material after high-temperature thermal curing at the temperature of more than 300 ℃ and overcomes the defect of insufficient adhesion of the existing photosensitive heat-resistant resin.

Detailed Description

The photosensitive resin composition improves the viscosity after heat curing by introducing a silane coupling agent with a double bond and imide structure, and particularly improves the viscosity of the photosensitive resin composition better by matching the silane coupling agent with other silane coupling agents, and still shows excellent adhesion with a substrate after heat treatment in an air atmosphere at a temperature of more than 300 ℃.

In the photosensitive resin composition of the present invention, the component (a) is preferably a polyimide resin, a polyamic acid or polyamic acid ester of a polyimide precursor, or a polybenzoxazole precursor, and the component (a) is a polymer mainly composed of a structure represented by the following general formula (1) and/or a polymer mainly composed of a structure represented by the following general formula (2). In the description herein, the term "polymer having a structure represented by the following general formula (1) as a main component" means that 50 mol% or more of all the structural units of the polymer are structural units represented by [ ] in the following general formula (1), and preferably 70 mol% or more, and more preferably 90 mol% or more. The term "polymer having a structure represented by the following general formula (2) as a main component" means that 50 mol% or more of all the structural units of the polymer are structural units represented by [ ] in the following general formula (2), and preferably 70 mol% or more, more preferably 90 mol% or more.

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In the general formula (1), R ₁ And R is ₂ Each independently represents a 2-to 8-valent organic group having 2 or more carbon atoms; r is R ₃ And R is ₄ Each independently represents hydrogen or a 1-valent organic group having 1 to 20 carbon atoms; n represents a range of 5 to 1000; l and m independently represent integers from 0 to 2, and p and q independently represent integers from 0 to 2, wherein p+q>0。

In the general formula (2), R ₅ An organic group having a valence of 4 to 8; r is R ₆ An organic group having a valence of 2 to 10; r is R ₇ And R is ₈ Represents a phenolic hydroxyl group, a sulfonic acid group or a thiol group, R ₇ And R is ₈ Each of the two groups may be a single group or may be a mixture of different groups; t represents a range of 3 to 1000; r and s represent integers of 0 to 4.

The component (a) used in the photosensitive resin composition of the present invention may be a polymer formed of only structural units represented by the general formula (1) or the general formula (2), or may be a mixture of these 2 polymers.

When the structural unit represented by the general structural formula (1) or (2) contains a fluorine atom, the interface of the film is water-repellent when developed in an alkaline developing solution, and thus penetration and the like at the interface are suppressed, so that the fluorine atom content is preferably 10% by weight or more to ensure the effect of preventing penetration at the interface, and 20% by weight or less to ensure the solubility of the photosensitive resin in an alkaline solvent and the adhesion of the cured film to a substrate after high-temperature treatment.

In the general formula (1), R ₁ An organic group having 2 to 8 carbon atoms and representing the structural component of an acid, i.e., R ₁ The residue of an acid having 2 to 8 valences and 2 or more carbon atoms. R is R ₁ The acid may be a residue of a 2-valent acid, and the 2-valent acid may be terephthalic acid, isophthalic acid, diphenylether dicarboxylic acid, biphenyl dicarboxylic acid, naphthalene dicarboxylic acid, or the like. R is R ₁ The residue of the acid may be 3-valent, and the acid 3-valent may be tricarboxylic acid such as trimellitic acid, 1,3, 5-trimellitic acid, etc. R is R ₁ The residue of an acid having a valence of 4, and the acid having a valence of 4 may be an aromatic tetracarboxylic acid such as 1,2,4, 5-benzene tetracarboxylic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, etc.; aliphatic tetracarboxylic acids such as cyclobutanetetracarboxylic acid and cyclopentanetetracarboxylic acid; and diester compounds in which 2 hydrogen atoms of the carboxyl group are changed to methyl groups or ethyl groups. In addition, R ₁ The acid may be a residue of an acid having a hydroxyl group on an aromatic ring such as hydroxyphthalic acid or trimellitic acid. R is R ₁ The acid may be a single acid residue, or may be 2 or more acid residues. In addition, from the viewpoints of solubility in an alkaline developer and photosensitivity, a residue containing 50 mol% or more of an acid having a hydroxyl group is preferable.

R is preferable from the viewpoint of heat resistance ₁ Having aromatic rings, more preferably R ₁ Is a 3-valent or 4-valent organic group having 6 to 30 carbon atoms.

In the general formula (2), R ₅ The residue of the acid dianhydride is an organic group having 4 to 10 valences, and among them, an organic group having 5 to 40 carbon atoms of an aromatic ring or a cyclic aliphatic group is preferable. Specific examples of the acid dianhydride include 3,3', 4' -biphenyltetracarboxylic acid dianhydride, 2',3,3' -benzophenone tetracarboxylic dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, and the like. They may be used alone or in combination of 2 or more.

R in the general formula (1) ₂ R in the general formula (2) ₆ Represents 2 carbon atomsThe organic group having a valence of 2 to 8 represents a structural component of diamine. R is preferable from the viewpoint of heat resistance ₂ 、R ₆ Has an aromatic ring. Specific examples of the diamine include diphenyl sulfide such as 3,4 '-diaminodiphenyl sulfide, 4' -diaminodiphenyl sulfide, etc., diphenyl sulfide such as gasoline, 1, 5-naphthalene diamine, 2, 6-naphthalene diamine, etc., diphenyl diamine such as m-phenylenediamine, p-phenylenediamine, etc., diaminodiphenyl ether such as 3,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl ether, etc., diaminodiphenyl methane such as 3,4 '-diaminodiphenyl methane, 4' -diaminodiphenyl methane, etc., diaminodiphenyl sulfone such as 3,4 '-diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfone, etc., bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, etc., bis (aminophenoxyphenyl) hexafluoropropane, diaminodihydroxypyrimidine, diaminopyridine, hydroxydiaminopyrimidine, diaminophenol, dihydroxybenzidine, diaminobenzoic acid, diaminoterephthalic acid, etc. The diamine may be a diamine in which at least part of hydrogen in the aromatic ring is substituted with an alkyl group or a halogen atom, or may be aliphatic cyclohexyldiamine, methylenedicyclohexylamine, hexamethylenediamine, or the like.

R of the general formula (1) ₃ R is R ₄ May be the same or different, R ₃ R is R ₄ Each independently represents hydrogen or a 1-valent organic group having 1 to 20 carbon atoms. R is preferable from the viewpoints of solubility in an alkaline developer and solution stability of the obtained photosensitive resin composition ₃ R is R ₄ 10 to 90 mol% of each independently is hydrogen, and R is more preferable ₃ R is R ₄ Each of which contains at least 1 or more 1-valent hydrocarbon groups having 1 to 16 carbon atoms, and the others are hydrogen atoms.

In addition, l and m in the general formula (1) represent the number of carboxyl groups or ester groups, and each independently represents an integer of 0 to 2, preferably 1 or 2. P and q in the general formula (1) independently represent integers of 0 to 4, and p+q > 0. N in the general formula (1) represents the number of repeating structural units of the polymer and is in the range of 5 to 1000. When n is less than 5, the solubility of the polymer in an alkaline solution is too great to obtain the contrast between the exposed area and the unexposed area; when n > 1000, the solubility of the polymer in an alkaline developer is too small, and the exposed area cannot be dissolved, and a desired image cannot be formed. In view of the solubility of the polymer in an alkaline developer, n is preferably 500 or less, and more preferably 100 or less. In addition, n is preferably 20 or more from the viewpoint of increasing elongation.

In the general formula (2), R is ₇ R is R ₈ Represents a phenolic hydroxyl group, a sulfonic acid group or a thiol group, R and s each represent R ₇ 、R ₈ Is a number of (3). R and s are preferably 4 or less from the viewpoint of stability of the obtained photosensitive resin composition solution. In addition, r+s > 0 is preferable from the viewpoint of solubility of the polymer in an alkaline developer.

T in the general formula (2) represents the number of repeating structural units of the polymer, and is preferably 3 or more, more preferably 10 or more. When t < 3, the solubility of the polymer in an alkaline developer is too great to obtain a contrast between the exposed area and the unexposed area. On the other hand, when t > 1000, the solubility of the polymer in the alkaline developer is too small, the exposed area cannot be dissolved, and a desired image cannot be formed. From the viewpoint of solubility of the polymer in an alkaline developer, t is preferably 200 or less, and more preferably 100 or less.

Furthermore, R of the general formula (1) may be used in a range not to deteriorate heat resistance in order to improve adhesion to a substrate ₁ And/or R ₂ And R of the formula (2) ₅ And/or R ₆ Copolymerized with aliphatic groups having a siloxane structure. Specifically, 1 to 20 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like are copolymerized as the diamine component.

In order to control the molecular weight (degree of polymerization) of the polymer, and to adjust the dissolution rate of the resin in an aqueous alkali solution, monoamines or monoanhydrides, monocarboxylic acids, monoacylchloride compounds, monoacylate compounds, etc. may be selected as the end-capping agent of the polymer.

The monoamine used as the blocking agent is preferably 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4, 6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, or the like. They may be used alone or in combination of 2 or more.

Anhydrides such as phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride are preferable as the monoanhydride, monocarboxylic acid, monoacylchloride compound, and monoactive esterified product used as the blocking agent; monocarboxylic acids such as 3-carboxyphenol, 4-carboxyphenol, 3-carboxyphenol, 4-carboxythiophenol, 1-hydroxy-7-hydroxynaphthalene, 1-mercapto-6-carboxynaphthalene, and 4-carboxybenzenesulfonic acid, and monoacylic acid compounds obtained by acid chlorination of the carboxylic groups; and monoacylic acid compounds obtained by acylating and chlorinating one carboxyl group of dicarboxylic acids such as terephthalic acid and phthalic acid; reactive esterified compounds obtained by reacting a monoacyl chloride compound with N-hydroxybenzotriazole and N-hydroxy-5-norbornene-2, 3-dicarboximide, and the like. They may be used alone or in combination of 2 or more.

The content of the blocking agent such as monoamine, monoanhydride, monoacylchloride, monocarboxylic acid, or monoactive ester is preferably 5 to 50 mol% relative to the total amine components. By reacting a plurality of capping agents, a plurality of different terminal groups may be introduced.

The polymer having the structure represented by the general formula (1) as a main component can be synthesized by the following synthesis method. When the target product is a polyamic acid ester, for example, tetracarboxylic dianhydride is reacted with alcohol in triethylamine under low temperature conditions to obtain a diester, then the remaining dicarboxylic acid is subjected to acid chlorination, and the acid chlorinated product is reacted with a diamine compound or a monoamine compound under the catalysis of pyridine in a nitrogen atmosphere. When the target product is a polyamide containing hydroxyl groups, for example, a bisphenol compound is subjected to a condensation reaction with a dicarboxylic acid or a monoamine compound in the presence of a dehydration condensing agent such as Dicyclohexylcarbodiimide (DCC) under low temperature conditions; alternatively, dicarboxylic acid chlorides are reacted with bisphenol compounds and monoamine compounds in the presence of a tertiary amine such as pyridine.

After the polymer having the structure represented by the general formula (1) as a main component is produced by the above method, the polymer is put into a large amount of water or a water/methanol mixture to precipitate a resin, and the resin is washed, filtered, dried and separated. By this operation, the unreacted monomer, dimer or trimer oligomer in the polymer can be removed, and the film characteristics of the photosensitive resin composition after heat curing can be improved.

The polymer having the structure represented by the general formula (2) used in the present invention can be synthesized by, for example, obtaining a polyimide precursor by a method of synthesizing a polymer having the structure represented by the general formula (1), and completely imidizing the polyimide precursor by a known imidization method; or stopping imidization in the middle of the reaction, and introducing a part of imide structure; or a method of introducing a part of the imide structure by mixing a polymer completely imidized with the polyimide precursor.

The component (B) used in the present invention is a quinone diazide compound disclosed in patent CN102292675B, preferably an ester compound obtained by bonding a sulfonic acid of quinone diazide to a polyhydroxy compound via an ester bond, and as the polyhydroxy compound, there can be mentioned: 2, 6-dimethoxymethyl-4-t-butylphenol, 2, 6-dimethoxy-p-cresol, 2, 6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylenebisphenol, and the like, but are not limited thereto. Commercial quinone diazide compounds (b) are preferable objects such as NT-300 (esterification reaction product of 2,3, 4-tetrahydroxybenzophenone with 6-diazo-5, 6-dihydroxy-5-oxo-1-naphthalenesulfonic acid), 4NT-350 and 4NT-300 (esterification reaction product of 2,3, 4-tetrahydroxybenzophenone with 6-diazo-5, 6-dihydroxy-5-oxo-1-naphthalenesulfonic acid), TPPA-300A and TPPA-250 (esterification reaction product of 4,4- [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl ] ethylene ] diphenol and (6-diazo-5, 6-dihydroxy-5-oxo-1-naphthalenesulfonic acid), HP-190 (esterification reaction product of tris (4-hydroxyphenyl) ethane and (6-diazo-5, 6-dihydroxy-5-oxo-1-naphthalenesulfonic acid) (manufactured by Nippon Dongba Synthesis industry Co., ltd.), and NT-300 is preferable.

In the photosensitive resin composition of the present invention, too low a content of the component (b) results in low sensitivity and insufficient development, and the amount of the quinone diazide compound of the component (b) is preferably 1 part by weight or more, more preferably 5 parts by weight or more, per 100 parts by weight of the component (a). In addition, an excessively high content of the component (b) leads to an increase in cost and also to a decrease in storage stability, and the amount of the quinone diazide compound of the component (b) is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, per 100 parts by weight of the component (a).

The component (c) used in the present invention is a silane coupling agent, which may be one kind or plural kinds, and the silane coupling agent necessarily includes a silane coupling agent having a double bond and an imide structure represented by the following general formula (3), and the silane coupling agent having the general formula (3) may be used alone or in combination with other silane coupling agents. The silane coupling agent of the structure of the general formula (3) has an imide structure similar to polyimide and also has a vinyl double bond structure, and has a remarkable promoting effect on adhesion of polyimide-based, polybenzoxazole-based heat-resistant resins to substrates such as silicon, ceramics, metals and the like, and is hardly decomposed even after imidization by a high-temperature heat treatment of 300 ℃ or more in nitrogen or after imidization by a heat treatment in air, and therefore, the stability after heat treatment of the photosensitive resin composition and the adhesion between a cured film formed after high-temperature treatment and the substrate can be greatly improved.

In the general formula (3), R ₉ 、R ₁₀ 、R ₁₁ Each independently may be hydrogen, C ₁ ～C ₁₀ Alkyl or C of (2) ₁ ～C ₁₀ Alkoxy, C ₁ ～C ₁₀ The alkyl group of (a) may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc., preferably methyl or ethyl; c (C) ₁ ～C ₁₀ The alkoxy group of (a) may be methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decyloxy, etc., preferably methoxy or ethoxy. R is R ₉ 、R ₁₀ 、R ₁₁ May be the same or different. For example R ₉ 、R ₁₀ 、R ₁₁ Can be simultaneously hydrogen and C ₁ ～C ₁₀ Alkyl of (C) at the same time ₁ ～C ₁₀ Or one of them may be hydrogen and the other two may be C at the same time ₁ ～C ₁₀ Alkyl or C of (2) ₁ ～C ₁₀ Or any one of C ₁ ～C ₁₀ The other two are simultaneously hydrogen or C ₁ ～C ₁₀ Or one of them may be C ₁ ～C ₁₀ Two other alkoxy groups are simultaneously C ₁ ～C ₁₀ Or R is an alkyl group or hydrogen ₉ 、R ₁₀ 、R ₁₁ All different.

Preferably, R ₉ 、R ₁₀ 、R ₁₁ Respectively and independently C ₁ ～C ₁₀ Alkyl or C of (2) ₁ ～C ₁₀ Alkoxy radicals of (i.e. R) ₉ 、R ₁₀ 、R ₁₁ Are all selected from C ₁ ～C ₁₀ Alkyl or C of (2) ₁ ～C ₁₀ More preferably R ₉ 、R ₁₀ 、R ₁₁ Respectively and independently C ₁ ～C ₄ Alkyl or C of (2) ₁ ～C ₄ Most preferably R ₉ 、R ₁₀ 、R ₁₁ Each independently is methoxy or ethoxy. R is R ₉ 、R ₁₀ 、R ₁₁ May be the same or different.

In the general formula (3), R ₁₂ 、R ₁₃ Each independently is hydrogen or C ₁ ～C ₁₀ Alkyl of C ₁ ～C ₁₀ The alkyl group of (a) may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc., preferably methyl or ethyl. R is R ₁₂ 、R ₁₃ May be the same or different. PreferablyOf R, of ₁₂ 、R ₁₃ Are all hydrogen.

In certain embodiments, the silane coupling agent of formula (3) may be of the structure: r is R ₉ 、R ₁₀ 、R ₁₁ Are methoxy groups, R ₁₂ 、R ₁₃ Are all hydrogen; r is R ₉ 、R ₁₀ 、R ₁₁ Are all ethoxy radicals, R ₁₂ 、R ₁₃ Are all hydrogen; r is R ₉ 、R ₁₀ 、R ₁₁ Are all pentoxy groups, R ₁₂ 、R ₁₃ Are all hydrogen; r is R ₉ 、R ₁₀ 、R ₁₁ Are all octoxy, R ₁₂ 、R ₁₃ Are all hydrogen; r is R ₉ 、R ₁₀ 、R ₁₁ Are all methyl, R ₁₂ 、R ₁₃ Are all hydrogen; r is R ₉ 、R ₁₀ 、R ₁₁ All are ethyl, R ₁₂ 、R ₁₃ Are all hydrogen; r is R ₉ 、R ₁₀ 、R ₁₁ Are all butyl, R ₁₂ 、R ₁₃ Are all hydrogen; r is R ₉ 、R ₁₀ 、R ₁₁ All are heptyl, R ₁₂ 、R ₁₃ Are all hydrogen; r is R ₉ 、R ₁₀ 、R ₁₁ Are all hydrogen, R ₁₂ 、R ₁₃ Are all hydrogen; r is R ₉ 、R ₁₀ Are methoxy groups, R ₁₁ Is methyl, R ₁₂ 、R ₁₃ Are all hydrogen; r is R ₉ 、R ₁₀ Are all ethoxy radicals, R ₁₁ Is methyl, R ₁₂ 、R ₁₃ Are all hydrogen; r is R ₉ 、R ₁₀ 、R ₁₁ Are methoxy groups, R ₁₂ 、R ₁₃ Are all methyl groups; r is R ₉ 、R ₁₀ 、R ₁₁ Are all ethoxy radicals, R ₁₂ 、R ₁₃ All are propyl groups; r is R ₉ 、R ₁₀ 、R ₁₁ Are all pentoxy groups, R ₁₂ Is methyl, R ₁₃ Is hydrogen; r is R ₉ 、R ₁₀ Are methoxy groups, R ₁₁ Is methyl, R ₁₂ Is hydrogen, R ₁₃ Is ethyl. These silane coupling agents each have a good effect of improving the adhesion of the heat-resistant resin of the general formula (1) to a substrate, wherein R ₉ 、R ₁₀ 、R ₁₁ Respectively and independently C ₁ ～C ₁₀ Alkyl or C of (2) ₁ ～C ₁₀ Alkoxy, R ₁₂ 、R ₁₃ The silane coupling agent has better performance when both are hydrogen.

The preparation method of the silane coupling agent of the general formula (3) comprises the following steps:

1) The furoic acid anhydride compound shown in the formula (4) and the silane compound with the end group of amino group shown in the formula (5) are subjected to amidation reaction to form amic acid.

2) After the amidation reaction, imidization reaction is performed to obtain a silane coupling agent shown in the general formula (3).

In the formulas (4) and (5), R ₉ 、R ₁₀ 、R ₁₁ 、R ₁₂ 、R ₁₃ Is defined as before.

Further, the amidation reaction is carried out in aprotic polar solvents, and the effect of each aprotic polar solvent is equivalent. In view of cost and convenience of the obtaining means, it is preferable that the aprotic polar solvent is selected from at least one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide and γ -butyrolactone, preferably N-methylpyrrolidone or/and N, N-dimethylacetamide.

Further, the amidation reaction may be performed at room temperature under mild conditions, and the two reactants of formula (4) and formula (5) may be added in a theoretical molar ratio.

Further, the amidation reaction product is an amic acid compound (structural formula is shown as follows, R ₉ 、R ₁₀ 、R ₁₁ 、R ₁₂ 、R ₁₃ The definition of (3) is the same as that described above), the imidization reaction is directly carried out on the reaction solution without extracting the product after the amidation reaction, and the silane coupling agent represented by the general formula (3) can be obtained. The imidization is preferably chemical imidization. There are many reports in the prior art of chemical imidization, which is a process of reacting carboxyl groups and amide groups in molecules under the action of acid anhydride and alkali to form cyclic imine. The anhydride used may beAny of the anhydrides reported in the prior art as being useful for imidization, such as acetic anhydride, trifluoroacetic anhydride and the like, preferably acetic anhydride, and the base used may be any of the bases reported in the prior art as being useful for imidization, such as pyridine, triethylamine, diisopropylethylamine and the like, preferably pyridine.

Further, in the case of chemical imidization, the amount of the base to be used is 2 times or more, for example, 2 to 10 times, for example, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times, the molar amount of the silane compound having an amino group as an end group; the amount of acetic anhydride to be used is 2 times or more, for example, 2 to 10 times, for example, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times, the molar amount of the silane compound having an amino group as the terminal group.

Further, it was verified by experiments that the silane coupling agent of the general formula (3) exhibits a better adhesion promoting effect when used in combination with a suitable silane coupling agent. For example, the silane coupling agent of the general formula (3) may be used in combination with either one or both of 3- (triethoxysilylthio) propyl trimethoxysilane and γ -ureidopropyl triethoxysilane, and the effect is superior to that of the silane coupling agent of the general formula (3) alone. When these several silane coupling agents are used in combination, the proportions thereof are not particularly limited, and for example, the silane coupling agent of the general formula (3), the (triethoxysilylthio) propyltrimethoxysilane (if any), and the γ -ureidopropyltriethoxysilane (if any) may be mixed in a mass ratio range of 1:0.1 to 10:0.1 to 10.

In the photosensitive resin composition, the addition of the silane coupling agent greatly improves the adhesive force between the resin composition and a substrate, and the too low content has poor tackifying effect, so that the too high content can cause the reduction of other properties of the composition. In order to ensure adhesion to a substrate after high-temperature treatment, the amount of the component (c) is preferably 0.1 part by weight or more, and at this part by weight or more, a more remarkable adhesion promoting effect is exhibited, and more preferably 0.25 part by weight or more, and still more preferably 0.5 part by weight or more, relative to 100 parts by weight of the component (a). In order to secure storage stability, it is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and still more preferably 3.5 parts by weight or less.

In the present invention, component (d) in the photosensitive resin composition is a solvent. Examples of the solvent include aprotic polar solvents such as N-methylpyrrolidone, γ -butyrolactone, tetrahydrofuran, dioxane, N-dimethylformamide, and dimethylsulfoxide; ketones such as methyl ethyl ketone and acetone; esters such as ethyl acetate and ethyl lactate; aromatic hydrocarbons such as toluene and xylene. The solvent may be 1 or 2 or more. The amount of the component (d) is preferably 80 to 5000 parts by weight, more preferably 150 to 1000 parts by weight, relative to 100 parts by weight of the component (a).

The following describes the method for producing the photosensitive resin composition:

for example, in a three-necked flask, the synthesized component (a) containing the general formula (1) or/and the general formula (2) as a main component is dissolved in the solvent (d), after the component (a) is completely dissolved, the component (b) of the quinone diazide compound photosensitizer is added, stirring is continued until the quinone diazide compound photosensitizer is completely dissolved, then the silane coupling agent of the component (c) is added, and finally the mixture is subjected to a filtering operation to obtain the photosensitive resin composition. The viscosity of the composition is 1 to 5000 mPas, preferably 500 to 3000 mPas, more preferably 1000 to 2000 mPas. In order to remove foreign matter, filtration may be performed using a filter having a pore size of 0.1 μm to 5 μm, and more preferably a filter having a pore size of 1 μm.

Next, a method of forming a cured film using the photosensitive resin composition of the present invention will be described. The photosensitive resin composition is coated on a substrate, and a suitable substrate is selected according to actual needs, and common substrates include: silicon wafer, ceramic wafer, aluminum sheet, glass sheet, copper sheet, ITO glass, etc., but is not limited thereto. Examples of the coating method include: coating methods such as spray coating, spin coating, and doctor blade coating. Wherein the coating film thickness varies depending on the coating method, the rotation speed, the viscosity, the concentration of the composition components, and the like. In the present invention, a 4-inch silicon wafer is preferably used as a substrate for coating, and spin coating is preferably used to control the thickness of the resin film on the silicon wafer to 2 to 15. Mu.m.

Subsequently, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin film. Drying typically uses ovens, heated tables, infrared lamps, and the like. In the present invention, a heating stage is preferably used, and the heating stage is preferably carried out at a temperature of 50 to 150℃for 1 minute to several hours. After cooling to room temperature, the thickness of the photosensitive resin film was measured.

Next, the photosensitive resin film is irradiated with actinic rays through a mask having a desired pattern, and exposed. The active light rays commonly used in exposure include ultraviolet rays, X-rays, electron beams, and the like. In the present invention, mercury lamps are preferably used, which include i-line (365 nm), h-line (405 nm), g-line (436 nm).

After exposure, the exposed areas are removed by using an alkaline developer to form a pattern. Common developing solutions are: aqueous solutions of tetramethyl ammonium hydroxide (TMAH), sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like, and aqueous solutions of compounds exhibiting basicity. In addition, one or more other substances may be added to the above alkaline solution, as the case may be, for example: polar solvents such as N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and the like; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; ketones such as cyclopentanone, cyclohexanone and isobutyl ketone. After development, the aqueous solution is preferably rinsed with water, or ethanol, isopropanol, ethyl lactate, propylene glycol monomethyl ether acetate, or the like may be added to the aqueous solution for rinsing. For example, positive photoresist developer and positive photoresist rinse are poured into two glass petri dishes, respectively. The temperature of the developing solution is controlled to be 25+/-1 ℃, and the exposed resin film is immersed into the developing solution, and then timing is started. After the exposed area exposes the silicon wafer substrate completely, the development is finished, the timing is stopped, and the time required by the whole process is recorded.

Finally, the resin pattern obtained after development is imidized (thermally imidized) at a temperature of 200 to 500 ℃ to be converted into a cured film. The heating treatment is usually carried out by selecting a stepwise temperature rise and maintaining it at different temperatures for a certain period of time or selecting a certain temperature range to continuously raise the temperature. As one example, there is a method of performing heat treatment at 130 ℃, 200 ℃, 350 ℃ for 30 minutes each, or a method of linearly raising the temperature from room temperature to 400 ℃ over 2 hours.

The present invention provides a photosensitive resin composition having excellent adhesion to a substrate. The cured film formed from the composition can be used for passivation films of semiconductors, surface protection of semiconductor devices, multi-layer wiring (RDL) insulating layers in chip packaging, insulating layers of OLED devices, and the like.

The following examples are given to illustrate the present invention and to aid a more complete understanding of those skilled in the art, but the present invention is not limited to these examples. The photosensitive resin composition in the examples was evaluated by the following method.

(1) Viscosity test

2ml of the photosensitive resin composition sample is taken and placed into a sample cell of a rotary viscometer (BROOKFIELD DV2T RV), a proper measuring range is selected, and the temperature is controlled at 25+/-0.1 ℃ for viscosity test.

(2) Adhesion peel test of cured film (imidized resin film) and substrate

A4-inch silicon wafer was coated with the photosensitive resin composition, followed by soft baking at 120℃for 3 minutes using a heating stage, to obtain a photosensitive resin film having a film thickness of 8 to 10. Mu.m. Then, the prepared photosensitive resin film was placed in an inert gas oven, and subjected to heat treatment under a nitrogen stream (oxygen content lower than 20 ppm). The cured film was obtained by heat-treating at 170℃for 30 minutes, then heating to 320℃over 1 hour, and treating at 320℃for 1 hour, and film thickness was measured by a step-by-step apparatus (KLA Tencor P-7) and controlled at 5. Mu.m.

The cured film was scored with 10 rows and 10 columns of squares using a dicer (model number, BYK-Gardner A-5125), and a peeling test was performed with an adhesive tape (dedicated transparent 3M adhesive tape) with reference to national Standard GB/T9286-1998 "cross-cut test of paint and varnish film", and the number of squares peeled off was recorded as the peeling condition before PCT.

The cured film was patterned into 10 rows by 10 columns of squares using a dicer (model number BYK-Gardner A-5125) in the same manner as described above, and the patterned cured film was subjected to PCT test (121 ℃ C., 2 atm saturated steam; dongguan Hongjin in technology PCT-30) for 200 hours. After the PCT test was completed, the peeling test was performed using an adhesive tape in the same manner as described above, and the number of peeled cells was recorded as the peeling condition after PCT.

When the number of the pieces peeled off in the adhesion peeling test was less than 10, the adhesion was considered good, and when it was 10 or more, the adhesion was considered poor.

Synthesis example 1

Synthesis of polyimide-based resin A-1 (polyesteramide resin):

to a 500mL three-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 31.02g (0.1 mol) of 4,4' -oxydiphthalic anhydride (ODPA) and 100g of N-methylpyrrolidone (NMP) were successively added under a nitrogen flow, and the mixture was stirred and dissolved at room temperature to obtain a dianhydride solution. Another three-necked flask equipped with a stirrer was charged with 29.30g (0.08 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF), 2.48g (0.01 mol) of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane (SiDA) and 100g of N-methylpyrrolidone in this order, followed by stirring and dissolution to obtain a diamine solution. And (3) dropwise adding the diamine solution into the dianhydride solution, reacting for 1h at normal temperature after the dropwise adding is finished, and then reacting for 2h at 50 ℃. After completion of the reaction, 2.18g (0.02 mol) of 4-aminophenol as a blocking agent was added thereto and reacted at 50℃for 2 hours. 23.83g of N, N-dimethylformamide dimethyl acetal was diluted with 45g of NMP, and the diluted solution was added dropwise to the reaction solution, and reacted at 50℃for 3 hours after completion of the addition. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and the polymer is separated out to obtain white precipitate. Filtering, washing with deionized water for three times, and drying in vacuum oven at 80deg.C for 72hr to obtain polymer, namely polyimide resin A-1.

The molecular weight of the polyimide-based resin A-1 was measured by gel permeation chromatography (GPC, shimadzu LC-20 AD) in terms of standard polystyrene, and the eluent was N-methylpyrrolidone, column oven temperature 40 ℃.

Polyimide resin A-1Weight average molecular weight (M) _w ) In the range of 1.7 to 1.9 ten thousand, number average molecular weight (M _n ) The molecular weight distribution is 1.4-1.5 ten thousand and is 1.2-1.6.

Synthesis example 2

Synthesis of polybenzoxazole resin A-2 (polybenzoxazole precursor resin):

32.96g (0.09 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF), 2.18g (0.02 mol) of 4-aminophenol, 15.82g (0.2 mol) of pyridine and 100g of N-methylpyrrolidone (NMP) were successively charged into a 500mL three-necked flask equipped with a stirrer, a dropping funnel and a thermometer under a nitrogen stream, and after the mixture was sufficiently dissolved, the temperature of the solution was cooled to-15 ℃. 29.51g (0.10 mol) of 4, 4-diphenylether dicarboxylic acid dichloride was dissolved in 50g of NMP to prepare a solution, and the solution was dropped into the flask with a dropping funnel, and the reaction mass was controlled to be below 0℃during the dropping. After the dripping is completed, stirring and reacting for 6hr under the condition of minus 10 ℃ to minus 15 ℃. After the reaction, the reaction mixture was poured into 3L of a 10wt% aqueous methanol solution to precipitate a polymer to obtain a white precipitate. Filtering, washing with deionized water for three times, and drying in a vacuum oven at 50deg.C for 72hr to obtain polymer, namely polybenzoxazole resin A-2.

The molecular weight of the polybenzoxazole resin A-2 was measured by gel permeation chromatography (GPC, shimadzu LC-20 AD) in terms of standard polystyrene, and the eluent was N-methylpyrrolidone, column oven temperature 40 ℃.

Weight average molecular weight (M) of polybenzoxazole resin A-2 _w ) In the range of 2.1 to 2.5 ten thousand, number average molecular weight (M _n ) The molecular weight distribution is 1.3-1.6 ten thousand and is 1.3-1.7.

Synthesis example 3

Synthesis of silane coupling agent B-1:

to a 500mL three-necked flask equipped with a stirrer and a thermometer, 17.93g (0.1 mol, japanese Kogyo chemical KBM-903) of (3-aminopropyl) trimethoxysilane and 150, m L of N, N-dimethylacetamide as solvents were successively added, and stirring was started. 11.22g (0.1 mol) of itaconic anhydride was weighed and dissolved in 100mL of N, N-dimethylacetamide. The 500mL three-neck flask is placed in an ice-water bath, itaconic anhydride solution is slowly added dropwise while stirring, and the temperature of the reaction material is controlled to be lower than 10 ℃. After the completion of the dropwise addition, the ice-water bath was removed, and the reaction was continued with stirring at room temperature for 20hr. After the reaction was completed, 15.82g (0.2 mol) of pyridine was added to the reaction system, and after stirring uniformly, 20.42g (0.2 mol) of acetic anhydride was slowly added to the mixture, and the mixture was reacted at room temperature for 20hr. After the completion of the reaction, evaporation under reduced pressure was carried out to remove the solvent, the formed acetic acid, the residual acetic anhydride, pyridine and other front distillates, thereby obtaining the purified silane coupling agent B-1.

The structural formula of the obtained silane coupling agent B-1 is shown as the general formula (3), wherein R ₉ Is methoxy, R ₁₀ Is methoxy, R ₁₁ Is methoxy, R ₁₂ Is hydrogen, R ₁₃ Is hydrogen. The nuclear magnetic information of the silane coupling agent B-1 is as follows:

¹ HNMR(CDCl ₃ )：δ0.58(t,2H),1.6(m,2H),2.85(s,2H),3.55(s,9H),3.48(t,2H),5.63(s,1H),6.11(s,1H)。

synthesis example 4

Synthesis of silane coupling agent B-2:

to a 500mL three-necked flask equipped with a stirrer and a thermometer, 22.1 g (0.1 mol) of (3-aminopropyl) triethoxysilane, 150mL of N, N-dimethylacetamide as a solvent, and 0.1mol were sequentially added, and stirring was started. 11.22g (0.1 mol) of itaconic anhydride was weighed and dissolved in 100mL of N, N-dimethylacetamide. The 500mL three-neck flask is placed in an ice-water bath, itaconic anhydride solution is slowly added dropwise while stirring, and the temperature of the reaction material is controlled to be lower than 10 ℃. After the completion of the dropwise addition, the ice-water bath was removed, and the reaction was continued at room temperature for 20hr. After the completion of the reaction, 23.73g (0.3 mol) of pyridine was added to the reaction system, followed by stirring, 30.63g (0.3 mol) of acetic anhydride was slowly added thereto, and the reaction was carried out at room temperature for 20hr. After the completion of the reaction, evaporation under reduced pressure was carried out to remove the solvent, the formed acetic acid, the residual acetic anhydride, pyridine and other front distillates, thereby obtaining the purified silane coupling agent B-2.

The structural formula of the obtained silane coupling agent B-2 is shown as the general formula (3), wherein R ₉ Is ethoxy, R ₁₀ Is ethoxy, R ₁₁ Is ethoxy, R ₁₂ Is hydrogen, R ₁₃ Is hydrogen. The nuclear magnetic information of the silane coupling agent B-2 is as follows:

¹ HNMR(CDCl ₃ )：δ0.58(t,2H),1.22(t,9H),1.6(m,2H),2.85(s,2H),3.48(t,2H),3.83(q,6H),5.63(s,1H),6.11(s,1H)。

synthesis example 5

Synthesis of silane coupling agent B-3:

to a 500mL three-necked flask equipped with a stirrer and a thermometer, 16.33g (0.1 mol, nanjing Dimond chemical KH-662) of 3-aminopropyl methyldimethoxy silane and 150mL of N, N-dimethylacetamide as solvents were sequentially added, and stirring was started. 11.22g (0.1 mol) of itaconic anhydride was weighed and dissolved in 100mL of N, N-dimethylacetamide. The 500mL three-neck flask is placed in an ice-water bath, itaconic anhydride solution is slowly added dropwise while stirring, and the temperature of the reaction material is controlled to be lower than 10 ℃. After the completion of the dropwise addition, the ice-water bath was removed, and the reaction was continued at room temperature for 20hr. After the completion of the reaction, 15.82g (0.2 mol) of pyridine was added to the reaction system, and after stirring uniformly, 42.01g (0.2 mol) of trifluoroacetic anhydride was slowly added thereto, and the reaction was carried out at room temperature for 20hr. After the completion of the reaction, evaporation under reduced pressure was carried out to remove the solvent, the formed acetic acid, the residual acetic anhydride, pyridine and other front distillates, thereby obtaining purified silane coupling agent B-3.

The structural formula of the obtained silane coupling agent B-3 is shown as the general formula (3), wherein R ₉ Is methyl, R ₁₀ Is methoxy, R ₁₁ Is methoxy, R ₁₂ Is hydrogen, R ₁₃ Is hydrogen. The nuclear magnetic information of the silane coupling agent B-3 is as follows:

¹ HNMR(CDCl ₃ )：δ0.14(s,3H),1.22(t,2H),1.6(m,2H),2.85(s,2H),3.48(s,6H),5.63(s,1H),6.11(s,1H)。

example 1

10.0g of the polymer A-1 obtained in Synthesis example 1 and 20.0. 20.0g N-methylpyrrolidone (NMP) solvent were added to a three-necked flask, stirred, and after the resin was completely dissolved, 2.0g of the quinone diazide compound NT-300 (manufactured by Nippon Toyo Kogyo Co., ltd.) and 0.2g of the silane coupling agent B-1 obtained in Synthesis example 3 were added, and after the mixture was sufficiently dissolved, the mixture was press-filtered through a 1.0 μm filter membrane to obtain a photosensitive resin composition.

Example 2

Example 1 was repeated except that the amount of the silane coupling agent B-1 was changed to 0.2g of the silane coupling agent B-2 obtained in Synthesis example 4.

Example 3

Example 1 was repeated except that the amount of the silane coupling agent B-1 was changed to 0.2g of the silane coupling agent B-3 obtained in Synthesis example 5.

Example 4

Example 1 was repeated except that the polymer A-1 was changed to the polymer A-2 obtained in Synthesis example 2.

Example 5

Example 2 was repeated except that the polymer A-1 was changed to the polymer A-2 obtained in Synthesis example 2.

Example 6

Example 3 was repeated except that the polymer A-1 was changed to the polymer A-2 obtained in Synthesis example 2.

Example 7

10.0g of the polymer A-1 obtained in Synthesis example 1 and 20.0. 20.0g N-methylpyrrolidone (NMP) as a solvent were put into a three-necked flask, stirred, and after the resin was completely dissolved, 2.0g of the quinone diazide compound NT-300 (manufactured by Nippon Toyo Kogyo Co., ltd.), 0.2g of the silane coupling agent B-1 obtained in Synthesis example 3 and 0.1g of gamma-ureido propyl triethoxysilane (Silquest A-1160) were added, and after the mixture was sufficiently dissolved, the mixture was press-filtered through a 1.0 μm filter membrane to obtain a photosensitive resin composition.

Example 8

10.0g of the polymer A-1 obtained in Synthesis example 1 and 20.0. 20.0g N-methylpyrrolidone (NMP) solvent were added to a three-necked flask, stirred, and after complete dissolution of the resin, 2.0g of quinone diazide compound NT-300 (manufactured by Nippon Denshoku Kogyo Co., ltd.), 0.2g of silane coupling agent B-1 obtained in Synthesis example 3, 0.1g of gamma-ureido propyl triethoxysilane (Silquest A-1160) and 0.05g of 3- (triethoxysilylthio) propyl trimethoxysilane (Nippon Sichuan chemical Co., X-12-1056 ES) were added, and after sufficient dissolution, the mixture was press-filtered through a 1.0 μm filter membrane to obtain a photosensitive resin composition.

Example 9

Example 7 was repeated except that the amount of the silane coupling agent B-1 was changed to 0.2g of the silane coupling agent B-2 obtained in Synthesis example 4.

Example 10

Example 8 was repeated except that the amount of the silane coupling agent B-1 was changed to 0.2g of the silane coupling agent B-2 obtained in Synthesis example 4.

Example 11

Example 7 was repeated except that the amount of the silane coupling agent B-1 was changed to 0.2g of the silane coupling agent B-3 obtained in Synthesis example 5.

Example 12

Example 8 was repeated except that the amount of the silane coupling agent B-1 was changed to 0.2g of the silane coupling agent B-3 obtained in Synthesis example 5.

Example 13

Example 7 was repeated except that the polymer A-1 was changed to the polymer A-2 obtained in Synthesis example 2.

Example 14

Example 8 was repeated except that the polymer A-1 was changed to the polymer A-2 obtained in Synthesis example 2.

Example 15

Example 9 was repeated except that the polymer A-1 was changed to the polymer A-2 obtained in Synthesis example 2.

Example 16

Example 10 was repeated except that the polymer A-1 was changed to the polymer A-2 obtained in Synthesis example 2.

Example 17

Example 11 was repeated except that the polymer A-1 was changed to the polymer A-2 obtained in Synthesis example 2.

Example 18

Example 12 was repeated except that the polymer A-1 was changed to the polymer A-2 obtained in Synthesis example 2.

Example 19

Example 1 was repeated except that the amount of the silane coupling agent B-1 was changed to 0.01 g.

Example 20

Example 1 was repeated except that the amount of the silane coupling agent B-1 was changed to 0.025 g.

Example 21

Example 1 was repeated except that the amount of the silane coupling agent B-1 was changed to 0.05 g.

Comparative example 1

Example 1 was repeated except that the silane coupling agent B-1 was changed to 0.2g KBM-903.

Comparative example 2

Example 1 was repeated except that the silane coupling agent B-1 was changed to 0.2g KBE-903.

Comparative example 3

Example 1 was repeated except that the silane coupling agent B-1 was changed to 0.2g KH-662.

Comparative example 4

Comparative example 1 was conducted except that 0.1g of Silquest A-1160 was added.

Comparative example 5

Comparative example 3 was conducted except that 0.1g of Silquest A-1160 and 0.05-g X-12-1056ES were added.

Comparative example 6

Comparative example 1 was conducted except that the polymer A-1 was changed to the polymer A-2.

Comparative example 7

Comparative example 2 was conducted except that the polymer A-1 was changed to the polymer A-2.

Comparative example 8

Comparative example 3 was conducted except that the polymer A-1 was changed to the polymer A-2.

Comparative example 9

Comparative example 4 was conducted except that the polymer A-1 was changed to the polymer A-2.

Comparative example 10

Comparative example 5 was conducted except that the polymer A-1 was changed to the polymer A-2.

The cured film samples prepared as described above were tested for adhesion to substrates according to the adhesion peel test method described above, and the results are shown in table 1.

TABLE 1

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As can be seen from the comparison of examples 1 to 6 and comparative examples 1 to 3, 6 to 8, the addition of the silane coupling agent having a double bond and an imide structure to the photosensitive resin composition of the present invention can significantly improve the adhesion of the resin to the substrate, and exhibits high adhesion to the substrate even after PCT treatment. As can also be seen from the comparison of examples 7-18 and comparative examples 4-5, 9-10, the silane coupling agent having a double bond and imide structure, in combination with A-1160 and X-12-1056ES, forms a coupling agent system that can further improve the adhesion of the resin composition to the substrate.

The silane coupling agent of the present invention has a remarkable accelerating effect on adhesion of polyimide-based heat-resistant resins and polybenzoxazole-based heat-resistant resins to a substrate, and can improve adhesion of heat-resistant resin films to the substrate. The photosensitive resin composition can be applied to a surface protective film, an interlayer insulating layer, a secondary wiring insulating layer, a flip chip device protective film, a protective film with a bump structure for a flip chip device, an interlayer insulating layer for a multilayer circuit, a flexible copper-clad plate insulating layer, a solder resist film, a liquid crystal aligning agent, and the like of a semiconductor device.

Claims

1. A photosensitive resin composition containing a silane coupling agent is characterized in that: the composition comprises the following components:

component (b): quinone diazide compounds;

component (c): a silane coupling agent including a silane coupling agent of a structure represented by the following general formula (3), 3- (triethoxysilylthio) propyl trimethoxysilane and gamma-ureidopropyl triethoxysilane;

component (d): a solvent;

；

In the general formula (1), R ₁ And R is ₂ Each independently represents a 2-to 8-valent organic group having 2 or more carbon atoms; r is R ₃ And R is ₄ Each independently represents hydrogen or a 1-valent organic group having 1 to 20 carbon atoms; n represents a range of 5 to 1000; l and m independently represent an integer of 0 to 2, and p and q independently represent an integer of 0 to 2, wherein p+q>0；

；

In the general formula (2), R ₅ Represents a 4-8 valent organic group; r is R ₆ Represents a 2-6 valent organic group; r is R ₇ And R is ₈ Represents a phenolic hydroxyl group, a sulfonic acid group or a thiol group, R ₇ And R is ₈ Each of the two groups may be a single group, or may be a mixture of different groups; t represents a range of 3 to 1000; r and s independently represent integers of 0 to 4;

；

in the general formula (3), R ₉ Is hydrogen, C ₁ -C ₁₀ Alkyl or C of (2) ₁ -C ₁₀ Alkoxy groups of (a); r is R ₁₀ Is hydrogen, C ₁ -C ₁₀ Alkyl or C ₁ -C ₁₀ Alkoxy groups of (a); r is R ₁₁ Is hydrogen, C ₁ -C ₁₀ Alkyl or C of (2) ₁ -C ₁₀ Alkoxy groups of (a); r is R ₁₂ Is hydrogen or C ₁ -C ₁₀ Alkyl of (a); r is R ₁₃ Is hydrogen or C ₁ -C ₁₀ Is a hydrocarbon group.

2. The photosensitive resin composition according to claim 1, wherein: in the general formula (3), R ₉ 、R ₁₀ 、R ₁₁ Respectively and independently C ₁ -C ₁₀ Alkyl or C of (2) ₁ -C ₁₀ Alkoxy groups of (a).

3. The photosensitive resin composition according to claim 2, wherein: in the general formula (3), R ₉ 、R ₁₀ 、R ₁₁ Respectively and independently C ₁ -C ₄ Alkyl or C of (2) ₁ -C ₄ Alkoxy groups of (a).

4. The photosensitive resin composition according to claim 3, wherein: in the general formula (3), R ₉ 、R ₁₀ 、R ₁₁ Each independently is methoxy or ethoxy.

5. The photosensitive resin composition according to claim 1, wherein: in the general formula (3), R ₁₂ 、R ₁₃ Each independently hydrogen.

6. The photosensitive resin composition according to claim 1, 2, 3, 4 or 5, characterized in that: the silane coupling agent of the general formula (3) is prepared by amidation reaction of a furoic acid anhydride compound shown in the formula (4) and a silane compound with an amino end group shown in the formula (5), and then imidization reaction;

；

in the formula (4) and the formula (5), R ₉ 、R ₁₀ 、R ₁₁ 、R ₁₂ 、R ₁₃ Is defined in accordance with any one of the preceding claims 1-5.

7. The photosensitive resin composition according to claim 6, wherein: in the preparation of the silane coupling agent of the general formula (3), the amidation reaction and the imidization reaction are carried out in an aprotic polar solvent.

8. The photosensitive resin composition according to claim 7, which isIs characterized in that: in preparing the silane coupling agent of the general formula (3), the aprotic polar solvent is selected from NMethyl pyrrolidone,N,NDimethylformamide (DMA),N,N-at least one of dimethylacetamide, dimethylsulfoxide and gamma-butyrolactone.

9. The photosensitive resin composition according to claim 6, wherein: when the silane coupling agent of the general formula (3) is prepared, the molar ratio of the furoic acid anhydride compound shown in the formula (4) to the silane compound with the end group being amino shown in the formula (5) is 1:0.9-1.1.

10. The photosensitive resin composition according to claim 6, wherein: in the preparation of the silane coupling agent of the general formula (3), the temperature of the amidation reaction is room temperature.

11. The photosensitive resin composition according to claim 6, wherein: in preparing the silane coupling agent of the general formula (3), after amidation reaction, alkali and acid anhydride are added into the reaction solution to carry out imidization reaction.

12. The photosensitive resin composition according to claim 11, wherein: when the silane coupling agent of the general formula (3) is prepared, the base is pyridine, triethylamine or diisopropylethylamine, and the anhydride is acetic anhydride or trifluoroacetic anhydride.

13. The photosensitive resin composition according to claim 11, wherein: when the silane coupling agent of the general formula (3) is prepared, the amount of the base is 2 to 10 times the molar amount of the silane compound having an amino group as a terminal group, and the amount of the acid anhydride is 2 to 10 times the molar amount of the silane compound having an amino group as a terminal group.

14. The photosensitive resin composition according to claim 1, 2, 3, 4 or 5, characterized in that: the mass ratio of the component (a) to the component (c) is 100:0.1-10.

15. The photosensitive resin composition according to claim 14, wherein: the mass ratio of the component (a) to the component (c) is 100:0.25 to 5.0.

16. The photosensitive resin composition according to claim 15, wherein: the mass ratio of the component (a) to the component (c) is 100:0.5-3.5.

17. The photosensitive resin composition according to claim 1, 2, 3, 4 or 5, characterized in that: the mass ratio of the component (a) to the component (b) is 100: 1-50 parts; the mass ratio of the component (a) to the component (d) is 1:0.8 to 50.

18. The photosensitive resin composition according to claim 17, wherein: the mass ratio of the component (a) to the component (b) is 100: 5-30 parts; the mass ratio of the component (a) to the component (d) is 1: 1.5-10.

19. The photosensitive resin composition according to claim 1, wherein: the component (d) is one or more of aprotic polar solvent, ketone solvent, ester solvent and aromatic hydrocarbon solvent.

20. The photosensitive resin composition according to claim 19, wherein: in the component (d), the aprotic polar solvent is selected from one or more of N-methylpyrrolidone, gamma-butyrolactone, tetrahydrofuran, dioxane, N-dimethylformamide and dimethylsulfoxide, the ketone solvent is selected from one or more of methyl ethyl ketone and acetone, the ester solvent is selected from one or more of ethyl acetate and ethyl lactate, and the aromatic hydrocarbon solvent is selected from one or more of toluene and xylene.