阅读说明：本技术 一种含硅烷偶联剂的感光性树脂组合物 (Photosensitive resin composition containing silane coupling agent ) 是由 李铭新 公聪聪 王华森 陈存浩 王建伟 于 2020-07-17 设计创作，主要内容包括：本发明公开了一种含硅烷偶联剂的感光性树脂组合物,所述感光性树脂组合物中引入具有双键和酰亚胺结构的硅烷偶联剂,通过该结构的硅烷偶联剂的加入,提高了感光性树脂组合物在高温热固化后与基材之间的粘合性。(The invention discloses a photosensitive resin composition containing a silane coupling agent, wherein the silane coupling agent with double bonds and an imide structure is introduced into the photosensitive resin composition, and the adhesion between the photosensitive resin composition and a base material after high-temperature thermosetting is improved through the addition of the silane coupling agent with the structure.)

1. A photosensitive resin composition containing a silane coupling agent, characterized in that: comprises 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;

a component (b): a quinone diazide compound;

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

a component (d): a solvent;

in the general formula (1), R₁And R₂Each independently represents a 2-to 8-valent organic group having 2 or more carbon atoms; r₃And R₄Each 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 are each independently an integer of 0 to 2, p and q are each independently an integer of 0 to 2, wherein p + q>0；

In the general formula (2), R₅Represents an organic group having a valence of 4 to 8; r₆Represents an organic group having a valence of 2 to 10; r₇And R₈Represents a phenolic hydroxyl group, a sulfonic acid group or a thiol group, R₇And R₈Each of which may be a single group or a mixture of different groups; t represents a range of 3 to 1000; r and s are respectively independent integers of 0-4;

in the general formula (3), R₉Is hydrogen, C₁-C₁₀Alkyl or C₁-C₁₀Alkoxy group of (a); r₁₀Is hydrogen, C₁-C₁₀Alkyl or C₁-C₁₀Alkoxy group of (a); r₁₁Is hydrogen, C₁-C₁₀Alkyl or C₁-C₁₀Alkoxy group of (a); r₁₂Is hydrogen or C₁-C₁₀Alkyl groups of (a); r₁₃Is hydrogen or C₁-C₁₀Alkyl group of (1).

2. The photosensitive resin composition according to claim 1, wherein: in the general formula (3), R₉、R₁₀、R₁₁Are each independently C₁-C₁₀Alkyl or C₁-C₁₀Alkoxy group of (a); preferably, R₉、R₁₀、R₁₁Are each independently C₁-C₄Alkyl or C₁-C₄Alkoxy group of (a); more preferably, R₉、R₁₀、R₁₁Each independently is methoxy or ethoxy.

3. The photosensitive resin composition according to claim 1, wherein: in the general formula (3), R₁₂、R₁₃Each independently is hydrogen.

4. The photosensitive resin composition according to claim 1,2 or 3, wherein: the silane coupling agent of the general formula (3) is prepared by amidation reaction of a furfuryl acid anhydride compound of the formula (4) and a silane compound having an amino group as a terminal group of the formula (5), followed by imidization;

in the formulae (4) and (5), R₉、R₁₀、R₁₁、R₁₂、R₁₃Is in accordance with the definition of any of the preceding claims 1-3.

5. The photosensitive resin composition according to claim 4, 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, preferably, the aprotic polar solvent is selected fromN-methyl pyrrolidone,N,N-dimethylformamide,N,N-at least one of dimethylacetamide, dimethylsulfoxide and γ -butyrolactone; preferably, the molar ratio of the furfuryl acid anhydride compound represented by the formula (4) to the silane compound represented by the formula (5) having an amino group as a terminal group is 1: 0.9-1.1; preferably, the temperature for the amidation and imidization reactions is room temperature.

6. The photosensitive resin composition according to claim 4, wherein: in the preparation of the silane coupling agent of the general formula (3), after amidation reaction, adding alkali and acid anhydride into the reaction solution to carry out imidization; preferably, the base is pyridine, triethylamine or diisopropylethylamine, and the anhydride is acetic anhydride or trifluoroacetic anhydride; preferably, the amount of the base used is 2 to 10 times the molar amount of the amino group-terminated silane compound, and the amount of the acid anhydride used is 2 to 10 times the molar amount of the amino group-terminated silane compound.

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein: the silane coupling agent of component (c) further comprises 3- (triethoxysilylthio) propyltrimethoxysilane and/or gamma-ureidopropyltriethoxysilane.

8. The photosensitive resin composition according to claim 1,2 or 3, wherein: the mass ratio of the component (a) to the component (c) is 100: 0.1-10, preferably 100: 0.25 to 5.0, and more preferably 100:0.5 to 3.5.

9. The photosensitive resin composition according to claim 1,2 or 3, wherein: the mass ratio of the component (a) to the component (b) is 100: 1-50, preferably 100: 5-30; the mass ratio of the component (a) to the component (d) is 1: 0.8-50, preferably 1:1.5 to 10.

10. 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; preferably, the aprotic polar solvent is selected from one or more of N-methylpyrrolidone, γ -butyrolactone, tetrahydrofuran, dioxane, N-dimethylformamide, and dimethylsulfoxide, the ketone-based solvent is selected from one or more of methyl ethyl ketone and acetone, the ester-based solvent is selected from one or more of ethyl acetate and ethyl lactate, and the aromatic hydrocarbon-based solvent is selected from one or more of toluene and xylene.

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 particle blocking, surface protection, interlayer dielectric or insulation of a semiconductor device, an insulating layer of an OLED device, and the like. The photosensitive resin composition contains a silane coupling agent with double bonds and an imide structure, and can improve the adhesion of the photosensitive resin to 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 are used for surface protective films, interlayer insulating films, and the like of semiconductor devices such as LSI (Large Scale integration). With the miniaturization of semiconductor devices, a resolution of several micrometers is also required for surface protective films, interlayer insulating films, and the like. Therefore, a positive photosensitive polyimide composition or a photosensitive polybenzoxazole composition which can be finely processed can be used for the above-mentioned applications. 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 retained in an element. Therefore, the adhesion of such films to substrates after thermal curing is of critical importance.

In the heat-resistant resins known at present, adhesion to substrates such as silicon wafers is not sufficient. Therefore, in order to improve the adhesion between the heat-resistant resin film and the base material, there have been proposed methods of pretreating the base material with a silane coupling agent or the like, adding a silane coupling agent to a heat-resistant resin precursor composition (hereinafter referred to as a coating paste), or adding an organic silicon compound capable of participating in polymerization during the synthesis of the heat-resistant resin precursor, to improve the adhesion of the heat-resistant resin film to the base material. Among these methods, the method of adding a silane coupling agent to a coating paste is the simplest. Silane coupling agents suitable for use with high heat resistant organic materials such as high molecular polymers like polyimide, polybenzoxazole, polyethersulfone, and the like generally have a chemical structure similar to that of the high molecular polymer to promote adhesion of the heat resistant material to the substrate.

In patent documents JP-a 2009-. Patent document CN102292675A discloses that a silane coupling agent containing an epoxy group is used in combination with a silane coupling agent containing a styryl group, and in the structure of the silane coupling agent containing a styryl group, an alkoxysilane is directly bonded to an aromatic ring, and because of its strong bonding energy, a resin film having excellent adhesion to a substrate can be obtained even after the obtained resin composition is subjected to a high-temperature heat treatment at 350 ℃ or higher or a heat treatment in air, but the silane coupling agent is expensive to produce. Liufeng and the like (synthesis research [ J ] of phenylacetylene phthalic anhydride modified silane coupling agent, 2009,31(07): 538) -540.) by utilizing 4-phenylacetylene phthalic anhydride (4-PEPA) to modify gamma-aminopropyl triethoxysilane (gamma-APS), 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 close to the polymerization temperature of ethynyl, so that hydrophobic terminal alkynyl is polymerized under the high temperature condition, and the hydrophilic terminal silicon group is well bonded with the substrate to achieve the effect of enhancing the adhesion. However, phenylethynyl phthalic anhydride is expensive and not suitable for large-scale industrial use.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention provides a silane coupling agent-containing photosensitive resin composition, which contains a silane coupling agent with double bonds and an imide structure, and the silane coupling agent is used alone or together with other silane coupling agents, so that the photosensitive resin composition still shows excellent adhesion with a substrate after being subjected to heat treatment at the temperature of more than 300 ℃ in an air atmosphere.

The silane coupling agent with double bonds and an imide structure is added into the photosensitive resin composition, the introduction of the silane coupling agent greatly improves the adhesion between a photosensitive resin film formed after the photosensitive resin composition is thermally cured and a base material (silicon, ceramic, metal and other base materials), and when the silane coupling agent is matched with other silane coupling agents for use, the adhesion is further improved.

The specific technical scheme of the invention is as follows:

a photosensitive resin composition containing a silane coupling agent (hereinafter referred to as photosensitive resin composition, the same shall apply hereinafter) contains 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;

a component (b): a quinone diazide compound;

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

a component (d): a solvent.

Further, in the general formula (1), R₁And R₂Each independently represents a 2-to 8-valent organic group having 2 or more carbon atoms; r₃And R₄Each 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 are each independently an integer of 0 to 2, p and q are each independently an integer of 0 to 2, wherein p + q>0。

Further, in the general formula (2), R₅Represents an organic group having a valence of 4 to 8; r₆Represents an organic group having a valence of 2 to 10; r₇And R₈Represents a phenolic hydroxyl group, a sulfonic acid group or a thiol group, R₇And R₈Each of which may be a single group or 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.

Further, in the general formula (3), R₉Is hydrogen, C₁-C₁₀Alkyl or C₁-C₁₀Alkoxy group of (a); r₁₀Is hydrogen, C₁-C₁₀Alkyl or C₁-C₁₀Alkoxy group of (a); r₁₁Is hydrogen, C₁-C₁₀Alkyl or C₁-C₁₀Alkoxy group of (2). R₉、R₁₀、R₁₁May be the same or different. R₁₂Is hydrogen or C₁～C₁₀Alkyl groups of (a); r₁₃Is hydrogen or C₁～C₁₀Alkyl group of (1). R₁₂、R₁₃May be the same or different.

Preferably, in the general formula (3), R₉Is C₁-C₁₀Alkyl or C₁-C₁₀More preferably C₁-C₄Alkyl or C₁-C₄Most preferably methoxy or ethoxy.

Preferably, in the general formula (3), R₁₀Is C₁-C₁₀Alkyl or C₁-C₁₀More preferably C₁-C₄Alkyl or C₁-C₄Most preferably methoxy or ethoxy.

Preferably, in the general formula (3), R₁₁Is C₁-C₁₀Alkyl or C₁-C₁₀More preferably C₁-C₄Alkyl or C₁-C₄Most preferably methoxy or ethoxy.

Preferably, in the general formula (3), R₁₂And R₁₃Are all hydrogen atoms.

Further, the silane coupling agent of the general formula (3) of the present invention is obtained by subjecting the furfuryl acid anhydride compound of the formula (4) and the silane compound of the formula (5) having an amino group as a terminal group to an amidation reaction and then to an imidization reaction.

In the above formulae (4) and (5), R₉、R₁₀、R₁₁、R₁₂、R₁₃The definitions of (a) are consistent with the definitions set forth above.

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

Further, the molar ratio of the furfuryl anhydride compound represented by the formula (4) to the silane compound represented by the formula (5) having an amino group as a terminal group is 1:0.9 to 1.1.

Further, after the amidation reaction, a base and an acid anhydride are added to the reaction solution to perform imidization. The alkali is pyridine, triethylamine or diisopropyl ethylamine, and the acid anhydride is acetic anhydride or trifluoroacetic anhydride. Preferably, the amount of the base used is 2 to 10 times the molar amount of the amino group-terminated silane compound, and the amount of the acid anhydride used is 2 to 10 times the molar amount of the amino group-terminated silane compound.

Further, the temperature of the amidation and imidization reaction is room temperature.

Further, in the component (c), besides the silane coupling agent described in the above general formula (3), other types of silane coupling agents reported in the prior art may be included, 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 beneficial to improve the adhesion of the inductive resin composition to a substrate after thermal curing. The silane coupling agent that can be used in combination with the silane coupling agent of the general formula (3) may be selected from silane coupling agents 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-ureidopropyl triethoxy silane, better tackifying effect is shown.

Further, the mass ratio of the component (a) to the component (b) is 100: 1-50, 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, and 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, and the solvent may be one or more of an aprotic polar solvent, a ketone solvent, an ester solvent, an aromatic hydrocarbon solvent, and the like. The aprotic polar solvent may be one or more of N-methylpyrrolidone, γ -butyrolactone, tetrahydrofuran, dioxane, N-dimethylformamide, dimethyl sulfoxide, and the like. The ketone solvent may be one or more of methyl ethyl ketone, acetone, and the like. The ester solvent may be one or more of ethyl acetate, ethyl lactate, etc. The aromatic hydrocarbon solvent may be one or more of toluene, xylene, and the like.

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 components are uniformly mixed to obtain the photosensitive resin composition, the composition is subjected to spin coating on a 4-inch silicon wafer, and then soft baking is carried out for 3 minutes at 120 ℃ by using a heating table to obtain a photosensitive resin film with the thickness of 8-10 microns. The photosensitive resin film was placed in an inert gas oven, heat-treated under a nitrogen stream (oxygen content less than 20ppm), first heat-treated at 170 ℃ for 30 minutes, then heated to 320 ℃ over 1 hour, and treated at 320 ℃ for 1 hour to give an imidized (cured) resin cured film exhibiting excellent PCT test adhesion to a substrate. It can be seen from this that the resin cured film produced 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 shield, a surface protection, an interlayer dielectric or insulation of a semiconductor device, an insulation layer of an OLED device, etc., and the application thereof as a surface protection film or an interlayer insulation film of a semiconductor device is also within the protection scope of the present invention.

The photosensitive resin composition contains the silane coupling agent with double bonds and an imide structure, and the introduction of the silane coupling agent enables the photosensitive resin composition to have excellent adhesiveness with a base material after thermal curing at a high temperature of more than 300 ℃, thereby overcoming the defect of insufficient adhesiveness of the existing photosensitive heat-resistant resin.

Detailed Description

The photosensitive resin composition improves the viscosity after thermosetting by introducing a silane coupling agent with double bonds and an imide structure, 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 at the temperature of more than 300 ℃ in an air atmosphere.

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

In the general formula (1), R₁And R₂Each independently represents an organic group having 2 to 8 valences and having 2 or more carbon atoms; r₃And R₄Each 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 are each independently an integer of 0 to 2, p and q are each independently an integer of 0 to 2, wherein p + q>0。

In the general formula (2), R₅Represents an organic group having a valence of 4 to 8; r₆Represents an organic group having a valence of 2 to 10; r₇And R₈Represents a phenolic hydroxyl group, a sulfonic acid group or a thiol group, R₇And R₈Each of which may be a single group or a mixture of different groups; t represents a range of 3 to 1000; r and s represent an integer of 0 to 4.

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

Further, 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 therefore, permeation into the interface is suppressed, and therefore, the fluorine atom content is preferably 10% by weight or more to ensure the effect of preventing interfacial permeation, and the fluorine atom content is preferably 20% by weight or less to ensure solubility of the photosensitive resin in an alkaline solvent and adhesion of the cured film to a substrate after high-temperature treatment.

In the above general formula (1), R₁An organic group having 2 or more to 8 valences of 2 or more carbon atoms and an acid component, namely R₁Represents a residue of an acid having a valence of 2 to 8 and having 2 or more carbon atoms. R₁The residue of the 2-valent acid may be mentioned, and the 2-valent acid may be terephthalic acid, isophthalic acid, diphenyletherdicarboxylic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, or the like. R₁The acid having a valence of 3 may be a residue, and the acid having a valence of 3 may be a tricarboxylic acid such as trimellitic acid or 1,3, 5-trimellitic acid. R₁May be a residue of a 4-valent acid, and the 4-valent acid may be an aromatic tetracarboxylic acid such as 1,2,4, 5-pyromellitic 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 groups are changed to methyl or ethyl groups. In addition, R₁Can also be hydroxyphthalic acid,Hydroxyl trimellitic acid and the like have a hydroxyl group on the aromatic ring. R₁The acid residue may be a single acid residue, or 2 or more acid residues. In addition, from the viewpoint of solubility in an alkaline developer and photosensitivity, it is preferable that the residue of an acid having a hydroxyl group is contained in an amount of 50 mol% or more.

From the viewpoint of heat resistance, R is preferred₁Having an aromatic ring, more preferably R₁Is a 3-or 4-valent organic group having 6 to 30 carbon atoms.

In the above general formula (2), R₅The residue of the acid dianhydride is an organic group having a valence of 4 to 10, and among them, an organic group having 5 to 40 carbon atoms and having an aromatic ring or a cyclic aliphatic group is preferable. Specific examples of the acid dianhydride include 3,3 ', 4,4' -biphenyltetracarboxylic dianhydride, 2 ', 3, 3' -benzophenonetetracarboxylic dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, and 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride. They may be used alone or in combination of 2 or more.

R in the general formula (1)₂R in the general formula (2)₆An organic group having 2 to 8 valences and containing 2 or more carbon atoms, and a diamine component. From the viewpoint of heat resistance, R is preferred₂、R₆Having an aromatic ring. Specific examples of the diamine include diphenyl sulfide such as 3,4 '-diaminodiphenyl sulfide and 4,4' -diaminodiphenyl sulfide, gasoline, naphthalene diamine such as 1, 5-naphthalene diamine and 2, 6-naphthalene diamine, phenylenediamine such as m-phenylenediamine and p-phenylenediamine, diaminodiphenyl ether such as 3,4 '-diaminodiphenyl ether and 4,4' -diaminodiphenyl ether, diaminodiphenyl methane such as 3,4 '-diaminodiphenyl methane and 4,4' -diaminodiphenyl methane, diaminodiphenyl sulfone such as 3,4 '-diaminodiphenyl sulfone and 4,4' -diaminodiphenyl sulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (aminophenoxyphenyl) sulfone, and the like, Bis (aminohydroxyphenylhexafluoropropane), diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxydiaminopyrimidine, bis (aminohydroxyphenylhexafluoropropane),Diaminophenol, dihydroxybenzidine, diaminobenzoic acid, diaminoterephthalic acid, and the like. The diamine may be a diamine obtained by substituting at least a part of the hydrogens of the aromatic ring with an alkyl group or a halogen atom, or an aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, hexamethylenediamine, or the like.

R of the general formula (1)₃And R₄May be the same or different, R₃And R₄Each independently represents hydrogen or a 1-valent organic group having 1 to 20 carbon atoms. From the viewpoint of solubility in an alkaline developer and solution stability of the obtained photosensitive resin composition, R is preferably used₃And R₄10 to 90 mol% of each independently is hydrogen, and R is more preferably₃And R₄Each of which contains at least 1 or more C1-16 valent hydrocarbon groups and the others are hydrogen atoms.

In addition, in the general formula (1), l and m represent the number of carboxyl groups or ester groups, each independently represent an integer of 0 to 2, preferably 1 or 2. P and q in the general formula (1) independently represent an integer 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 high, and the contrast between the exposed area and the unexposed area cannot be obtained; when n > 1000, the solubility of the polymer in an alkaline developer is too low, and the exposed region cannot be dissolved, resulting in failure to form a desired image. From the viewpoint of solubility of the polymer in an alkaline developer, n is preferably 500 or less, more preferably 100 or less. In addition, from the viewpoint of improving the elongation, n is preferably 20 or more.

In the general formula (2), R₇And R₈Represents a phenolic hydroxyl group, a sulfonic group or a thiol group, and R and s each represents R₇、R₈The number of the cells. From the viewpoint of stability of the obtained photosensitive resin composition solution, r and s are preferably 4 or less. In addition, from the polymer in alkaline developer solubility, preferably r + s > 0.

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 the alkaline developer is too high to obtain a contrast between the exposed and unexposed regions. On the other hand, when t > 1000, the solubility of the polymer in an alkaline developer is too low, the exposed region 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, more preferably 100 or less.

Further, in order to improve the adhesion to the substrate, R of the general formula (1) may be used within a range not to lower the heat resistance₁And/or R₂And R of the general formula (2)₅And/or R₆Copolymerized with an aliphatic group having a siloxane structure. Specifically, the diamine component may be bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, or the like, in an amount of 1 to 20 mol% copolymerized.

In order to control the molecular weight (polymerization degree) of the polymer and to adjust the dissolution rate of the resin in an aqueous alkali solution, a monoamine or a monoanhydride, a monocarboxylic acid, a monoacid chloride compound, a monoactivated ester compound or the like may be selected as an end-capping agent for the polymer.

Monoamines used as the blocking agent are 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-aminonaphthalene, 2, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. They may be used alone or in combination of 2 or more.

The mono-acid anhydride, mono-carboxylic acid, mono-acid chloride compound, and mono-active ester used as the end-capping agent are preferably acid anhydrides such as phthalic anhydride, maleic anhydride, nadic acid, cyclohexane dicarboxylic anhydride, and 3-hydroxyphthalic anhydride; 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 monoacid chloride compounds obtained by acid-chlorinating their carboxyl groups; and a monoacid chloride compound obtained by acid chlorination of one carboxyl group of dicarboxylic acids such as terephthalic acid and phthalic acid; and an active ester obtained by reacting a monoacid chloride compound with N-hydroxybenzotriazole and N-hydroxy-5-norbornene-2, 3-dicarboximide. These can be used alone or in combination of 2 or more.

The content of the blocking agent such as monoamine, monoanhydride, monoacid chloride, monocarboxylic acid, or mono-active ester is preferably 5 to 50 mol% based on the total amine components. By reacting a plurality of blocking agents, a plurality of different terminal groups can 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 objective product is a polyamic acid ester, for example, tetracarboxylic dianhydride is reacted with an alcohol in triethylamine under low temperature conditions to obtain a diester, the remaining dicarboxylic acid is then acid-chlorinated, and the acid-chlorinated product is reacted with a diamine compound or a monoamine compound in a nitrogen atmosphere under the catalytic action of pyridine. When the objective product is a hydroxyl group-containing polyamide, for example, a bisaminophenol compound is condensed with a dicarboxylic acid or a monoamine compound under low temperature conditions in the presence of a dehydration condensation agent such as Dicyclohexylcarbodiimide (DCC); alternatively, dicarboxylic acid chloride is reacted with a bisaminophenol compound or a monoamine compound in the presence of a tertiary amine such as pyridine.

The polymer having a structure represented by the general formula (1) as a main component is produced by the above method, and then the polymer is put into a large amount of water or a mixed solution of water and methanol to precipitate a resin, and the resin is washed, filtered, dried and separated. By this operation, unreacted monomers, dimers, trimers or other oligomers in the polymer can be removed, and the film characteristics of the photosensitive resin composition after thermal curing can be improved.

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

The component (b) used in the present invention is a quinonediazide compound disclosed in patent CN102292675B, preferably an ester compound in which a sulfonic acid of quinonediazide is bonded to a polyhydroxy compound through an ester bond, and as the polyhydroxy compound, there are listed: 2, 6-dimethoxymethyl-4-tert-butylphenol, 2, 6-dimethoxy-p-cresol, 2, 6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol and the like, but are not limited thereto. Commercially available quinonediazide compounds (b) are preferred, for example, 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, 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 ] phenylene ] ethylidene ] 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-oxy-1-naphthalenesulfonic acid) (manufactured by Toyo Synthesis industries, Japan), preferably NT-300.

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 component (b) quinonediazide compound used 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). Further, an excessively high content of the component (b) leads to an increase in cost and a decrease in storage stability, and the amount of the quinonediazide compound used 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, and the silane coupling agent 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 a structure represented by the general formula (3) may be used alone or may be used in combination with other silane coupling agents. The silane coupling agent having a 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 effect of promoting adhesion of polyimide-based, polybenzoxazole-based, heat-resistant resins to substrates such as silicon, ceramics, and metals, and is hardly decomposed even after the imidization by heating at a high temperature of 300 ℃ or higher in nitrogen gas or after the imidization by heating in air, and therefore, the stability of the photosensitive resin composition after the heat treatment and the adhesion between a cured film formed after the heat treatment and the substrate can be greatly improved.

In the general formula (3), R₉、R₁₀、R₁₁Each independently may be hydrogen, C₁～C₁₀Alkyl or C₁～C₁₀Alkoxy of C₁～C₁₀The alkyl group of (b) may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc., preferably methyl or ethyl; c₁～C₁₀The alkoxy group of (b) may be methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, etc., preferably methoxy or ethoxy. R₉、R₁₀、R₁₁May be the same or different. For example R₉、R₁₀、R₁₁Can be simultaneously hydrogen and C₁～C₁₀Alkyl of (C) at the same time₁～C₁₀Or one of them may be hydrogen and the other two may be C₁～C₁₀Alkyl or C₁～C₁₀Or one of them C₁～C₁₀Alkyl of (a) and the other two are simultaneously hydrogen or C₁～C₁₀Or one of them may be C₁～C₁₀Alkoxy of (A) and two of (B) are simultaneously C₁～C₁₀Or alkyl or hydrogen of, or R₉、R₁₀、R₁₁All are different.

Preferably, R₉、R₁₀、R₁₁Are each independently C₁～C₁₀Alkyl or C₁～C₁₀Alkoxy of (i.e. R)₉、R₁₀、R₁₁Are all selected from C₁～C₁₀Alkyl or C₁～C₁₀More preferably, R₉、R₁₀、R₁₁Are each independently C₁～C₄Alkyl or C₁～C₄Most preferably, R₉、R₁₀、R₁₁Each independently is methoxy or ethoxy. R₉、R₁₀、R₁₁May be the same or different.

In the general formula (3), R₁₂、R₁₃Are each independently hydrogen or C₁～C₁₀Alkyl of (C)₁～C₁₀The alkyl group of (b) may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc., preferably methyl or ethyl. R₁₂、R₁₃May be the same or different. Preferably, R₁₂、R₁₃Are all hydrogen.

In certain embodiments, the silane coupling agent of formula (3) may be of the structure: r₉、R₁₀、R₁₁Are all methoxy radicals, R₁₂、R₁₃Are all hydrogen; r₉、R₁₀、R₁₁Are all ethoxy, R₁₂、R₁₃Are all hydrogen; r₉、R₁₀、R₁₁Are all pentyloxy radicals, R₁₂、R₁₃Are all hydrogen; r₉、R₁₀、R₁₁Are each octyloxy, R₁₂、R₁₃Are all hydrogen; r₉、R₁₀、R₁₁Are each methyl, R₁₂、R₁₃Are all hydrogen; r₉、R₁₀、R₁₁Are all ethyl radicals, R₁₂、R₁₃Are all hydrogen; r₉、R₁₀、R₁₁Are all butyl, R₁₂、R₁₃Are all hydrogen；R₉、R₁₀、R₁₁Are all heptyl, R₁₂、R₁₃Are all hydrogen; r₉、R₁₀、R₁₁Are each hydrogen, R₁₂、R₁₃Are all hydrogen; r₉、R₁₀Are all methoxy radicals, R₁₁Is methyl, R₁₂、R₁₃Are all hydrogen; r₉、R₁₀Are all ethoxy, R₁₁Is methyl, R₁₂、R₁₃Are all hydrogen; r₉、R₁₀、R₁₁Are all methoxy radicals, R₁₂、R₁₃Are both methyl; r₉、R₁₀、R₁₁Are all ethoxy, R₁₂、R₁₃Are both propyl; r₉、R₁₀、R₁₁Are all pentyloxy radicals, R₁₂Is methyl, R₁₃Is hydrogen; r₉、R₁₀Are all methoxy radicals, R₁₁Is methyl, R₁₂Is hydrogen, R₁₃Is ethyl. These silane coupling agents each have an excellent effect of improving the adhesion between the heat-resistant resin and the substrate described by the general formula (1) wherein R₉、R₁₀、R₁₁Are each independently C₁～C₁₀Alkyl or C₁～C₁₀Alkoxy radical of (2), R₁₂、R₁₃The silane coupling agent has better performance when all the silane coupling agents are hydrogen.

The silane coupling agent of the general formula (3) is prepared as follows:

1) the itaconic anhydride compound represented by the formula (4) and the silane compound represented by the formula (5) having an amino group as a terminal group are subjected to an amidation reaction to form an amic acid.

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

In the formulae (4) and (5), R₉、R₁₀、R₁₁、R₁₂、R₁₃The definitions of (a) and (b) are all consistent with the foregoing.

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

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

Further, the product of the amidation reaction is an amic acid compound (structural formula, R is shown below)₉、R₁₀、R₁₁、R₁₂、R₁₃The definitions of which are the same as those described above), the silane coupling agent represented by the above general formula (3) can be obtained by directly subjecting the reaction solution to imidization without extracting the product after the amidation reaction. The imidization is preferably chemical imidization. In the prior art, chemical imidization is reported in many cases, and chemical imidization refers to a process of reacting intramolecular carboxyl groups and amide groups under the action of acid anhydride and alkali to form cyclic imines. The acid anhydride used may be any acid anhydride reported in the art that can be used for imidization, such as acetic anhydride, trifluoroacetic anhydride, etc., preferably acetic anhydride, and the base used may be any base reported in the art that can be used for imidization, such as pyridine, triethylamine, diisopropylethylamine, etc., preferably pyridine.

Further, in the 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, or 10 times the molar amount of the silane compound having an amino group as a terminal group; the amount of acetic anhydride 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, or 10 times the molar amount of the silane compound whose terminal group is an amino group.

Further, it was confirmed through 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 or both of 3- (triethoxysilylthio) propyltrimethoxysilane and γ -ureidopropyltriethoxysilane, and the effect is superior to that of the silane coupling agent of the general formula (3) alone. When these silane coupling agents are used in combination, their proportions are not particularly limited, and for example, the silane coupling agent of the general formula (3), (triethoxysilylthio) propyltrimethoxysilane (if any), and γ -ureidopropyltriethoxysilane (if any) may be mixed in a mass ratio range of 1:0.1 to 10.

In the photosensitive resin composition, the silane coupling agent is added, so that the adhesive force between the resin composition and a base material is greatly improved, the tackifying effect is poor when the content is too low, and the other performances of the composition are reduced when the content is too high. In order to ensure adhesion to a substrate after high-temperature treatment, the amount of component (c) is preferably 0.1 part by weight or more per 100 parts by weight of component (a), and when the amount is more than this, a significant adhesion-promoting effect is exhibited, more preferably 0.25 part by weight or more, and still more preferably 0.5 part by weight or more. In addition, in order to ensure the 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, the 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 dimethyl sulfoxide; ketones such as methyl ethyl ketone and acetone; esters such as ethyl acetate and ethyl lactate; and aromatic hydrocarbons such as toluene and xylene. The solvent can be selected from 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 method for producing the photosensitive resin composition is described below:

for example, a photosensitive resin composition can be obtained by dissolving a component (a) composed mainly of the general formula (1) or/and the general formula (2) in a solvent (d) in a three-necked flask, adding the component (b) to the quinonediazide compound-based photosensitizer after the component (a) is completely dissolved, continuing stirring until the quinonediazide compound-based photosensitizer is completely dissolved, adding the silane coupling agent of the component (c), and finally subjecting the mixture to a filtration operation. The viscosity of the composition is 1 to 5000 mPas, preferably 500 to 3000 mPas, and 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 for 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 such as: 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, doctor blading, and the like. Among them, the coating film thickness varies depending on the coating method, the rotation speed, the viscosity, the concentration of the composition component, and the like. In the present invention, a 4-inch silicon wafer is preferably used as a substrate of the coating film, and the coating is preferably performed by a spin coating method, wherein the thickness of the resin film on the silicon wafer is controlled to be 2 to 15 μm.

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 is preferably carried out at a temperature in the range of 50 ℃ to 150 ℃ for 1 minute to several hours. The thickness of the photosensitive resin film was measured after cooling to room temperature.

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

After the exposure, the exposed region is removed by using an alkaline developer to form a pattern. Common developing solutions are: an aqueous solution of tetramethylammonium hydroxide (TMAH), an aqueous solution of a compound exhibiting alkalinity such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, or the like. Further, one or more other substances, such as: polar solvents such as N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide; 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 the development, the development is preferably rinsed with water, and the development may be rinsed by adding ethanol, isopropyl alcohol, ethyl lactate, propylene glycol monomethyl ether acetate, or the like to water. For example, positive photoresist developer and positive photoresist rinse are poured into two glass petri dishes, respectively. The temperature of the developing solution was controlled to 25 ℃. + -. 1 ℃, and the exposed resin film was immersed in the developing solution, and then timing was started. And after the exposure area completely exposes the silicon wafer substrate, ending the development, stopping timing, and recording the time required by the whole process.

Finally, the resin pattern obtained after development is imidized (thermal imidization) at a temperature of 200 to 500 ℃ to be converted into a cured film. In the heat treatment, the temperature is usually raised stepwise, and the temperature is maintained at different temperatures for a certain period of time or continuously raised in a certain temperature range. Examples thereof include a method of performing heat treatment at 130 ℃,200 ℃ and 350 ℃ for 30 minutes, and a method of linearly raising the temperature from room temperature to 400 ℃ over 2 hours.

The invention provides a photosensitive resin composition having excellent adhesiveness with a substrate. The cured film formed from the composition can be used for a passivation film of a semiconductor, surface protection of a semiconductor device, a multilayer wiring (RDL) insulating layer in chip packaging, an insulating layer of an OLED device, and the like.

The following examples are given to illustrate the present invention and to assist those of ordinary skill in the art in more complete understanding, but the present invention is not limited to these examples. The photosensitive resin compositions in the examples were evaluated by the following methods.

(1) Viscosity measurement

A sample of 2ml of the photosensitive resin composition was placed in a sample cell of a rotational viscometer (BROOKFIELD DV2T RV), and a viscosity test was performed at 25 ℃. + -. 0.1 ℃ with a suitable range of measurement.

(2) Adhesion peel test of cured film (imide resin film) to substrate

A photosensitive resin composition is coated on a 4-inch silicon wafer, and then soft-baking is carried out for 3 minutes at 120 ℃ by using a heating table, so that a photosensitive resin film with the film thickness of 8-10 mu m after soft-baking is obtained. Then, the prepared photosensitive resin film was placed in an inert gas oven and heat-treated under a nitrogen flow (oxygen content less than 20 ppm). Firstly, heat treatment is carried out at 170 ℃ for 30 minutes, then the temperature is raised to 320 ℃ for 1 hour, and the curing film is obtained after the treatment at 320 ℃ for 1 hour, and a thickness test of the film is carried out by utilizing a step profiler (KLA Tencor P-7), and the thickness of the film is controlled to be 5 um.

The cured film was scribed with 10 lines and 10 columns of squares using a scriber (model, BYK-Gardner A-5125), a peel test was performed with an adhesive tape (special transparent 3M tape) in accordance with the national standard GB/T9286-.

The cured film was scribed in 10 lines by 10 columns by a scriber (model, BYK-Gardner A-5125) in the same manner as described above, and the cured film scribed in the squares was subjected to a PCT test (121 ℃ C., 2 atm saturated steam; Dongguan Hong scientific PCT-30) for 200 hours. After the completion of the PCT test, a peel test was performed using an adhesive tape in the same manner as described above, and the number of cells peeled off was recorded as the peeling state after PCT.

The number of cells peeled off in the adhesion peel test was considered to be good when the number was less than 10, and poor when the number was 10 or more.

Synthesis example 1

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

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

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

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

Synthesis example 2

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

32.96g (0.09mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF), 2.18g (0.02mol) of 4-aminophenol, 15.82g (0.2mol) of pyridine and 100g of N-methylpyrrolidone (NMP) were charged in this order into a 500mL three-necked flask equipped with a stirrer, a dropping funnel and a thermometer under a nitrogen stream, and after sufficiently dissolving, the temperature of the solution was cooled to-15 ℃. 29.51g (0.10mol) of 4, 4-diphenyletherdiformylchloride were dissolved in 50g of NMP to prepare a solution, and the solution was dropped into the flask via a dropping funnel while controlling the temperature of the reaction mass at 0 ℃ or lower. After the dropwise addition is finished, the mixture is continuously stirred and reacts for 6 hours at the temperature of between 10 ℃ below zero and 15 ℃ below zero. After the reaction, the reaction mixture was poured into 3L of a 10 wt% aqueous methanol solution to precipitate a polymer, thereby obtaining a white precipitate. Filtering, washing with deionized water for three times, placing in a vacuum oven, and drying at 50 deg.C for 72hr to obtain polymer, i.e. polybenzoxazole resin A-2.

The molecular weight of polybenzoxazole resin A-2 was measured by gel permeation chromatography (GPC, Shimadzu LC-20AD) in terms of standard polystyrene, and the eluent was N-methylpyrrolidone, and the column oven temperature was 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) 1.3 to 1.6 ten thousand and a molecular weight distribution in the range of 1.3 to 1.7.

Synthesis example 3

Synthesis of silane coupling agent B-1:

a500 mL three-necked flask equipped with a stirrer and a thermometer was charged with 17.93g (0.1mol, Japan shin-Etsu chemical KBM-903) of (3-aminopropyl) trimethoxysilane and 150m L g of N, N-dimethylacetamide in this order, and stirring was started. Itaconic anhydride (11.22 g, 0.1mol) was weighed out and dissolved in 100mL of N, N-dimethylacetamide. And (3) placing the 500mL three-neck flask into an ice water bath, slowly dropwise adding the itaconic anhydride solution while stirring, and controlling the temperature of the reaction material to be lower than 10 ℃. After the addition was complete, the ice-water bath was removed and the reaction was continued with stirring at room temperature for 20 hr. After the reaction was completed, 15.82g (0.2mol) of pyridine was added to the reaction system, and after stirring the mixture uniformly, 20.42g (0.2mol) of acetic anhydride was slowly added thereto to carry out a reaction at room temperature for 20 hours. After the reaction, the reaction mixture was evaporated under reduced pressure to remove the solvent, acetic acid formed, residual acetic anhydride and pyridine and other front fractions, thereby obtaining a 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 R₉Is methoxy, R₁₀Is methoxy, R₁₁Is methoxy, R₁₂Is hydrogen, R₁₃Is hydrogen. The nuclear magnetic information of the silane coupling agent B-1 is as follows:

¹HNMR(CDCl₃)：0.58(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:

a500 mL three-necked flask equipped with a stirrer and a thermometer was charged with 22.14 g (0.1mol, KBE-903, Japan shin-Etsu chemical) of (3-aminopropyl) triethoxysilane, and 150mL of N, N-dimethylacetamide in this order, and stirring was turned on. Itaconic anhydride (11.22 g, 0.1mol) was weighed out and dissolved in 100mL of N, N-dimethylacetamide. And (3) placing the 500mL three-neck flask into an ice water bath, slowly dropwise adding the itaconic anhydride solution while stirring, and controlling the temperature of the reaction material to be lower than 10 ℃. After the addition was complete, the ice-water bath was removed and the reaction was continued at room temperature for 20 hr. After completion of the reaction, 23.73g (0.3mol) of pyridine was added to the reaction system, and after stirring the mixture uniformly, 30.63g (0.3mol) of acetic anhydride was slowly added thereto to conduct a reaction at room temperature for 20 hours. After the reaction, the reaction mixture was evaporated under reduced pressure to remove the solvent, acetic acid formed, residual acetic anhydride and pyridine and other front fractions, thereby obtaining a 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 R₉Is ethoxy, R₁₀Is ethoxy, R₁₁Is ethoxy, R₁₂Is hydrogen, R₁₃Is hydrogen. The nuclear magnetic information of the silane coupling agent B-2 is as follows:

¹HNMR(CDCl₃)：0.58(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:

a500 mL three-necked flask equipped with a stirrer and a thermometer was charged with 16.33g (0.1mol, King-Monte chemical KH-662, Nanjing) of 3-aminopropylmethyldimethoxysilane and 150Ml of N, N-dimethylacetamide in this order, and stirring was started. Itaconic anhydride (11.22 g, 0.1mol) was weighed out and dissolved in 100mL of N, N-dimethylacetamide. And (3) placing the 500mL three-neck flask into an ice water bath, slowly dropwise adding the itaconic anhydride solution while stirring, and controlling the temperature of the reaction material to be lower than 10 ℃. After completion of the dropwise addition, the ice-water bath was removed, and the reaction was continued at room temperature for 20 hr. After completion of the reaction, 15.82g (0.2mol) of pyridine was added to the reaction system, and after stirring the mixture uniformly, 42.01g (0.2mol) of trifluoroacetic anhydride was slowly added thereto to conduct a reaction at room temperature for 20 hours. After the reaction, the reaction mixture was evaporated under reduced pressure to remove the solvent, acetic acid formed, residual acetic anhydride and pyridine and other front fractions, thereby obtaining a 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 R₉Is methyl, R₁₀Is methoxy, R₁₁Is methoxy, R₁₂Is hydrogen, R₁₃Is hydrogen. The nuclear magnetic information of the silane coupling agent B-3 is as follows:

¹HNMR(CDCl₃)：0.14(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)。