阅读说明：本技术 一种正型感光性聚酰胺类化合物及其应用 (Positive photosensitive polyamide compound and application thereof ) 是由 王治国 邵光强 白晨 于 2021-01-20 设计创作，主要内容包括：本发明公开了一种正型感光性聚酰胺类化合物,由二酐和二胺聚合而成,二酐为羧酸二酐,二胺的结构如下：本发明的有益效果是：本发明正型感光性聚酰胺类化合物中含有可形成侧链噁唑的侧链单元,可与重氮萘醌化合物制成感光树脂组合物,该感光性树脂组合物制备的感光性树脂膜具有残膜率高、收缩率低且感光度、解像力优异的特性,从而可以制得稳定的高分辨率图案,符合制备上述电子元件的要求。(The invention discloses a positive photosensitive polyamide compound, which is polymerized by dianhydride and diamine, wherein the dianhydride is carboxylic acid dianhydride, and the structure of the diamine is as follows:)

1. A positive photosensitive polyamide compound obtained by polymerizing dianhydride and diamine, characterized in that,

the dianhydride is carboxylic acid dianhydride;

the diamine has a structure shown as formula a:

wherein R is₁Selected from-F or-CF₃，R₂Is selected from-OH or-SH.

2. The positive photosensitive polyamide compound according to claim 1, wherein the dianhydride is pyromellitic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, 3',4,4' -benzophenonetetracarboxylic dianhydride, 3',4,4' -diphenyl ether tetracarboxylic dianhydride, 3',4,4' -diphenylsulfonetetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoroisopropylidene dianhydride, 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1, 2-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-tetramethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, or mixtures thereof, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, 3, 4-dicarboxy-1, 2,3, 4-tetrahydroxy-1-naphthalenesuccinic dianhydride, 5- (2, 5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic dianhydride, 2,3, 5-tricarboxy-2-cyclopentaneacetic dianhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 2,3,4, 5-tetrahydrofurantetracarboxylic dianhydride or 3,5, 6-tricarboxy-2-norbornaneacetic dianhydride.

3. The positive photosensitive polyamide compound according to claim 1 or 2, wherein the formula a has a structure according to formula a1-a 5:

4. the positive photosensitive polyamide compound according to claim 3, wherein the diamine is selected from p-phenylenediamine, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, bis (3-amino-4-hydroxyphenyl) fluorene, 3, 5-diaminobenzoic acid, 3-carboxy-4, 4 '-diaminodiphenyl ether, 3-sulfonic acid-4, 4' -diaminodiphenyl ether, p-phenylenediamine, Dithiohydroxy-phenylenediamine, 3,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl ether, 3,4 '-diaminodiphenyl methane, 4' -diaminodiphenyl methane, 3,4 '-diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfone, 3,4 '-diaminodiphenyl sulfide, 4' -diaminodiphenyl sulfide, 1, 4-bis (4-aminophenoxy) benzene, m-phenylenediamine, 1, 5-naphthalenediamine, 2, 6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl } ether, 1, 4-bis (4-aminophenoxy) benzene, bis (4-aminophenoxy) phenyl } ether, bis (4-aminophenoxy) benzene, bis (4-aminophenoxy) phenyl, bis (4, 2,2 '-dimethyl-4, 4' -diaminobiphenyl, 2 '-diethyl-4, 4' -diaminobiphenyl, 3,3 '-dimethyl-4, 4' -diaminobiphenyl, 3,3 '-diethyl-4, 4' -diaminobiphenyl, 2',3,3' -tetramethyl-4, 4 '-diaminobiphenyl, 3,3',4,4 '-tetramethyl-4, 4' -diaminobiphenyl, 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 2 '-bis [3- (4-amino-benzamido) -4-hydroxyphenyl ] hexafluoropropane, 3,3' -dihydroxy-bis [4- (4-amino-benzamido) ] biphenyl or alkyl or halogen atom-substituted bis [4- (4-amino-benzamido) ] biphenyl And a compound obtained by substituting a part of hydrogen atoms of the aromatic ring.

5. A positive photosensitive composition is characterized by comprising the following components in parts by weight: 5 to 15 parts of the positive photosensitive polyamide compound as claimed in any one of claims 1 to 4, 0.4 to 1.5 parts of a diazonaphthoquinone compound, and 50 to 100 parts of a solvent.

6. The positive photosensitive composition according to claim 5, wherein the diazonaphthoquinone compound is selected from a1, 2-naphthoquinone-2 diazo-4-sulfonate compound or a1, 2-naphthoquinone-2 diazo-5-sulfonate compound, and an esterification precursor of the sulfonate compound is a low molecular weight polyhydric phenol compound.

7. The positive photosensitive composition according to claim 5, wherein the solvent is one or a combination of γ -butyrolactone, N-methyl pyrrolidone, or propylene glycol monomethyl ether.

8. A cured film obtained by curing a photosensitive varnish prepared from the positive photosensitive composition according to claims 5 to 7.

9. An electronic component comprising the cured film according to claim 8.

Technical Field

The invention relates to the technical field of semiconductors, in particular to a positive photosensitive polyamide compound and application thereof.

Background

Cured films obtained by curing photosensitive resin compositions containing polyimide and polybenzoxazole are widely used as insulating films, protective films, planarization films, and the like of semiconductor devices and display devices. In particular, in a display device, for example, an insulating layer of an organic EL display, a black matrix of a liquid crystal display, or the like.

Positive photosensitive polyimide is favored by researchers for its low cost and environmental friendliness. A positive photosensitive resin obtained by mixing a polyamic acid and a diazonaphthoquinone compound as a dissolution inhibitor is required to have an effect that a difference in solubility between an exposed portion and an unexposed portion is almost sufficient to produce a high-resolution pattern, and thus a film made of the positive photosensitive resin is required to have characteristics of a high residual film ratio, a low shrinkage ratio, and excellent sensitivity and resolution.

Disclosure of Invention

In view of the above problems, the present invention provides a positive photosensitive polyamide compound obtained by polymerizing a dianhydride and a diamine, wherein the dianhydride is a carboxylic acid dianhydride and the diamine has a structure represented by the formula a:

wherein R is₁Selected from-F or-CF₃，R₂Is selected from-OH or-SH.

Further, formula a has a structure as shown in formula a1-a 5:

the diamine used in the present invention may be selected from the following, in addition to the diamine having the structure shown in formula a: p-phenylenediamine, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, bis (3-amino-4-hydroxyphenyl) fluorene, 3, 5-diaminobenzoic acid, 3-carboxy-4, 4 '-diaminodiphenyl ether, 3-sulfonic acid-4, 4' -diaminodiphenyl ether, dithio-hydroxyanilines, 3,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl ether, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) ether, 3,4' -diaminodiphenylmethane, 4' -diaminodiphenylmethane, 3,4' -diaminodiphenylsulfone, 4' -diaminodiphenylsulfone, 3,4' -diaminodiphenylsulfide, 4' -diaminodiphenylsulfide, 1, 4-bis (4-aminophenoxy) benzene, m-phenylenediamine, 1, 5-naphthalenediamine, 2, 6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl } ether, 1, 4-bis (4-aminophenoxy) benzene, 2' -dimethyl-4, 4' -diaminobiphenyl, 2' -diethyl-4, 4 '-diaminobiphenyl, 3' -dimethyl-4, 4 '-diaminobiphenyl, 3' -diethyl-4, 4 '-diaminobiphenyl, 2',3,3' -tetramethyl-4, 4' -diaminobiphenyl, 3',4,4 '-tetramethyl-4, 4' -diaminobiphenyl, 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 2 '-bis [3- (4-amino-benzamido) -4-hydroxyphenyl ] hexafluoropropane, 3' -dihydroxy-bis [4- (4-amino-benzamido) ] biphenyl, or a compound obtained by substituting a part of hydrogen atoms of the above aromatic ring with an alkyl group or a halogen atom.

The carboxylic dianhydride of the present invention is specifically selected from pyromellitic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, 3',4,4' -benzophenonetetracarboxylic dianhydride, 3',4,4' -diphenyl ether tetracarboxylic dianhydride, 3',4,4' -diphenylsulfonetetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoroisopropylidene dianhydride, 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1, 2-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-tetramethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, 3, 4-dicarboxy-1, 2,3, 4-tetrahydroxy-1-naphthalene succinic dianhydride, 5- (2, 5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic dianhydride, 2,3, 5-tricarboxyl-2-cyclopentaneacetic dianhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 2,3,4, 5-tetrahydrofurantetracarboxylic dianhydride or 3,5, 6-tricarboxyl-2-norbornaneacetic dianhydride.

The positive photosensitive polyamide-based compound can be specifically classified into three types of polyamides according to the combination of different dianhydrides and diamines: polyamic acids, polyamic acid esters, and polyimides. The preparation methods of different types of polyamides are slightly different, and are specifically as follows:

the polyamic acid can be prepared by a conventional method including the steps of: firstly, dissolving a mixture containing dianhydride a and diamine B in a solvent, carrying out polymerization reaction at the temperature of 0-100 ℃ for 1-24h, and directly adding a diazonaphthoquinone compound B to prepare a photoresist after the reaction is finished; the solvent may be distilled off under reduced pressure to obtain a polyamic acid solid, or the reaction system may be poured into a large amount of a poor solvent to dry the precipitate for use; the solvent is one or a mixture of more of N-methyl-2-pyrrolidone, gamma-butyrolactone, N-dimethylacetamide, N-dimethylformamide, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol methyl ethyl ether, ethylene glycol dimethyl ether and diethylene glycol monomethyl ether ethyl ester, and the dosage of the solvent is 5-80 times of the weight of the product.

The preparation method of the polyamic acid ester comprises the following steps: heating in the presence of an esterifying agent, during which the carboxylic acid functions in the polyamic acid are converted to carboxylate groups by esterification; the esterification reaction can be further carried out on the polyamic acid solution, wherein the esterification rate of the amic acid is 1-100%, the temperature of the esterification reaction is 0-100 ℃, the reaction time is 1-120h, the esterification reagent can be alcohol compounds such as methanol and ethanol, and can also be acetal compounds such as DMFDMA and DMADEA, and the molar ratio of the product to the esterification reagent is 1: 1-10.

The preparation method of the polyimide comprises the following steps: heating the polyamic acid obtained by the above method in the presence of a catalyst, during which the amic acid functional group in the polyamic acid is converted to an imide group by imidization, which can be further reacted in the above polyamic acid solution; wherein the imidization rate of the amic acid is 30 to 100%, the temperature of the imidization reaction is 0 to 200 ℃, preferably 20 to 60 ℃, and the reaction time is 1 to 120 hours, preferably 2 to 30 hours.

The polyamic acid, polyamic acid ester, and polyimide compound may be a terminal-modified polymer that is adjusted by a molecular weight adjuster. By using the terminal-modified polymer, the molecular weight of the polymer is controlled. The end-modified polymer can be prepared by adding a molecular weight modifier c to the polymerization reaction for preparing the polyamic acid. Such molecular weight regulators c include, but are not limited to: (1) monobasic acid anhydrides such as maleic anhydride, phthalic anhydride or succinic anhydride; (2) monoamine compounds such as aniline, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, 3-aminophenol, p-aminophenol and the like; (3) monoisocyanate-based compounds such as phenyl isocyanate or naphthyl isocyanate.

The positive photosensitive polyamide compound can be used for preparing a positive photosensitive composition, and the composition comprises the following components in parts by weight: 5-15 parts of positive photosensitive polyamide compound, 0.4-1.5 parts of diazonaphthoquinone compound and 50-100 parts of solvent.

The diazonaphthoquinone compound is selected from 1, 2-naphthoquinone-2 diazo-4-sulfonate compound or 1, 2-naphthoquinone-2 diazo-5-sulfonate compound, and refers to an ester formed by naphthoquinone diazide sulfonyl chloride and a compound having a hydroxyl group, wherein the compound having a hydroxyl group is bisphenol A, triphenol A, 4-isopropylidenediphenol, 1, 1-bis 4- (hydroxyphenyl) cyclohexane, 4' -dihydroxyphenylsulfone, 4-hexafluoroisopropylidenediphenol, 4' -trihydroxytriphenylmethane, 1,1, 1-tris 4- (hydroxyphenyl) ethane, 4' - [1- [4- [1- (4-hydroxyphenyl) 1-methylethyl ] phenyl ] ethylidene ] bisphenol, One of phenol compounds such as methyl 3,4, 5-trihydroxybenzoate, propyl 3,4, 5-trihydroxybenzoate, isoamyl 3,4, 5-trihydroxybenzoate, 2-ethylbutyl 3,4, 5-trihydroxybenzoate, 2, 4-dihydroxybenzophenone, 2,3, 4-trihydroxybenzophenone, 2', 4,4' -tetrahydroxybenzophenone, 2,3,4,4' -tetrahydroxybenzophenone, and 2,3,4,2', 4' -pentahydroxybenzophenone. The solvent is one or more of gamma-butyrolactone, N-methyl pyrrolidone or propylene glycol monomethyl ether.

The preparation method of the positive photosensitive composition comprises the following steps: mixing the positive photosensitive polyamide compound and a solvent to prepare varnish, adding the diazonaphthoquinone compound, and uniformly mixing.

The positive photosensitive resin composition of the present invention may contain a compound having an alkoxymethyl group, and since the alkoxymethyl group undergoes a crosslinking reaction in a temperature range of 150 ℃ or higher, a cured film having excellent mechanical properties can be obtained by crosslinking through the post-development heat treatment described below, and a compound having 2 or more alkoxymethyl groups is preferable, and a compound having 4 or more alkoxymethyl groups is more preferable.

If necessary, in order to increase the coating performance of the positive photosensitive composition and the substrate, a surfactant, a lipid such as ethyl lactate and propylene glycol monomethyl ether acetate, an alcohol such as ethanol, a ketone such as cyclohexanone and methyl isobutyl ketone, and an ether compound such as tetrahydrofuran and dioxane may be mixed.

In order to improve the adhesion to a substrate such as a silicon substrate, a silane coupling agent, a titanium chelating agent, or the like may be added to the positive photosensitive composition in an amount of 0.5 to 10% by weight, or the substrate may be pretreated with such a chemical solution; when added to the positive photosensitive composition, the amount of the silane coupling agent such as methacryloxydimethoxysilane or 3-aminopropyltrimethoxysilane, titanium chelating agent or aluminum chelating agent added is 0.5 to 10 wt% based on the polymer in the photosensitive resin composition.

In the treatment of a substrate, the coupling agent is dissolved in a solvent such as isopropyl alcohol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc., in an amount of 0.5 to 20 wt% to prepare a solution, and the solution is subjected to surface treatment by a method such as spin coating, dipping, spraying, steam treatment, etc. Thereafter, the substrate is reacted with the coupling agent at a temperature of 50 to 300 ℃ depending on the case.

The positive photosensitive composition of the present invention can be used for preparing a cured film: the photosensitive resin composition varnish is applied to a substrate, and as the substrate, a silicon plate, ceramics, gallium arsenide, soda-lime glass, quartz glass, or the like can be used, but is by no means limited thereto; as the coating method, there are methods such as spin coating, spray coating, roll coating and the like by a spin coater; the thickness of the coating layer varies depending on the coating method, the concentration of the solid content of the composition, the viscosity, and the like, and is usually 0.1 to 10 μm after drying; drying the substrate coated with the photosensitive resin composition varnish to obtain a photosensitive resin composition film; drying with oven, hot plate, infrared ray, etc. at 50-180 deg.C for 1 min to several hours; a mask having a desired pattern is placed on the photosensitive resin composition film, and the film is exposed to chemical radiation such as ultraviolet rays, visible light, electron beams, and X-rays, and the i-line (365nm), the h-line (405nm), and the g-line (436nm) of a mercury lamp can be used.

In order to form a pattern of the resin, the exposed portion is removed by using a developer after exposure. As the developer, an aqueous solution of tetramethylammonium hydroxide, an aqueous solution of compounds exhibiting alkalinity such as diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine and hexamethylenediamine, is preferably used. In addition, depending on the case, polar solvents such as N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, γ -butyrolactone, and dimethylacrylamide, alcohols such as methanol, ethanol, and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone, and the like may be added to these alkaline aqueous solutions, either alone or in combination, followed by rinsing with water after development, and rinsing with water, and alcohols such as ethanol and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and the like may be added to water.

After the development, the resin film is heated to 180-500 ℃ to be converted into the resin film, and the heating treatment can be carried out at a selected temperature, at a temperature which is raised in stages, or in a temperature range which is selected and continuously raised for 5 minutes to 5 hours. For example, the heat treatment is carried out at 130 ℃, 200 ℃ and 350 ℃ for 30 minutes, or the linear temperature rise is carried out from room temperature to 250 ℃ for 1 hour, or to 400 ℃ for 2 hours.

The resin film formed from the photosensitive resin composition of the present invention can be used as a passivation film for a semiconductor, a protective film for a semiconductor element, an insulating layer in a display device having an organic electroluminescent element or the like mounted thereon, or the like.

The insulating layer formed in a display device using the composition of the present invention relates to a display device including a first electrode formed on a substrate and a second electrode provided so as to face the first electrode, and is particularly suitable for use in, for example, LCDs, ECDs, ELDs, display devices using organic electroluminescent elements (organic electroluminescent devices), and the like. The organic electroluminescent device is a display device comprising an organic electroluminescent element including a first electrode formed on a substrate, a thin film layer formed on the first electrode and including a light-emitting layer made of at least an organic compound, and a second electrode formed on the thin film layer.

The invention has the beneficial effects that: the positive photosensitive polyamide compound contains a side chain unit capable of forming side chain oxazole, and can be prepared into a photosensitive resin composition with a diazonaphthoquinone compound.

Detailed Description

The present invention is described below with reference to examples, which are provided for illustration only and are not intended to limit the scope of the present invention.

Preparation of compounds

1. Synthesis of Compound a1

The reaction process is as follows:

(1) synthesis of intermediate Compound a1-1

Putting 2-hydroxy 3-amino-1, 5-dinitrobenzene (19.91g, 100 mmol), 1, 2-propylene oxide (8.71, 150 mmol) and 200mL of ethyl acetate into a 500mL three-neck round-bottom flask, cooling the reaction system to-10-0 ℃, starting to dropwise add a solution of p-fluorobenzoyl chloride (17.44g, 110 mmol) and 100mL of ethyl acetate into the reaction system, reacting at-10-0 ℃ for 5h after 2h, heating to 20-30 ℃, stirring and keeping the temperature for 0.5h, filtering, crystallizing a filter cake by using a tetrahydrofuran/methanol (2:3) mixed solvent to obtain 29g of yellow solid, obtaining yield 90%, and performing high-resolution mass spectrometry on the product, wherein M/Z is 321.0355 and is confirmed to be a1-1 target product;

(2) synthesis of Compound a1

The obtained compound b-1-1a (16.06g, 50 mmol), 10% palladium on carbon (1.6g, 70% water, 30% solid content) and 400g of tetrahydrofuran were charged into a 1L autoclave, the autoclave was sealed, and after replacement with hydrogen gas for 3 to 5 times, the pressure of hydrogen gas was increased to 1.0 to 1.5MPa, and the reaction was carried out at 50 to 60 ℃ with stirring. After the reaction was completed, the catalyst was removed through a membrane, and then the filtrate was desolventized, and the obtained solid was added with a mixed solvent of 40g of ethanol and 40g of ethyl acetate, and stirred for 30 minutes, filtered, and dried to obtain a solid compound a1 in 74.5% yield.

High resolution mass spectrum, ESI source, positive ion mode, theoretical value 261.0914, test value 261.0886 of this compound a 1. Elemental analysis (C13H12N3O2F), theoretical value C: 59.77, H: 4.63, N: 16.08, O: 12.25, F: 7.27; found value C: 59.77, H: 4.62, N: 16.07, O: 12.26, F: 7.28.

the compounds a2-a5 can be synthesized by respectively using dinitro compounds and p-fluorobenzoyl chloride or p-trifluoromethylbenzoyl chloride corresponding to respective parent compounds according to a synthesis route 1, amide synthesis is firstly carried out, and then hydrogenation reduction is carried out to obtain target products, and the high resolution mass spectrum results, the element analysis results, the synthesis yield and the structural formula of the dinitro compounds used for synthesis of the corresponding target compounds are shown in the following table 1.

TABLE 1 Mass Spectrometry, elemental analysis data yield, and raw Material Structure data for Compounds a2-a5

2. Synthesis of Positive photosensitive Polyamide Compound

Synthesis of Positive photosensitive polyimide b1

23.498g (0.09 mol) of diamine compound a1, 2.182g (0.02 mol) of 3-aminophenol, 31.001g (0.1 mol) of 3,3',4,4' -diphenylether tetracarboxylic dianhydride (hereinafter abbreviated as ODPA) were dissolved in 321.19g of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) and reacted at an internal temperature of a 500ml three-necked flask for 24 hours, then the reaction solution was heated to 50 ℃ and 11.909g (0.1 mol) of N, N ' -dimethylformamide dimethyl acetal was added dropwise, and after 0.5 hour addition, the reaction was incubated for 0.5 hour, 6g (0.1 mol) of acetic acid was added dropwise and acidified for 0.5 hour; this solution was added to 2.5L of pure water, followed by filtration, and the filter cake was transferred to a vacuum drying oven and dried at 80 ℃ for 36 hours to obtain a powdery organic solvent-soluble positive photosensitive polyimide b 1.

The other positive photosensitive polyamide-based compounds b2-b7 were synthesized differently depending on the kinds of diamine, end-capping agent and dianhydride used, as shown in Table 2.

c1：

c2：

c3：

a-1: bis (3-amino-4-hydroxyphenyl) hexafluoropropane

a-2: bis (3-amino-4-hydroxyphenyl) methane

a-3：

a-4：

d1：

d2：

Monomers and amounts used in tables 2.b2-b7

Polyamide	Dianhydride (mol%)	Diamine (mol%)	End-capping reagent (mol%)
				b2	c1(100)	a2(65)a-1(15)	d1(40)
b3	c1(70)c3(30)	a3(55)a-4(25)	d2(40)
				b4	c1(80)c3(20)	a4(50)a-3(50)	0
b5	c2(100)	a5(60)a-1(25)	d2(30)
				b6	c2(50)、c3(50)	a2(50)a-4(35)	d1(30)
b7	c2(100)	a4(75)a-2(15)	d1(20)

Comparative examples the monomers used and the amounts used of the polyamide compounds b-1 to b-4 are shown in Table 3.

Table 3 monomers and amounts used for b-1 to b-4

Polyamide	Dianhydride (mol%)	Diamine (mol%)	End-capping reagent (mol%)
				b-1	c1(100)	a-4(90)	d1(20)
b-2	c1(100)	a-3(65)、a-1(15)	d1(40)
				b-3	c1(80)c3(20)	a-3(100)	0
b-4	c2(100)	a-1(75)a-2(15)	d1(20)

Second, application example

Abbreviations for the compounds used in the application examples:

B-1：Backborn：DNQ(D)：

DNQ/Backborn＝2.5；Mono/Di/Tri＝3/28/69。

B-2:Backborn：DNQ(D)：

DNQ/Backborn＝2.3；Mono/Di/Tri＝6/35/59。

e1：

e2：

GBL is gamma-butyrolactone.

NMP is N-methyl pyrrolidone.

PGME is propylene glycol monomethyl ether.

Application example 1

A positive photosensitive varnish is prepared by the following steps: under yellow light, 10g of polymer b1 is dissolved in 100g of NMP, stirred at room temperature until the polymer b1 is completely dissolved, added with 1.5g B-1 and 1g e1 and stirred until the polymer b1 is completely dissolved, kept stand for 12h and filtered, thus obtaining the polymer.

Application examples 2 to 5 positive type photosensitive varnish and comparative application examples 1 to 4 photosensitive varnish were prepared in the same manner as in the application examples except that the polyamide, the diazonaphthoquinone compound and the solvent were used, and the specific formulation was as shown in table 4.

TABLE 4 proportioning of application examples 2-5(Y2-Y5) and comparative application examples 1-4(D1-D4)

	Polymer (g)	Diazonaphthoquinone Compound (g)	Crosslinking agent (g)	Solvent (g)
					Y2	b2(10)	B-1(1.2)B-2(0.5)	e2(1.5)	PGME(50)GBL(50)
Y3	b4(10)	B-1(1)B-2(0.3)	e2(1.2)	NMP(50)PGME(50)
					Y4	b2(10)	B-1(1.5)	e2(1.2)	GBL(100)
Y5	b7(10)	B-2(1.5)	e1(1.5)	NMP(100)
					D1	b-1(10)	B-1(1.5)	e1(1)	PGME(50)GBL(50)
D2	b-2(10)	B-1(1)B-2(0.5)	e2(1.5)	PGME(50)GBL(50)
					D3	b-3(10)	B-1(1B-2(0.3)	e2(1.2)	NMP(50)PGME(50)
D4	b-4(10)	B-2(1.5)	e1(1.5)	NMP(100)

The positive photosensitive varnish for application examples 1 to 5 and the photosensitive varnish for comparative application examples 1 to 4 were treated and examined as follows:

preparation of photosensitive resin film

1. A photosensitive resin composition (hereinafter referred to as a varnish) was applied onto a 6-inch silicon plate so that the film thickness after prebaking was 2 μm, and then prebaked at 120 ℃ for 3 minutes by a hot plate (SPHP-8, model name, American semiconductor Co., Ltd., Suzhou) to obtain a photosensitive polyimide precursor film.

2. Method for measuring film thickness

The film thickness of the photosensitive resin film was measured using a step meter made by Bruker, model number DektakXT.

3. Exposure method

A test mask pattern was attached to an exposure apparatus (model H94-25C, southern Sichuan, Ltd.) and exposed to ultraviolet light of a full wavelength at an ultraviolet intensity of 13mW/cm2 (converted to a light intensity of 365nm wavelength) for a prescribed time.

4. Development

The developing solution was prepared by immersing the substrate in a 2.38% aqueous solution of tetramethylammonium hydroxide at 23 ℃ for 60 seconds. Subsequently, the film was rinsed with water for 60 seconds and then dried.

Second, detecting

a. Calculation of residual film rate

The residual film rate is calculated according to the following formula:

residual film ratio (%). film thickness after development ÷ film thickness after prebaking × 100%

b. Calculation of sensitivity

The exposure amount required for completely dissolving and disappearing the exposed part after exposure and development is obtained.

c. Calculation of shrinkage

Pre-baking the silicon plate coated with the varnish, measuring the thickness of the film after the pre-baking, then carrying out main curing on the resin film on the silicon plate, heating the silicon plate to 250 ℃ by using a hot plate, drying for 60min, cooling to 50 ℃, measuring the thickness of the film after the main curing, and calculating the shrinkage rate according to the following formula:

shrinkage (%) (film thickness after prebaking-film thickness after main curing) ÷ film thickness after prebaking × 100%.

d. Calculation of resolving power

The minimum pattern size at the optimum exposure level after exposure and development is called resolution.

TABLE 5 test of application examples 1 to 5(Y1-Y5) and comparative application examples 1 to 4(D1-D4)

	Sensitivity (mJ/cm)2)	Residual film ratio (%)	Resolution power (mum)	Shrinkage (%)
					Y1	65	93	5	11
Y2	72	92	6	14
					Y3	68	95	5	15
Y4	75	91	6	14
					Y5	75	95	8	13
D1	/	/	/	18
					D2	100	85	20	20
D3	90	88	50	25
					D4	95	90	40	22

Note: d1 was completely dissolved during development.

The photosensitive resin film prepared by the method has the characteristics of high residual film rate, low shrinkage rate, excellent light sensitivity and resolution and can prepare stable high-resolution patterns. The positive photosensitive polyimide resin composition of the present invention is suitable for an interlayer insulating film, a passivation film, a buffer coating film, an insulating film for a multilayer printed wiring board, and the like of a semiconductor device, and is also useful as a protective film for a thin film transistor of a liquid crystal display device, an electrode protective film of an organic EL device, and the like.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.