CN112180685B

CN112180685B - Positive photosensitive resin composition, cured film and pattern processing method of cured film

Info

Publication number: CN112180685B
Application number: CN202011174857.7A
Authority: CN
Inventors: 周小明; 肖桂林; 朱双全
Original assignee: Hubei Dinglong Co ltd; Wuhan Rouxian Technology Co ltd
Current assignee: Hubei Dinglong Co ltd; Wuhan Rouxian Technology Co ltd
Priority date: 2020-10-28
Filing date: 2020-10-28
Publication date: 2024-06-25
Anticipated expiration: 2040-10-28
Also published as: CN112180685A

Abstract

The invention provides a positive photosensitive resin composition, a cured film and an image processing method of the cured film, wherein the positive photosensitive resin composition can be developed through an alkaline developer after exposure, and has good exposure sensitivity, good pattern, high resolution and good thermal expansion coefficient of the cured film; the positive photosensitive resin composition provided by the invention comprises: 100 parts by weight of an alkali-soluble resin (a), 10-30 parts by weight of a photoacid generator (b), 20-60 parts by weight of a thermal crosslinking agent (c) and an organic solvent (d), wherein the alkali-soluble resin (a) comprises diamine with a structure of a general formula (1) and/or tetracarboxylic acid with a structure of a structural formula (2), the alkali-soluble resin (a) further comprises dicyanomethylene derivatives of dianhydride with a structure of a general formula (a 5), and the alkali-soluble resin (a) is polyamide acid/polyimide resin or polyamide acid ester/polyamide acid resin.

Description

Positive photosensitive resin composition, cured film and pattern processing method of cured film

Technical Field

The present invention relates to a positive photosensitive resin composition, and more particularly, to a positive photosensitive resin composition, a cured film, and a pattern processing method of the cured film, which are suitable for use as a surface protective film, an interlayer insulating film, an insulating layer of an organic field-effect transistor (TFT), an insulating layer of a Thin Film Transistor (TFT), and the like of a semiconductor element.

Background

Polyimide (PI) is an ideal polymer material with excellent heat resistance, mechanical property, electrical insulation property and chemical stability, and is commonly used in the fields of aerospace, semiconductors, photoelectrons, microelectronics and the like; the photosensitive polyimide (PSPI) can realize image processing without other photoresist, and compared with the traditional Polyimide (PI), the photosensitive polyimide (PSPI) further shortens the process route and is an ideal insulating material in the fields of electronics and microelectronics.

In a positive heat-resistant resin precursor composition in which a part is dissolved in an alkaline developer by exposure, chinese patent publication No. CN1246389C discloses a composition in which a soluble resin such as polyamic acid is added with a diazidonaphthoquinone photoacid generator, a thermal crosslinking agent, and an organic solvent, but since the solubility of carboxyl groups in the polyamic acid is too large, an ideal pattern is hardly obtained by the dissolution resistance of the diazidonaphthoquinone to alkali, and thus, in order to adjust the alkali solubility of the polyamic acid, polyamic acid/polyimide, polyamic acid ester/polyamic acid resin have been developed; the introduction of phenolic hydroxyl groups and carboxyl groups into the resin precursor composition by an appropriate method can significantly affect the alkali solubility, thermal expansion coefficient, transmittance or elastic modulus of the resin precursor composition, and thus diamines and dianhydrides containing phenolic hydroxyl groups and carboxyl groups are currently widely used for the synthesis of polyimides.

Chinese patent publication No. CN107406590a discloses that introducing phenolic hydroxyl group-containing or carboxyl group-containing into the main chain of alkali-soluble resin can give a photosensitive resin precursor composition better exposure sensitivity and higher development resolution, but in the current prior art, a more phenolic hydroxyl group-containing monomer is used, and the monomer of this structure has a rigid skeleton structure and a smaller thermal expansion coefficient, but when the photosensitive resin is subjected to pattern processing (i-line exposure), energy loss is caused due to absorption of the resin itself, and there is a problem that it is difficult to give good photosensitive characteristics to the photosensitive resin; chinese patent publication No. CN106795283a discloses that a photosensitive resin is synthesized using a hexafluoropropylene structure and a dianhydride of an alicyclic structure, and has high transparency and high photoreaction efficiency of a sensitizer at an exposed portion, but the alicyclic structure has a strong chain link flexibility, which causes a problem of a cured film of the photosensitive resin having a high thermal expansion coefficient.

At present, hydroxyl is introduced through a biphenyl structure in the synthesis process of photosensitive resin, but the resin itself absorbs light to cause energy loss, so that the problem of difficulty in obtaining good photosensitive characteristics is solved; the photosensitive resin synthesized by using the dianhydride of the alicyclic structure has good photosensitive characteristics, but the alicyclic chain has larger flexibility, and the problem that the thermal expansion system of the photosensitive resin cured film is higher and the alkali solubility is too high exists. Therefore, in view of the problems existing in the prior art, there is a need to develop a photosensitive resin composition having both moderate alkali solubility, good photosensitive properties and a low thermal expansion coefficient.

Disclosure of Invention

Problems to be solved by the invention:

Aiming at the defects existing in the prior art, the invention introduces the structures of the general formulas (1) and (2) containing phenolic hydroxyl into the photosensitive resin, and diamine connected through an amide bond and dianhydride or tetraacid with an alicyclic structure (weak i-line absorption) lead the photosensitive resin composition to have proper alkali solubility, good exposure sensitivity, higher development resolution and high film residue rate, and simultaneously lead the main chain structure of the photosensitive resin to have an amide bond structure and a benzene ring structure with local strong rigidity, so that the photosensitive resin cured film has good photosensitive property and simultaneously has the characteristic of lower thermal expansion coefficient.

The first aspect of the invention adopts the following technical scheme:

A positive photosensitive resin composition, characterized by comprising: 100 parts by weight of alkali-soluble resin (a), 10-30 parts by weight of photoacid generator (b), 20-60 parts by weight of thermal crosslinking agent (c) and organic solvent (d);

The alkali-soluble resin (a) contains diamine having the structure of general formula (1) and/or tetracarboxylic acid or dianhydride having the structure of structural formula (2);

Wherein R in the structural formula (1) represents a 2-to 4-valent organic group, and R ₁ represents-COOH or-OH;

the main chain of the alkali-soluble resin (a) contains a polymer formula (3) of the general formulae (a 1) and (a 2) as main repeating units;

the general formulae (a 1) and (a 2) are:

wherein R ₁₃ represents an organic group having 1 to 20 carbon atoms.

The general formula (3) is:

Wherein, P and/or Q in the general formula (3) represent a reaction residue of diamine comprising the structure of the general formula (1), and X comprises a reaction residue of tetracarboxylic acid or dianhydride of the structure of the structural formula (2); y represents the reaction residue of a dianhydride or a dicyanomethylene derivative of a dianhydride of formula (a 5);

As another aspect, the alkali-soluble resin (a) comprises a polymer formula (4) of the general formulae (a 3) and (a 4) as main repeating units;

the general formulae (a 3) and (a 4) are:

Wherein R ₂ represents a hydrogen atom and/or an organic group having 1 to 20 carbon atoms,

The general formula (4) is:

Wherein, in the general formula (4), P and/or Q represent a reaction residue comprising diamine of the general formula (1), and X and/or Y represent a reaction residue comprising tetracarboxylic acid or dianhydride of the general formula (2);

Preferably, the general formula (1) is prepared by reacting one or more of the following diamine compounds: p-phenylenediamine, 2' -bistrifluoromethyl-4, 4' -diaminobiphenyl, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4' -diamino-2, 2' -bistrifluoromethyl diphenyl ether.

Further, 20-40mol% of X and/or Y in the repeating units (a 1), (a 2), (a 3) and (a 4) in the general formula (3) and the general formula (4) is derived from the structural formula (2), and 20mol% or more and less of X+Y is or less and 40mol% or less is derived from the structural formula (2); wherein, the repeating units (a 1), (a 2), (a 3) and (a 4) in the general formula (3) and the general formula (4) have 10-20mol% of P and/or Q from the structural formula (1), and the P+Q is more than or equal to 10mol% and less than or equal to 20mol% from the structural formula (1); m and n in the general formula (3) and the general formula (4) are integers of 10-50000.

Further, the main chain end capping group of the alkali-soluble resin (a) has a structure shown in general formulas (5) and/or (6), wherein A is derived from primary monoamine, B is derived from dianhydride, and the main chain end capping group of the alkali-soluble resin (a) accounts for 0-50% of the total amine and/or the total anhydride in terms of mole ratio.

Further, P and Q in the alkali-soluble resin (a) are one or more of an aromatic structure, a fat structure and a silicon-containing structure.

Further, at least one of the groups X, Y, P and Q of the alkali-soluble resin (a) contains fluorine atoms, the mass ratio of the fluorine atoms to the alkali-soluble resin (a) is 5-25%, and at least one of the groups X, Y, P and Q of the alkali-soluble resin (a) contains one or more of hydroxyl, carboxyl and sulfonic acid groups.

Preferably, P, Q of the repeating units (a 1), (a 2), (a 3), (a 4) comprises one or more of the following reaction residues of diamine compounds: 2,2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4' -diaminodiphenyl ether, 2' -bistrifluoromethyl-4, 4' -diaminodiphenyl ether, 4' -diaminotetrafluorodiphenyl ether, 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, and diamine compounds in the following figures, and diamine compounds in the following figures.

X and Y in the repeating units (a 1), (a 3), (a 4) comprise one or more of the following reaction residues of dianhydride compounds: 2,2' -bis (3, 4-dicarboxylic acid phenyl) hexafluoropropane dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 2',3,3' -benzophenone tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, 3', 4' -diphenyl ether tetracarboxylic dianhydride, and the following structures.

Y in the repeating unit (a 2) is a reaction residue of a dicyanomethylene derivative of dianhydride shown in the following figure.

The second aspect of the present invention adopts the following technical scheme, and the film obtained after curing the positive photosensitive resin composition.

The third aspect of the present invention adopts the following technical scheme, and a pattern processing method of a cured film includes the following steps:

i) The positive photosensitive resin composition is coated on a substrate, and then

Drying at 40-120deg.C for 1-10min to form positive photosensitive resin composition film;

ii) exposing the film to light under a mask;

iii) Removing the exposed part of the coating film by using an alkali developer, developing and cleaning;

iii) curing and drying the developed film at 100-400 ℃ to obtain a cured film containing a desired pattern.

The invention has the beneficial effects that: the general formula (1) and (2) structures containing phenolic hydroxyl groups are introduced into the photosensitive resin, so that the photosensitive resin composition has proper alkali solubility, better exposure sensitivity, higher development resolution and high residual film rate, and simultaneously, the photosensitive resin main chain structure has an amide bond structure and a benzene ring structure with strong local rigidity, so that the photosensitive resin cured film has the characteristic of lower thermal expansion coefficient.

Detailed Description

The present invention will be described in detail below.

< Positive photosensitive resin composition >

The photosensitive resin composition according to the present invention comprises: an alkali-soluble resin (a), a photoacid generator (b), a thermal crosslinking agent (c) and an organic solvent (d).

Alkali-soluble resin (a)

In the photosensitive resin composition of the present invention, the alkali-soluble resin (a) contains a polymer represented by the general structural formula (3) as a main component, or a polymer represented by the general structural formula (4) as a main component, and the alkali-soluble resin can be heated or added with a proper catalyst to obtain a polymer containing a polyimide ring, which can greatly improve heat resistance and solvent resistance;

The alkali-soluble resin (a) used in the present invention is represented by a polymer formula (3) having general formulae (a 1) and (a 2) as main repeating units, or a polymer formula (4) having general formulae (a 3) and (a 4) as main repeating units;

wherein m in the general formulae (3) and (4) is an integer of 10 to 50000, and n is an integer of 10 to 50000;

wherein the general formulae (a 1), (a 2), (a 3) and (a 4) are shown in the following figures:

In the above general formulae (3) and (4), the reactive residues in which X and Y in the repeating units (a 1), (a 2), (a 3) and (a 4) are dianhydrides include: pyromellitic dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 2,3,5, 6-pyridinetetracarboxylic dianhydride, bicyclo [3.1.1] hept-2-enetetracarboxylic dianhydride, 3',4' -biphenyltetracarboxylic dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 3,4,9, 10-perylenetetracarboxylic dianhydride, bicyclo [2.2.2] octanetetracarboxylic dianhydride, 2, 3',4' -biphenyl tetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, N '-bis [5,5' -hexafluoropropane-2, 2-diyl-bis (2-hydroxyphenyl) ] bis (3, 4-dicarboxybenzamide), adamantane tetracarboxylic dianhydride, 2',3,3' -biphenyltetracarboxylic dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, cyclobutane tetracarboxylic dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 2',3,3' -benzophenone tetracarboxylic dianhydride, 3',4' -diphenyl ether tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,2,5, 6-naphthalene tetracarboxylic dianhydride, bicyclo [2.2.1] heptane tetracarboxylic dianhydride, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) hexafluoropropane dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, bicyclo [3.3.1] tetracarboxylic dianhydride, dianhydride of the following structure, and the like, which may be used alone or in combination of two or more.

Wherein, R ₃ in the above formula represents-O-, -C (CF ₃)₂-、-C(CH₃)₂ -; one of-CO-, -COO-or-SO ₂ -, R ₄ and R ₅ each represent one of-H, -OH and-SH.

Further, the inventors have found that a tetracarboxylic acid or dianhydride compound having a phenolic hydroxyl group structure and containing an alicyclic structure has an obvious effect in adjusting the alkali solubility of the alkali-soluble resin (a) and the thermal expansion coefficient of a cured film of the photosensitive resin composition, and in the prior art, a method for introducing phenolic hydroxyl groups into the alkali-soluble resin (a) is to use a biphenyl type tetracarboxylic acid or dianhydride monomer containing phenolic hydroxyl groups, although the prepared cured film of the photosensitive resin has a lower thermal expansion coefficient, the main chain structure contains a large amount of benzene ring structures, so that the resin itself has stronger absorption of light and causes energy loss, therefore, the cured film of the photosensitive resin synthesized by using a biphenyl dianhydride or a hydride of the tetracarboxylic acid containing phenolic hydroxyl groups has good transparency and excellent photosensitive performance, but because the main chain molecules are flexible units-alicyclic structures, the thermal expansion coefficient of the cured film of the photosensitive resin is higher, and the cured film of the photosensitive resin has good mechanical strength, and the thermal expansion coefficient of the photosensitive resin cannot be improved by the mechanical structure, namely, the epoxy resin has a better mechanical property can not be synthesized by the epoxy resin has a good thermal expansion coefficient of the epoxy resin, and the alicyclic structure has a better thermal expansion coefficient of the epoxy resin has a better thermal expansion coefficient than 2;

The specific synthesis method is as follows:

Adding polyhydroxy compound (30-40 mmol) and 200-300mL solvent into a three-mouth bottle, cooling to 0 ℃ in an ice bath, adding a certain amount of phosphorus tribromide or phosphorus trichloride into the three-mouth bottle, heating to room temperature after the dripping is finished, stirring for reacting for 10-14h, pouring the product into ice water, repeatedly washing with hydrochloric acid and extracting with diethyl ether for 2-3 times, drying the diethyl ether extract phase with a drying agent, and removing diethyl ether in vacuum to obtain a brominated or chlorinated product;

Adding a certain amount of nickel powder (15-20 mmol), maleic anhydride (25-30 mmol) and dimethyl ether (10-30 mL) into a three-necked flask, introducing inert gas for protection and stirring for 1h, then taking a certain amount of the product (10-20 mmol) to be dissolved in the dimethyl ether, slowly adding the dimethyl ether into the three-necked flask through an adding funnel, stirring for 1-2h at room temperature, starting to slightly heat the reaction mixture and turning green within 5-10 minutes after starting to rotate, continuing to react for 12-36h at room temperature, pouring into 3% hydrochloric acid (100 mL), and extracting a hydrochloric acid solution with dichloromethane; the dichloromethane extract was washed with a sodium hydrogensulfite solution for residual bromine, then dried over anhydrous disodium sulfate, and dichloromethane was removed in vacuo to give tetracarboxylic acid compound (2).

Further, the inventors have found that proper introduction of fluorine atoms can be suitably hydrophobic at the membrane interface upon development with an aqueous alkali solution, can effectively inhibit permeation to the interface, and can improve the solubility of the polymer in an organic solvent, and the following can be exemplified as X or Y structures of some fluorine atom-containing dianhydrides, as shown in the following figures:

By introducing fluorine atoms in the form of-CF ₃ and-C (CF ₃)₂ -groups), the packing density of macromolecules is remarkably reduced due to the large volume of the groups, so that the alkali-soluble resin (a) has higher solubility in organic solvents, and the introduction of fluorine atoms can reduce the charge transfer effect inside and outside the molecule, so that the alkali-soluble resin (a) has lighter color and higher transparency, and furthermore, the fluorine atom has low electron polarization rate, and usually exhibits lower cohesive energy and surface free energy, so that the alkali-soluble resin (a) has lower water absorption, can be hydrophobic and oleophobic, and the dianhydride is preferred from the viewpoints of being capable of adjusting the solubility in an alkali developer and further improving the transparency, based on the advantages: 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) hexafluoropropane dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, cyclobutane tetracarboxylic dianhydride, 2',3,3' -benzophenone tetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, 2-bis (2, 3-dicarboxyphenyl) hexafluoropropane dianhydride, 4,4' -hexafluoroisopropylidene diphthalic anhydride, 3', 4' -tetracarboxylic acid diphenyl ether dianhydride, 3', 4' -diphenyl ether tetracarboxylic acid dianhydride, 4,4' -diphenyl ether tetracarboxylic dianhydride and the following structure:

The introduction of fluorine atoms can bring about good solubility in organic solvents, good transparency and excellent interface hydrophobic and oleophobic properties, and obtain good effect of preventing interfacial penetration and proper dissolution rate, but excessive fluorine atoms can raise the thermal expansion coefficient of the alkali-soluble resin (a) and have poor adhesion with other materials, so that the preferred mass ratio of fluorine atoms to the alkali-soluble resin (a) in the embodiment of the invention is 5-25%.

Further preferred among the above dianhydrides are: 2,2' -bis (3, 4-dicarboxylic acid phenyl) hexafluoropropane dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 2',3,3' -benzophenone tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, 3', 4' -diphenyl ether tetracarboxylic dianhydride, and dianhydride compounds in the following drawings.

Preferably, for the above general formula (3), 20 to 40mol% of X or Y in the repeating units (a 1), (a 2) is derived from the structural formula (2), and 20mol% or more of X+Y or less than 40mol% is derived from the structural formula (2).

Preferably, in the above general formula (4), 20 to 40mol% of X or Y in the repeating units (a 3), (a 4) is derived from the structural formula (2), and 20mol% or more of X+Y or less than 40mol% is derived from the structural formula (2).

In the above general formula (3), wherein Y in the repeating unit (a 2) can also be obtained by reacting a dicyano-methylene derivative of a dianhydride as a monomer component with a diamine compound, wherein Y is preferably a dicyano-methylene derivative of a dianhydride of the structure as shown in the structural formula (a 5), and the dicyano-methylene derivatives of two dianhydrides in (a 5) are isomers, often present in a mixture during synthesis, but are the same in structure as the product of the reaction with a diamine to give an imide, and therefore the following structures can be used singly or in combination of two or more;

Wherein, R ₁₃ in the structural formula (a 5) represents a compound comprising-O-; -C (CF ₃)₂-、-C(CH₃)₂ -, -CO-; an organic group having 1 to 20 carbon atoms which is one of-COO-and-SO ₂ -groups;

In the examples of the present invention, dianhydride (0.01 to 0.05 mol) and dicyanomethane (0.01 to 0.05 mol) were added to a three-necked flask and dissolved in 200 to 500mL of Tetrahydrofuran (THF). Diisopropylamine (0.010-0.100 mol) is added dropwise within 1-3h, after dripping, stirring is continued for 20-24h at room temperature to obtain yellow precipitate, filtering, washing filter cake with THF, and then vacuum drying at 100deg.C for 2-3 days;

taking 3-5mol of the dried filter cake, dissolving the filter cake into 50mL of dichloromethane, introducing nitrogen, then adding 1.0-2.0mL of phosphorus oxychloride (POCl ₃), stirring at room temperature under nitrogen for reaction for 20-24h, filtering, washing the filter cake with dried dichloromethane to obtain a crude product, recrystallizing the crude product in acetic anhydride, and drying to obtain dicyano methylene derivative of dianhydride (a mixture of two isomers, wherein the structure of a product which is reacted with diamine to generate imide is the same, so separation is not needed).

Further, the dicyanomethylene derivative of the dianhydride of the structural formula (a 5) synthesized by the above synthesis method is preferably a structure shown in the following figure.

Wherein, R ₃ represents a group selected from the group consisting of-O-; -C (CF ₃)₂-、-C(CH₃)₂ -, -CO-; -one of the COO-or-SO ₂ -groups;

R ₄ and R ₅ each represent a selected one of the groups-H, -OH and-SH; in the resin synthesis, the amount of the dicyano methylene derivative of the dianhydride of the structural formula (a 5) and the amount of the dianhydride of the structural formula (a 1) in the alkali-soluble resin (a) are quantitatively controlled to obtain the ratio (m/n) of the repeating units (a 1) and (a 2), and the amounts of the phenolic hydroxyl groups, the amide bonds and the alicyclic structures in the repeating units (a 1) and (a 2) are further controlled, so that the purposes of adjusting the alkali solubility, the photosensitive property and the thermal expansion coefficient of the resin composition are achieved.

For general formula (1), wherein R ₀ is preferably one of p-phenylenediamine, 2' -bistrifluoromethyl-4, 4' -diaminobiphenyl (TFMB), 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF), 4' -diamino-2, 2' -bistrifluoromethyl diphenyl ether:

When R ₀ is selected to represent p-phenylenediamine, R ₁ = -OH, the structure of formula (1) is:

The invention also provides a synthesis method of the diamine with the structure, which comprises the following steps:

Stirring 0.5mol-1.0mol of 2, 5-dihydroxy-1, 4-dibenzoic acid in a certain amount of thionyl chloride for 2-4 hours at room temperature, filtering, and drying the filtrate under reduced pressure to obtain a brown solid;

Dissolving 0.1-0.2mol of p-phenylenediamine in a certain amount of acetone and propylene oxide, dropwise adding a solution prepared by dissolving 0.1-1.0mol of the just-obtained brown solid in 100mL of acetone, reacting for 4-6 hours at room temperature after the dropwise addition is finished, filtering out the precipitated white solid, and vacuum drying at 50 ℃ to obtain the diamine.

When R ₀ is selected to represent 2,2 '-bistrifluoromethyl-4, 4' -diaminobiphenyl (TFMB), R ₁ = -OH, the structure of formula (1) is:

When R ₀ is selected to represent 2,2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF), R ₁ = -OH, the structure of formula (1) is:

When R ₀ is selected to represent 4,4 '-diamino-2, 2' -bistrifluoromethyl diphenyl ether, R ₁ = -OH, the structure of formula (1) is:

When R ₀ is selected to represent 2,2' -bistrifluoromethyl-4, 4' -diaminobiphenyl (TFMB), 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF), 4' -diamino-2, 2' -bistrifluoromethyl diphenyl ether, the preparation method is the same as when R ₀ is selected to represent p-phenylenediamine, except that the p-phenylenediamine is replaced by the above three diamines.

The repeating units (a 1), (a 2), (a 3), (a 4) in the general formulae (3) and (4) of the alkali-soluble resin (a) contain one or more of the following diamine compounds: m-phenylenediamine, p-phenylenediamine, 1, 5-naphthalenediamine, 2, 6-naphthalenediamine, 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, 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', aromatic diamines such as 3,3' -tetramethyl-4, 4' -diaminobiphenyl, 3', 4' -tetramethyl-4, 4' -diaminobiphenyl, 2' -bis (trifluoromethyl) -5,5' -dihydroxybenzidine, 3,4' -diaminodiphenyl ether, 3,4' -diaminodiphenylmethane, 4' -diaminodiphenylmethane, and the like, 3,4 '-diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfone, 3,4 '-diaminodiphenyl sulfide, 4' -diaminodiphenyl sulfide, 1, 4-bis (4-aminophenoxy) benzene, 4 '-diaminodiphenyl ether, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl } ether, 3, 5-diaminobenzoic acid, 3-carboxy-4, 4' -diaminodiphenyl ether, and diamines of the following structures, and the like. These may be used alone or in combination of two or more.

In the diamine compound, R ₄～R₁₂, except R ₆, respectively represents one or more of the combination of-H, -OH and-SH groups, R ₆ represents a group selected from the group consisting of-O-; -C (CF ₃)₂-、-C(CH₃)₂ -, -CO-; -one of the COO-or-SO ₂ -groups;

By adjusting the type and proportion of the R ₄～R₁₂ group, the dissolution rate of the alkali water in the structural formula (3) can be adjusted, and a photosensitive resin composition having a proper dissolution rate can be obtained, and the diamine compound is preferable in order to obtain a proper dissolution rate of the alkali water: 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, 4 '-diaminodiphenyl ether, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl } ether, 3, 5-diaminobenzoic acid, 3-carboxy-4, 4' -diaminodiphenyl ether, p-phenylenediamine, 2 '-bistrifluoromethyl-4, 4' -diaminobiphenyl, 4 '-diamino-2, 2' -bistrifluoromethyl-diphenyl ether, 2 '-bistrifluoromethyl-4, 4' -diaminodiphenyl ether, 2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4' -diaminotetrafluorodiphenyl ether, diamine of the structure shown below, and the like.

Further preferred among the above diamines is: 2,2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4' -diaminodiphenyl ether, 2' -bistrifluoromethyl-4, 4' -diaminodiphenyl ether, 4' -diaminotetrafluorodiphenyl ether, and diamine compounds in the following figures.

Wherein, for the general formula (3), 10 to 20mol% of P or Q in the repeating units (a 1), (a 2) is derived from the structural formula (1), and 10mol% or more of P+Q or less than 20mol% is derived from the structural formula (1).

Wherein, for the general formula (4), 10 to 20mol% of P or Q in the repeating units (a 3), (a 4) is derived from the structural formula (1), and 10mol% or more of P+Q or less than 20mol% is derived from the structural formula (1).

Further, since fluorine atoms are introduced in the examples of the present invention, the adhesiveness of the resin composition to the substrate is reduced to some extent, and in order to neutralize this adverse effect, the adhesiveness of the resin composition to the substrate is improved, and in the embodiments of the present invention, P and/or Q in the alkali-soluble resin (a) further contain a diamine having a siloxane structure in an amount of 0 to 10mol% in terms of the molar percentage of the diamine having a siloxane structure in P and/or Q of the general formulae (3) and (4) within a range not to reduce heat resistance; specifically, as the diamine component, there may be mentioned: diamines such as 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane (SiDA) and bis (p-aminophenyl) octamethylpentasiloxane are preferably 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane (SiDA).

In the terminal structure of the polymer of the structural unit shown in the general formula (5), A in the general formula (5) is derived from primary monoamine of a blocking agent; as the primary monoamine of the end-capping agent, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminophenol, 3-aminophenol, 4-aminophenol, 3-amino-4, 6-dihydroxypyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid and the like are preferable. The primary monoamines mentioned above may be used singly or in combination of two or more, and the primary monoamines as the blocking agent account for 0 to 50mol%, particularly preferably 5 to 30mol%, of the total amine components

In the terminal structure of the polymer of the structural unit shown in the general formula (6), B is derived from dianhydride of the end-capping agent; examples of the dianhydride as the blocking agent include phthalic anhydride, maleic anhydride, norbornene dianhydride, and cyclohexane dicarboxylic anhydride, and the above dianhydrides may be used alone or in combination of two or more. The dianhydride as the end-capping agent is 0 to 50mol%, particularly preferably 5 to 30mol%, based on the total anhydride component.

Photoacid generator (b)

The positive photosensitive resin composition of the present invention further uses (b) a photoacid generator, and examples thereof include quinone diazide compounds (naphthoquinone diazide sulfonate compounds), sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, and the like, which may be used alone or in combination of two or more thereof; these quinone diazide compounds can be synthesized by esterification of phenolic hydroxyl compounds with quinone diazide sulfonyl chlorides. In the present invention, a compound in which 5-naphthoquinone diazide sulfonyl group or 4-naphthoquinone diazide sulfonyl group is bonded to a compound having a phenolic hydroxyl group is preferably used.

Specific examples of the phenolic hydroxyl compound which can be cited are shown in the following structures:

As the quinone diazide compound, any one or more of naphthoquinone diazide sulfonate structures are preferably used in combination. Specifically, the photoacid generators PAC-1 to PAC-20 for the following commercial use may be mentioned, and any one or more of the following can be used in combination.

The photoacid generator (b) is added in an amount of 5 to 40 parts by weight, preferably 10 to 30 parts by weight, relative to 100 parts by weight of the (a) alkali-soluble resin.

Thermal crosslinking agent (c)

The positive photosensitive resin composition of the present invention contains a thermal crosslinking agent (c); the thermal crosslinking agent (c) can perform a crosslinking reaction with the alkali-soluble resin (a) by heating, thereby improving the chemical resistance of the cured film; examples of the thermal crosslinking agent (c) include epoxy compounds (c 1) and alkoxy/hydroxymethyl compounds (c 2); among them, (c 1) the Epoxy group compound is preferably a compound having two or more Epoxy groups in one molecule, and examples thereof include bisphenol a type Epoxy resins, bisphenol a type oxetane resins, bisphenol F type Epoxy resins, bisphenol F type oxetane resins, epoxy group-containing silicones such as propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl (glycidoxypropyl) siloxane, and the like, but are not limited to these, and specific examples include products of epoilon, EXA, and the like of the japanese ink chemical industry, bisphenol a type Epoxy compounds of the epokote series by Yuka Shell Epoxy co.ltd, EP series by ADEKA corporation, and the like. (c2) The alkoxy/hydroxymethyl compound preferably contains two or more alkoxy groups and/or hydroxymethyl functional groups in one molecule, and examples thereof include the trade name DML, triML, DMOM, HMOM, TMOM and the like of Benzhou chemical and the MX and MW series of tri-and chemical. The positive photosensitive resin composition of the present invention contains at least one of the above-mentioned thermal crosslinking agents.

The amount of the thermal crosslinking agent (c) added is 15 to 100 parts by weight, preferably 20 to 60 parts by weight, relative to 100 parts by weight of the alkali-soluble resin (a).

Organic solvent (d)

The positive photosensitive resin composition of the present invention contains an organic solvent (d); specific examples of the usable organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, propyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, bis (2-methoxyethyl) ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, methyl ethyl ketone, cyclohexanone, cyclopentanone, butanol, isobutanol, pentanol, γ -butyrolactone, N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, and the like, but are not limited thereto.

< Cured film >

The cured film according to the present invention is a film obtained by curing the positive photosensitive resin composition according to the present invention.

< Method of patterning >

The method of patterning a resin pattern using the positive photosensitive resin composition of the present invention will be described in detail.

Examples of the method for applying the positive photosensitive resin composition include spin coating, spray coating, blade coating, screen coating, and slit coating; it is generally preferable to apply the film so that the film thickness after drying becomes 0.5 to 50. Mu.m; drying by using an oven, a heating plate, an infrared oven and the like, and drying for 1-10 min at the temperature of 40-120 ℃ or carrying out stage programming drying treatment to volatilize the organic solvent; examples of the substrate include, but are not limited to, silicon wafers, ceramics, gallium arsenic, organic circuit boards, inorganic circuit boards, and substrates having circuit constituent materials disposed on these substrates.

After the coating and drying process, a positive photosensitive resin composition film is formed on the substrate; exposing the film by irradiating the film with exposure light through a mask having a desired pattern; an exposure light source, preferably using i (365 nm), h (405 nm), g (436 nm) rays of a mercury lamp; an exposure apparatus, such as a reduction projection type exposure apparatus, a mask aligner, and a mirror projection type exposure apparatus, is used.

After exposure, the exposed portion of the film is removed by using a developer, and as the developer, an aqueous solution of an alkali compound such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, dimethylamine, dimethylaminoethanol, cyclohexylamine, ethylenediamine, etc. is preferable; in addition, one or a combination of a plurality of organic solvents such as N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, methanol, ethanol, isopropanol, ethyl lactate, cyclopentanone, cyclohexanone, and acetone are added to these alkaline aqueous solutions.

The developing mode is one of spray developing, dipping developing and ultrasonic dipping developing methods; conditions such as development time, development temperature, development step, etc., may be such that the exposed portion is removed; after development, the film is preferably rinsed with water, and more preferably rinsed with an aqueous solution of an alcohol or ester of ethanol, isopropanol, or ethyl lactate; baking the film at 60-150 deg.c, preferably 60-120 deg.c for 5 s-60 min before developing; after the rinsing is finished, the film is heated and dried at the temperature of 60-200 ℃ for 1-60 min.

After exposure, development and rinsing, the positive photosensitive resin composition of the invention is subjected to stepwise temperature programming/constant temperature heat treatment at the temperature of 100-400 ℃ to form a cured film by curing; the heating/constant temperature heat treatment method includes, for example, heating from room temperature at a heating rate of 5 ℃/min, then performing constant temperature heat treatment at 120 ℃ and 180 ℃ for 30min, and then heating to 250 ℃ for 2h; or heating from room temperature to 250 ℃ in 2h at a heating rate of 5 ℃/min, and then performing constant-temperature heat treatment at 250 ℃ for 2h; the heating/constant temperature heat treatment is carried out under normal pressure, nitrogen or vacuum; the cured film containing the desired pattern is obtained by curing, and has heat resistance.

The cured film having a desired pattern formed from the positive photosensitive resin composition of the present invention is used for, but not limited to, a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic Electroluminescent (EL) element, an insulating layer of a Thin Film Transistor (TFT), and the like.

Examples

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. First, the evaluation methods in each of the synthesis examples and comparative examples will be described; for the evaluation, a resin composition (hereinafter referred to as varnish) previously filtered by a 1 μm polytetrafluoroethylene filter was used.

Imidization Rate of synthetic resin

Method for measuring imidization ratio of alkali-soluble resin (a): a solution of N-methylpyrrolidone (hereinafter referred to as NMP) having a solid content concentration of 50% by mass of a polyimide resin was applied to a 6-inch silicon wafer by spin coating, followed by baking at 120℃for 3 minutes using a heating plate (SKW-636 manufactured by Dainippon Screen Co., ltd.) to prepare a pre-baked film having a thickness of 10 μm.+ -. 1. Mu.m; dividing the pre-baked film into two parts, marking one half of the pre-baked film as a film (B) before curing, putting the other half of the pre-baked film into an inert gas oven (Koyo Thermo Systems is manufactured by INH-21 CD), heating to 350 ℃ for 60min after 30min to the curing temperature, and heating to 350 ℃; then slowly cooling to below 50 ℃ in an oven to obtain a solidified film (A); the infrared absorption spectrum of the obtained cured film (A) and film (B) before curing was measured using a Fourier transform infrared spectrophotometer FT-720 (manufactured by horiba Seisakusho Co., ltd.); the peak intensity in the vicinity of 1377cm ^-1 of the C-N stretching vibration derived from the imide ring was obtained, and the value of "peak intensity of film (B) before curing/peak intensity of cured film (A)" was taken as the imidization rate.

Production of developing film

A positive photosensitive resin composition (varnish) was applied to a 6-inch silicon wafer so that the film thickness after prebaking became 10 μm, and then prebaked at 120℃for 4 minutes using a heating plate (SCW-636; manufactured by Daika screen Co., ltd.); exposing the film with a small developing device (AC 3000) for lithography at a step pitch of 10mJ/cm ² at an exposure amount of 0 to 1000mJ/cm ² for i (365 nm), h (405 nm), g (436 nm) lines; after exposure, the pre-baked film of the photosensitive polyimide was developed in an aqueous solution of 2.38 mass% of tetramethylammonium (hereinafter, referred to as TMAH, manufactured by the multi-molar chemical industry) for 90 seconds, and then rinsed with water to obtain a developed film having an isolated pattern of 10 μm.

Calculation of film residue Rate

Residual film ratio (%) =film thickness after development ∈film thickness after prebaking×100%.

Sensitivity to

Using a coating and developing apparatus ACT-8 (Tokyo Electron Limited), a varnish was coated on a 6-inch silicon wafer by spin coating, and prebaked at 120℃for 3 minutes; exposure was performed using an i-line stepper NSR-2005i9C (manufactured by Nikon); after exposure, the exposure was repeated 2 times by spin-coating immersion (puddle method) using 2.38 wt% TMAH using a developing device of ACT-8 (discharge time of developer: 10s, spin-coating immersion time: 40 s), and then rinsed with pure water, followed by spin-drying, and the lowest exposure amount at which the exposed portion was completely dissolved was taken as sensitivity.

Resolution ratio

A cured film of the composition was produced by the method described in example 1 below, using a double-sided alignment single-sided exposure apparatus (mask aligner PEM-6M; manufactured by Union Optical Co., ltd.) and performing patterned exposure using i (365 nm), h (405 nm), g (436 nm) lines of an ultra-high pressure mercury lamp via a gray-scale mask (MDRM MODEL-5-FS; manufactured by OptoLine International Co.) for sensitivity measurement, and then performing development using a lithography small-sized developing apparatus (AD-2000; manufactured by Zerewriter Co., ltd.) and then using a high-temperature inert oven (INH-9 CD-S; manufactured by Koyo Thermo Systems Co.); using an FPD/LSI inspection microscope (OPTIPHOT-330; manufactured by UNION Co., ltd.), the resolution pattern of the cured film thus produced was observed; the minimum pattern size of the line and space pattern obtained without residue was taken as the resolution.

Evaluation of developed film Pattern

The viscosity of the unexposed portion and the residue of the exposed portion were visually observed with respect to the photosensitive resin composition film formed by development; the developed film was judged to be satisfactory when there was no problem in the pattern, and the unexposed portion was judged to be defective when there was tackiness in the exposed portion or residue in the exposed portion.

Determination of coefficient of Linear thermal expansion (CTE)

The resin was dissolved in GBL (gamma-butyrolactone) to prepare a 40% solution, spin-coated on an 8-inch silicon wafer, and then baked with a heating plate (Tokyo Electron Limited, prepared as a coating and developing apparatus Act-8) at 120℃for 3 minutes to obtain a resin film.

Heating the pre-baked coating film to 300 ℃ under a nitrogen flow (oxygen concentration of 20ppm or less) at a rate of 3.5 ℃/min, holding for 30min, and cooling to 50 ℃ at a rate of 5 ℃/min, thereby producing a resin laminate; then, a slit was cut around the obtained resin laminate, and the resin laminate was immersed in hot water at 65 ℃ for 1 to 4 minutes, then physically pulled, peeled off from the substrate, and air-dried.

The resin laminate of glass was measured under a nitrogen flow using a thermal mechanical analyzer (EXSTAR 6000TMA/SS6000, manufactured by SII nano Technology Co., ltd.); the temperature raising method is carried out according to the following conditions: in the stage 1, the temperature is raised to 150 ℃ at a temperature raising rate of 5 ℃/min, adsorbed water of the sample is removed, and in the stage 2, the temperature is cooled to room temperature at a temperature lowering rate of 5 ℃/min; in stage 3, the present measurement was performed at a temperature rising rate of 5℃per minute, and the coefficient of linear expansion (CTE) was determined from the average value of the coefficients of linear expansion at 50 to 200 ℃. The determination was performed by the following evaluation method.

Excellent (a): 35 ppm/DEG C or less

Good (B): exceeding 35 ppm/DEG C and being 40 ppm/DEG C or less

Poor (C): exceeding 40 ppm/DEG C

Hereinafter, embodiments of the present invention will be described in detail. First, abbreviations corresponding to some monomers involved in examples will be described.

6FDA:2,2' -bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride

THF: tetrahydrofuran (THF)

DIPA: diisopropylamine

TFMB:2,2 '-bistrifluoromethyl-4, 4' -diaminobiphenyl

BAHF:2,2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane

ODA:4,4' -diaminodiphenyl ether

SiDA:1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane

NMP: n-methylpyrrolidone

6FAP:2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane

ODPA:3,3', 4' -diphenyl ether tetracarboxylic dianhydride

Synthesis example 1

Synthesis of dicyanomethylene derivative Y1 of dianhydride of aromatic tetracarboxylic acid

In a three-necked flask, 6FDA (0.0245 mol) and dicyanomethane (0.049 mol) were added to dissolve 300mL of THF. DIPA (0.099 mol) was added dropwise over 1h, after which stirring was continued at room temperature for 20h to give a yellow precipitate, which was filtered, the filter cake was washed with THF and then dried in vacuo at 100deg.C for 2 days.

Taking 3.36mol of the dried filter cake, dissolving the filter cake into 50mL of dichloromethane, introducing nitrogen, then adding 1.2mL of POCl ₃, stirring and reacting for 20h at room temperature under nitrogen, filtering, washing the filter cake with the dried dichloromethane to obtain a crude product, recrystallizing the crude product in acetic anhydride, and then drying to obtain 6FDA dicyano methylene derivative Y1 (a mixture of two isomers, and the structure of a product which is the same as that of a product of an imide generated by a diamine reaction is not needed to be separated).

Synthesis example 2

Synthesis of aminophenol compound Y2

Stirring 0.6mol of 2, 5-dihydroxyl-1, 4-dibenzoic acid in 110mL of thionyl chloride at room temperature for 2h, filtering, and drying the filtrate under reduced pressure to obtain a brown solid; 0.11mol of p-phenylenediamine was dissolved in 200mL of acetone and 0.3mol of propylene oxide; to this was added dropwise a solution of 0.05mol of the brown solid just obtained in 100mL of acetone; after completion of the dropwise addition, the reaction was carried out at room temperature for 4 hours, and then the precipitated white solid was filtered off and dried under vacuum at 50℃to obtain a diaminophenol compound Y2 represented by the following formula.

Synthesis example 3

Synthesis of aminophenol Compound Y3

The synthesis method of the aminophenol compound Y3 is different from Y2 in that p-phenylenediamine is replaced by TFMB, and other conditions are unchanged, so that the aminophenol compound Y3 is obtained.

Synthesis example 4

Synthesis of aminophenol Compound Y4

The synthesis method of the aminophenol compound Y4 is different from that of Y2 in that p-phenylenediamine is replaced by BAHF, and other conditions are unchanged, so that the aminophenol compound Y4 is obtained.

Synthesis example 5

Synthesis of aminophenol Compound Y5

The synthesis method of the aminophenol compound Y5 is different from Y2 in that p-phenylenediamine is replaced by 4,4 '-diamino-2, 2' -bistrifluoromethyl diphenyl ether, and other conditions are unchanged, so that the aminophenol compound Y5 is obtained.

Synthesis example 6

Synthesis of chloro-substituted product Y6 of tetracarboxylic acid compound containing alicyclic structure

Polyhydroxy compound (36.20 mmol) and 300mL of diethyl ether in the following chart were added to a three-necked flask, the temperature was lowered to 0℃in an ice bath, then phosphorus tribromide (434 mmol) was added dropwise to the three-necked flask, after the addition was completed, the temperature was slowly raised to room temperature, and the reaction was stirred for 12 hours, the product was poured into ice water, washed with brine and extracted twice with diethyl ether repeatedly, the diethyl ether extract phase was dried with magnesium sulfate, and then diethyl ether was removed in vacuo to obtain a brominated product.

Nickel powder (17.90 mmol), maleic anhydride (28.64 mmol) and dimethyl ether (20 mL) were added to a three-necked flask, protected by argon and stirred for 1h, then the above brominated product (14.21 mmol) was dissolved in dimethyl ether (20 mL) and then slowly added to the three-necked flask through an addition funnel, stirred for 1h at room temperature, the reaction mixture started to slightly heat up and turned green within 5-10min after starting to rotate and started to react for 24h at room temperature, and then poured into 3% hydrochloric acid (100 mL). The hydrochloric acid solution was then extracted with dichloromethane (50 mL each). The dichloromethane extract was washed with a solution of sodium bisulphite for residual iodine, then dried over anhydrous disodium sulphate, and dichloromethane was removed in vacuo to give the tetracarboxylic acid compound in the following figure.

0.1Mol of the above tetracarboxylic acid was stirred in 110mL of thionyl chloride at room temperature for 2 hours, filtered, and the filtrate was dried under reduced pressure to give yellow solid Y6.

Synthesis example 7

Synthesis of alkali-soluble resin (a) A1

ODA (0.008 mol), siDA (0.002 mol), Y2 (0.010 mol), 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (0.018 mol), NMP (100 g) and pyridine (9.5 g) were added together under a dry nitrogen stream to a three-necked flask, and cooled to-15℃and Y6 (0.010 mol) was dissolved in NMP (10 g), and the reaction was completed by dropping for 0.5 hours, then warmed to 0℃and Y1 (0.030 mol) was dissolved in NMP (30 g) to be added, reacted for 2 hours at 25℃and then 3-aminophenol (0.004 mol) was added, and the reaction was continued for 24 hours at 25℃and then warmed to 40℃for 2 hours and then warmed to 60℃for 2 hours. At 2L ethanol: water=2:1 (volume ratio) to give a white precipitate, which is filtered off, the filter cake is taken up in ethanol: water=2:1 (volume ratio) and then vacuum-dried at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A1, and infrared absorption spectrum was measured, and imide ratio was 85.0%.

Synthesis example 8

Synthesis of alkali-soluble resin A2

ODA (0.008 mol), siDA (0.002 mol), Y2 (0.010 mol), bis (3-amino-4-hydroxyphenyl) hexafluoropropane (0.018 mol), NMP (100 g) and pyridine (28.5 g) were added together under a dry nitrogen flow to a three-necked flask, and cooled to-15℃and Y6 (0.030 mol) was added dropwise to dissolve NMP (20 g), after completion of the reaction for 0.5h, then warmed to 0℃and 6FDA (0.010 mol) was added to dissolve NMP (10 g), reacted for 2h at 25℃and then 3-aminophenol (0.004 mol) was added, and the reaction was continued at 25℃for 24h, then warmed to 40℃and reacted for 2h at 60 ℃. At 2L ethanol: water=2:1 (volume ratio) to give a white precipitate, which is filtered off, the filter cake is taken up in ethanol: water=2:1 (volume ratio) and then vacuum-dried at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A2, and infrared absorption spectrum was measured, and imide ratio was 72.0%.

Synthesis example 9

Synthesis of alkali-soluble resin A3

Under a dry nitrogen flow, derivative amine (0.025 mol), Y3 (0.010 mol), siDA (0.002 mol), dissolved in NMP (100 g), pyridine (19 g) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane in the following figures were added together into a three-necked flask, cooled to-15 ℃, Y6 (0.020 mol) was added dropwise to dissolve in NMP (20 g), the reaction was completed for 0.5h, then heated to 0 ℃,3', 4' -biphenyltetracarboxylic dianhydride (0.020 mol), NMP (20 g), and reacted for 2h at 25℃were added thereto, then reacted for 48h at 25℃and then heated to 40℃for 2h. At 2L ethanol: water=1:3 (volume ratio) to give a white precipitate, which is filtered off, the filter cake is taken up in ethanol: water=1:3 (volume ratio) and then vacuum-dried at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A3, and infrared absorption spectrum was measured, and imide ratio was 52.0%.

Synthesis example 10

Synthesis of alkali-soluble resin A4

Y4 (0.015 mol), ODA (0.020 mol), siDA (0.002 mol) and dissolved in NMP (100 g) were added together in a three-necked flask under a dry nitrogen flow, pyridine (19 g) was added together and cooled to-15℃and Y6 (0.025 mol) was dissolved in NMP (20 g) and reacted for 0.5 hours dropwise, then heated to 0℃and 2,2', 3' -benzophenone tetracarboxylic dianhydride (0.015 mol) and NMP (20 g) were added together and reacted for 2 hours at 25℃and 3-aminobenzoic acid (0.006 mol) was added and reacted for 48 hours at 25℃and then heated to 40℃for 6 hours. At 2L ethanol: water=1:3 (volume ratio) to give a white precipitate, which is filtered off, the filter cake is taken up in ethanol: water=1:3 (volume ratio) and then vacuum-dried at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A4, and infrared absorption spectrum was measured, and imide ratio was 61.6%.

Synthesis example 11

Synthesis of alkali-soluble resin A5

2,2 '-Bistrifluoromethyl-4, 4' -diaminodiphenyl ether (0.010 mol), 6FAP (0.017 mol), Y3 (0.010 mol), siDA (0.002 mol), dissolved in NMP (100 g), pyridine (14.8 g) was added and cooled to-15℃and Y6 (0.015 mol) dissolved in N-methylpyrrolidone NMP (20 g) was added dropwise to react for 0.5h, then heated to 0℃and cyclobutanetetracarboxylic dianhydride (0.015 mol), 3', 4' -tetracarboxylic diphenylether dianhydride (0.015 mol) was added thereto and NMP (20 g) were added thereto, reacted for 2h at 25℃and then 4-aminophenol (0.002 mol) was added and reacted for 48h at 25℃and then heated to 40℃to react for 4h. At 2L ethanol: water=1:3 (volume ratio) to give a white precipitate, which is filtered off, the filter cake is taken up in ethanol: water=1:3 (volume ratio) and then vacuum-dried at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A5, and infrared absorption spectrum was measured, and imide ratio was 36.9%.

Synthesis example 12

Synthesis of alkali-soluble resin A6

Under a dry nitrogen flow, 4' -diaminotetrafluorodiphenyl ether (0.018 mol), Y4 (0.015 mol), siDA (0.003 mol), pyridine (28.5 g) dissolved in NMP (100 g) and pyridine (20 g) in the following figures were added together to a three-necked flask, cooled to-15℃and Y6 (0.030 mol) dissolved in NMP (20 g) was added dropwise, the reaction was completed for 0.5 hours, then heated to 0℃and dianhydride (0.010 mol) and NMP (20 g) in the following figures were added together, reacted for 2 hours at 25℃and 4-aminophenol (0.008 mol) and reacted for 48 hours at 25℃were then heated to 60℃for 6 hours. At 2L ethanol: water=1:3 (volume ratio) to give a white precipitate, which is filtered off, the filter cake is taken up in ethanol: water=1:3 (volume ratio) and then vacuum-dried at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A6, and infrared absorption spectrum was measured, and imide ratio was 49.5%.

Synthesis example 13

Synthesis of alkali-soluble resin A7

Y5 (0.034 mol), siDA (0.003 mol), NMP (100 g) and pyridine (9.5 g) were added together to a three-necked flask under a dry nitrogen stream, and cooled to-15℃and Y6 (0.015 mol) was added dropwise to NMP (10 g) to complete the reaction for 0.5 hours, then heated to 0℃and 6 FAP-derived dianhydride (0.025 mol) and NMP (30 g) in the following scheme were added together thereto, reacted at 25℃for 2 hours, then 3-aminophenol (0.006 mol) and reacted at 25℃for 48 hours, and then heated to 60℃for 6 hours. At 2L ethanol: water=1:3 (volume ratio) to give a white precipitate, which is filtered off, the filter cake is taken up in ethanol: water=1:3 (volume ratio) and then vacuum-dried at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A7, and infrared absorption spectrum was measured, and imide ratio was 37.1%.

Synthesis example 14

Synthesis of alkali-soluble resin A8

Under a dry nitrogen flow, the fluoroarylamine (0.008 mol), Y5 (0.010 mol), 6FAP (0.014 mol), siDA (0.002 mol), pyridine (28.5 g) dissolved in NMP (100 g) and pyridine (30 g) in the following figures were added together into a three-necked flask, cooled to-15℃and Y6 (0.030 mol) dissolved in NMP (30 g) was added dropwise to complete the reaction for 0.5 hours, then heated to 0℃and 6 FAP-derived dianhydride (0.010 mol) and NMP (10 g) in the following figures were added together, reacted for 2 hours at 25℃and then 3-aminobenzoic acid (0.012 mol) and reacted for 48 hours at 25℃were added thereto, followed by heating to 60℃to react for 6 hours. At 2L ethanol: water=1:3 (volume ratio) to give a white precipitate, which is filtered off, the filter cake is taken up in ethanol: water=1:3 (volume ratio) and then vacuum-dried at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A8, and infrared absorption spectrum was measured to obtain an imide ratio of 74.1%.

Synthesis example 15

Synthesis of alkali-soluble resin A9

Y4 (0.038 mol), siDA (0.002 mol), dissolved in NMP (100 g) and pyridine (8.5 g) were added together in a three-necked flask under a dry nitrogen flow, and cooled to-15℃and Y6 (0.010 mol) dissolved in NMP (30 g) was added dropwise, the reaction was completed for 0.5h, then heated to 0℃and 6FDA (0.031 mol) and NMP (40 g) were added together, reacted for 2h at 25℃and 48h at 25℃and then heated to 40℃and reacted for 2h at 40℃and then xylene (10 mL) was added for azeotropy, and heated to 150℃and reacted for 5h. At 2L ethanol: water=1:3 (volume ratio) to give a white precipitate, which is filtered off, the filter cake is taken up in ethanol: water=1:3 (volume ratio) and then vacuum-dried at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A9, and infrared absorption spectrum was measured, and imide ratio was 91.0%.

Synthesis example 16

Synthesis of alkali-soluble resin A10

Diamine compound (0.024 mol), Y5 (0.014 mol), siDA (0.002 mol), pyridine (23.5 g) in the following figures were added together in a three-necked flask, dissolved in NMP (100 g), cooled to-15℃and Y6 (0.025 mol) was added dropwise to dissolve in NMP (20 g) to complete the reaction for 0.5 hours, then heated to 0℃and 3,3', 4' -biphenyltetracarboxylic dianhydride (0.015 mol) and NMP (20 g) were added together, reacted at 25℃for 48 hours, then xylene (10 mL) was added to azeotropy, and heated to 150℃to react for 5 hours under a dry nitrogen stream. At 2L ethanol: water=1:3 (volume ratio) to give a white precipitate, which is filtered off, the filter cake is taken up in ethanol: water=1:3 (volume ratio) and then vacuum-dried at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin a10, and infrared absorption spectrum was measured, and imide ratio was 92%.

Synthesis example 17

Synthesis of alkali-soluble resin A11

Diamine compound (0.012 mol), Y5 (0.022 mol), siDA (0.002 mol), pyridine (23.5 g) in the following figures were added together to a three-necked flask, dissolved in NMP (100 g), cooled to-15℃and Y6 (0.035 mol) was added dropwise to dissolve in NMP (20 g), reacted for 0.5 hours, then warmed to 0℃and 6FDA (0.005 mol), 20g (NMP) were added together, reacted for 2 hours at 25℃and 3-aminophenol (0.008 mol), reacted for 48 hours at 25℃and then xylene (10 mL) was added together to azeotropy, and heated to 150℃to react for 5 hours under a dry nitrogen stream. At 2L ethanol: water=1:3 (volume ratio) to give a white precipitate, which is filtered off, the filter cake is taken up in ethanol: water=1:3 (volume ratio) and then vacuum-dried at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin a11, and infrared absorption spectrum was measured, and imide ratio was 93.4%.

Synthesis example 18

Synthesis of alkali-soluble resin A12

Y3 (0.016 mol), 6FAP (0.016 mol), siDA (0.004 mol), pyridine (13.5 g) dissolved in NMP (100 g) and pyridine (20 g) were added together to a three-necked flask under a dry nitrogen flow, and cooled to-15℃and Y6 (0.02 mol) dissolved in NMP (20 g) was added dropwise, and the reaction was completed for 0.5 hours, then heated to 0℃and ODPA (0.02 mol) and NMP (20 g) were added thereto and reacted for 2 hours at 25℃and then 4-aminosalicylic acid (0.008 mol) and 48 hours at 25℃were added, then xylene (10 mL) was added azeotroped, and the temperature was raised to 150℃and reacted for 5 hours. At 2L ethanol: water=1:3 (volume ratio) to give a white precipitate, which is filtered off, the filter cake is taken up in ethanol: water=1:3 (volume ratio) and then vacuum-dried at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin a12, and infrared absorption spectrum was measured, and imide ratio was 89.0%.

Synthesis example 19

Synthesis of alkali-soluble resin B1

Y5 (0.018 mol), 6FAP (0.016 mol), siDA (0.002 mol), pyridine (13.5 g) dissolved in NMP (100 g) and pyridine (13.5 g) were added together to a three-necked flask under a dry nitrogen flow, and cooled to-15 ℃, Y6 (0.015 mol) dissolved in NMP (20 g) was added dropwise, the reaction was completed for 0.5h, then heated to 0 ℃, ODPA (0.025 mol) and NMP (20 g) were added together, the reaction was completed for 2h at 25 ℃, then 4-aminosalicylic acid (0.008 mol) and 48h at 25 ℃ were added, then heated to 50 ℃, and N, N-dimethylformamide dimethyl acetal solution (0.080 mol) diluted with NMP (10 g) was added dropwise within 10min, and the reaction was completed for 4h at 50 ℃ after completion of the dropwise addition; at 2L ethanol: water=1:3 (volume ratio) to give a white precipitate, which is filtered off, the filter cake is taken up in ethanol: water=1:3 (volume ratio) and then vacuum-dried at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin B1, and infrared absorption spectrum was measured, and imide ratio was 39.0%.

Synthesis example 20

Synthesis of alkali-soluble resin B2

Y3 (0.021 mol), ODA (0.014 mol), siDA (0.001 mol), dissolved in NMP (100 g), pyridine (9 g) were added together to a three-necked flask under a dry nitrogen flow, and cooled to-15℃and Y6 (0.010 mol) dissolved in NMP (10 g) was added dropwise, then the reaction was completed for 0.5 hours, then heated to 0℃and bis (3-amino-4-hydroxyphenyl) hexafluoropropane derivative dianhydride (0.030 mol) and NMP (40 g) in the following figures were added thereto, reacted for 2 hours at 25℃and then 4-aminosalicylic acid (0.008 mol) was added, reacted for 48 hours at 25℃and then heated to 50℃and N, N-dimethylformamide dimethyl acetal solution (0.060 mol) diluted with NMP (10 g) was added dropwise over 10 minutes, and reacted for 4 hours at 50℃after completion of the dropwise. At 2L ethanol: water=1:3 (volume ratio) to give a white precipitate, which is filtered off, the filter cake is taken up in ethanol: water=1:3 (volume ratio) and then vacuum-dried at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin B2, and infrared absorption spectrum was measured, and imide ratio was 25.5%.

Synthesis example 21

Synthesis of alkali-soluble resin B3

Y3 (0.015 mol), 6FAP (0.020 mol), siDA (0.002 mol), pyridine (9 g) dissolved in NMP (100 g) and pyridine (9 g) were added together to a three-necked flask under a dry nitrogen flow, and cooled to-15℃to drop Y6 (0.010 mol) dissolved in NMP (10 g), and reacted for 0.5 hours, then warmed to 0℃to add 6FDA (0.015 mol), ODPA (0.015 mol) and NMP (30 g) thereto, reacted for 2 hours at 25℃to add 3-aminophenol (0.006 mol) and reacted for 48 hours at 25℃and then warmed to 50℃to drop N, N-dimethylformamide dimethyl acetal solution (0.060 mol) diluted with NMP (10 g) within 10 minutes, and reacted for 4 hours at 50℃after the drop. At 2L ethanol: water=1:3 (volume ratio) to give a white precipitate, which is filtered off, the filter cake is taken up in ethanol: water=1:3 (volume ratio) and then vacuum-dried at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin B3, and infrared absorption spectrum was measured, and imide ratio was 26.1%.

Synthesis example 22

Synthesis of alkali-soluble resin A13

Y3 (0.016 mol), 6FAP (0.016 mol), siDA (0.004 mol) and NMP (100 g) were dissolved in the same under a dry nitrogen stream, ODPA (0.020 mol), 6FDA (0.020 mol) and NMP (40 g) were added thereto and reacted at 25℃for 2 hours, then 4-aminosalicylic acid (0.008 mol) was added and reacted at 25℃for 48 hours, then xylene (10 mL) was added and azeotroped, and the temperature was raised to 150℃for 5 hours. At 2L ethanol: water=1:3 (volume ratio) to give a white precipitate, which is filtered off, the filter cake is taken up in ethanol: water=1:3 (volume ratio) and then vacuum-dried at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin a13, and infrared absorption spectrum was measured, and imide ratio was 91.0%.

Synthesis example 23

Synthesis of alkali-soluble resin A14

Diamine compound (0.032 mol), siDA (0.002 mol), pyridine (23.5 g) in the following figures were added to a three-necked flask together with NMP (100 g) and pyridine (23.5 g) under a dry nitrogen flow, and cooled to-15℃and Y6 (0.025 mol) was added dropwise to NMP (20 g) to react for 0.5 hours, then heated to 0℃and 6FDA (0.015 mol) and NMP (20 g) were added thereto together, reacted for 2 hours at 25℃and then 3-aminophenol (0.008 mol) and 48 hours at 25℃were added, then xylene (10 mL) was added to azeotropy, and heated to 150℃to react for 5 hours. At 2L ethanol: water=1:3 (volume ratio) to give a white precipitate, which is filtered off, the filter cake is taken up in ethanol: water=1:3 (volume ratio) and then vacuum-dried at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin a11, and infrared absorption spectrum was measured, and imide ratio was 94.4%.

Synthesis example 24

Synthesis of alkali-soluble resin B4

4,4' -Diaminotetrafluorodiphenyl ether (0.018 mol), 6FAP (0.016 mol), siDA (0.003 mol) in the following figures were dissolved in NMP (100 g) under a dry nitrogen stream. ODPA (0.040 mol) and NMP (40 g) were added thereto together, and reacted at 25℃for 2 hours, then 3-aminophenol (0.006 mol) was added thereto, reacted at 40℃for 2 hours, then warmed to 50℃and N, N-dimethylformamide dimethyl acetal solution (0.080 mol) diluted with NMP (10 g) was added dropwise over 10 minutes, and reacted at 50℃for 4 hours after completion of the dropwise addition. The temperature of the solution was lowered to room temperature, and precipitated in 2L of water to give a white precipitate, the precipitate was filtered, and the cake was washed with water several times, and then dried in vacuo at 50℃for 72 hours to give a powder of alkali-soluble resin B4, imide ratio.

Synthesis example 25

Synthesis of alkali-soluble resin A15

Under a dry nitrogen flow, 4 '-diaminotetrafluorodiphenyl ether (0.018 mol), 4' -diaminodiphenyl sulfone (0.015 mol), siDA (0.003 mol), pyridine (28.5 g) and pyridine (100 g) in the following figures were added together to a three-necked flask, Y1 (0.010 mol) was added dropwise to the flask at room temperature to dissolve NMP (20 g), the reaction was completed for 0.5 hours, bis (3, 4-dicarboxyphenyl) sulfone dianhydride (0.030 mol) and NMP (20 g) were added thereto together, the reaction was carried out at 25℃for 2 hours, 4-aminophenol (0.008 mol) and the reaction at 25℃for 48 hours, and the temperature was raised to 60℃to react for 6 hours. At 2L ethanol: water=1:3 (volume ratio) to give a white precipitate, which is filtered off, the filter cake is taken up in ethanol: water=1:3 (volume ratio) and then vacuum-dried at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin a15, and infrared absorption spectrum was measured, and imide ratio was 22.0%.

Synthesis example 26

Synthesis of alkali-soluble resin B5

Bis (3-amino-4-hydroxyphenyl) methane (0.018 mol), bis (3-amino-4-hydroxyphenyl) ether (0.016 mol), siDA (0.002 mol), pyridine (13.5 g) dissolved in NMP (100 g) and pyridine (20 g) were added together under a dry nitrogen flow to a three-necked flask, and cooled to-15℃Y6 (0.015 mol) dissolved in NMP (20 g) was added dropwise, followed by a reaction at 0℃for 0.5 hours, ODPA (0.025 mol) and NMP (20 g) were added together, a reaction at 25℃for 2 hours, followed by 4-aminosalicylic acid (0.008 mol) and a reaction at 25℃for 48 hours, followed by a reaction at 50℃for 10 minutes, followed by a reaction at 50℃for 4 hours with N, N-dimethylformamide dimethyl acetal solution (0.080 mol) diluted with NMP (10 g) being added dropwise. At 2L ethanol: water=1:3 (volume ratio) to give a white precipitate, which is filtered off, the filter cake is taken up in ethanol: water=1:3 (volume ratio) and then vacuum-dried at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin B5, and infrared absorption spectrum was measured, and imide ratio was 36.0%.

Example 1

Hereinafter, example 1 will be given as an example, and specific description will be given.

To an alkali-soluble resin A1 solution (10 g) of Synthesis example 7 as an alkali-soluble resin (a), a quinone diazide compound PAC-1 (0.6 g) and PAC-7 (0.6 g) as a photoacid generator (b), HMOM-TPHAP (manufactured by Benzhou chemical Co., ltd.) (1.5 g) and EP-4003S (manufactured by ADEKA) (3 g) as a thermal crosslinking agent (c), and GBL (10 g) as a solvent (d) were added, and the resultant was evaluated by the above-mentioned method.

The obtained varnish was applied to a silicon substrate by a spin coater, dried at 80℃for 8 minutes, exposed to light, and developed for 55 seconds by using a small developing device for lithography (AC 3000; manufactured by Ozehi industries, ltd.) with an aqueous solution of 2.38% by mass TMAH, and rinsed with water for 30 seconds. After development, the resultant was thermally cured at 230℃using a high-temperature inert gas oven (INH-9 CD-S; koyo Thermo Systems, manufactured by Kagaku Co., ltd.) to prepare a cured film having a film thickness of about 1.5. Mu.m; the heat curing conditions were heat curing under nitrogen atmosphere at 230℃for 60min.

The varnishes of examples 2 to 15 and comparative examples 1 to 5 were prepared in the same manner as in example 1, except that the alkali-soluble resin (a) was used separately.

The composition of the varnish for evaluation and the evaluation results are shown in table 1.

TABLE 1

According to the invention, the film can be developed with an alkaline aqueous solution, has excellent sensitivity and resolution, clear pattern, high residual film rate of unexposed parts and good thermal expansion coefficient after solidification. Suitable for use as a protective film for semiconductor elements, a planarizing layer, an interlayer insulating film, an insulating film for displays, an insulating layer for organic fields to light-emitting elements, an insulating layer for thin film transistors TFTs, and the like.

Claims

1. A positive photosensitive resin composition, characterized by comprising: 100 parts by weight of alkali-soluble resin (a), 10-30 parts by weight of photoacid generator (b), 20-60 parts by weight of thermal crosslinking agent (c) and organic solvent (d);

the alkali-soluble resin (a) comprises a diamine having the structure of formula (1) and a tetracarboxylic acid or dianhydride having the structure of formula (2);

Wherein R ₀ in the structural formula (1) represents a 2-to 4-valent organic group, and R ₁ represents-COOH or-OH;

the general formulae (a 1) and (a 2) are:

The general formula (3) is:

wherein, P and/or Q in the general formula (3) represent a reaction residue of diamine comprising the structure of the general formula (1), and X comprises a reaction residue of tetracarboxylic acid comprising the structure of the structural formula (2); y represents the reaction residue of a dianhydride or a dicyanomethylene derivative of a dianhydride of formula (a 5);

Wherein R ₁₃ represents an organic group having 1 to 20 carbon atoms;

In the general formula (3), 20-40mol% of X and/or Y in the repeating units (a 1) and (a 2) is derived from the structural formula (2), and 20mol% or more and less than or equal to X+Y or less than or equal to 40mol% is derived from the structural formula (2);

10-20mol% of P and/or Q in the repeating units (a 1) and (a 2) in the general formula (3) are derived from the structural formula (1), and 10mol% or more and less of P+Q is or less and 20mol% or less are derived from the structural formula (1);

m and n in the general formula (3) are integers of 10-50000;

At least one of the X, Y, P and Q groups of the alkali-soluble resin (a) contains fluorine atoms, the fluorine atoms account for 5-25% of the mass of the alkali-soluble resin (a), and at least one of the X, Y, P and Q groups of the alkali-soluble resin (a) contains one or more of hydroxyl, carboxyl and sulfonic groups.

2. The positive-type photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (a) comprises a polymer formula (4) of formulae (a 3) and (a 4) as main repeating units;

the general formulae (a 3) and (a 4) are:

the general formula (4) is:

Wherein R ₂ represents a hydrogen atom and/or an organic group having 1 to 20 carbon atoms;

Wherein, in the general formula (4), P and Q represent reaction residues comprising diamine of the general formula (1), and X and Y represent reaction residues comprising tetracarboxylic acid of the general formula (2);

in the general formula (4), 20-40mol% of X and/or Y in the repeating units (a 3) and (a 4) is derived from the structural formula (2), and 20mol% or more and less than or equal to X+Y or less than or equal to 40mol% is derived from the structural formula (2);

10-20mol% of the P and/or Q in the repeating units (a 3) and (a 4) in the general formula (4) are derived from the structural formula (1), and 10mol% or more and less of P+Q is or less and 20mol% or less are derived from the structural formula (1);

m and n in the general formula (4) are integers of 10-50000;

3. The positive photosensitive resin composition according to claim 1 or 2, wherein the general formula (1) is produced by reacting one or more of the following diamine compounds: p-phenylenediamine, 2' -bistrifluoromethyl-4, 4' -diaminobiphenyl, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4' -diamino-2, 2' -bistrifluoromethyl diphenyl ether.

4. The positive photosensitive resin composition according to any one of claims 1 to 2, wherein the main chain end-capping group of the alkali-soluble resin (a) has a structure represented by general formulae (5) and/or (6), wherein A is derived from a primary monoamine and B is derived from a dianhydride, and the main chain end-capping group of the alkali-soluble resin (a) is present in an amount of 0 to 50% by mole based on the total amine and/or the total anhydride

5. The positive photosensitive resin composition according to claim 4, wherein P and Q in the alkali-soluble resin (a) are one or more of an aromatic structure, a fat structure and a silicon-containing structure.

6. The positive photosensitive resin composition according to claim 1 or 2, wherein P, Q of the repeating units (a 1), (a 2), (a 3), (a 4) comprises one or more of the following reaction residues of diamine compounds: 2,2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4' -diaminodiphenyl ether, 2' -bistrifluoromethyl-4, 4' -diaminodiphenyl ether, 4' -diaminotetrafluorodiphenyl ether, 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, and diamine compounds in the following figures, and diamine compounds in the following figures;

X and Y in the repeating units (a 1), (a 3), (a 4) comprise one or more of the following reaction residues of dianhydride compounds: 2,2' -bis (3, 4-dicarboxylic acid phenyl) hexafluoropropane dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 2',3,3' -benzophenone tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, 3', 4' -diphenyl ether tetracarboxylic dianhydride, and the following structures;

7. A cured film obtained by curing the positive photosensitive resin composition according to any one of claims 1 to 6.

8. A method of patterning a cured film, comprising the steps of:

i) Coating the positive photosensitive resin composition according to any one of claims 1 to 6 on a substrate, and drying at 40 to 120 ℃ for 1 to 10min to form a positive photosensitive resin composition film;

ii) exposing the film to light under a mask;