CN112180685A

CN112180685A - Positive photosensitive resin composition, cured film and cured film pattern processing method

Info

Publication number: CN112180685A
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: 2021-01-05

Abstract

The invention provides a positive photosensitive resin composition, a cured film and an image processing method of the cured film, the positive photosensitive resin composition can be developed by an alkaline developer after exposure, the exposure sensitivity is good, the pattern is good, the resolution is high, and the thermal expansion coefficient of the cured film is good; the positive photosensitive resin composition provided by the invention comprises: 100 parts of alkali-soluble resin (a), 10-30 parts of photoacid generator (b), 20-60 parts of thermal cross-linking agent (c) and organic solvent (d), wherein the alkali-soluble resin (a) comprises diamine with a structure shown in a general formula (1) and/or tetraacid with a structure shown in a structural formula (2), the alkali-soluble resin (a) further comprises dicyanomethylene derivative of dianhydride with a structure shown in a general formula (a5), and the alkali-soluble resin (a) is polyamic acid/polyimide resin or polyamic acid ester/polyamic acid resin.

Description

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

Technical Field

The present invention relates to a positive photosensitive resin composition, and more particularly, to a positive photosensitive resin composition suitable for use as a surface protective film of a semiconductor device, an interlayer insulating film, an insulating layer of an organic field-emission light-emitting element, an insulating layer of a thin film transistor TFT, or the like, a cured film, and a method for patterning the cured film.

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, further shortens the process route compared with the traditional Polyimide (PI), and is an ideal insulating material in the fields of electronics and microelectronics.

Chinese patent publication No. CN1246389C discloses a composition in which a naphthoquinone diazide photoacid generator, a thermal crosslinking agent, and an organic solvent are added to a soluble resin such as polyamic acid, but since solubility of carboxyl groups in polyamic acid is too high, a desired pattern is hardly obtained by a dissolution-inhibiting effect of naphthoquinone diazide to alkali, and thus, in order to adjust alkali solubility of polyamic acid, polyamic acid/polyimide, polyamic acid ester/polyamic acid resin have been developed; introduction of phenolic hydroxyl groups and carboxyl groups into a resin precursor composition by an appropriate method can significantly affect the alkali solubility, coefficient of thermal expansion, transmittance, or elastic modulus of the resin precursor composition, and thus diamines and dianhydrides containing phenolic hydroxyl groups and carboxyl groups are currently being used in the synthesis of polyimides.

Chinese patent publication No. CN107406590A discloses that introducing phenolic hydroxyl group or carboxyl group into the main chain of alkali-soluble resin can impart better exposure sensitivity and higher development resolution to photosensitive resin precursor composition, but the present introduction method using more phenolic hydroxyl group in the prior art is to use biphenyl hydroxyl group-containing monomer, which has rigid skeleton structure and smaller thermal expansion coefficient, but when performing pattern processing (i-line exposure) on photosensitive resin, the problem of difficult imparting good photosensitive property to photosensitive resin is caused by energy loss due to absorption of resin itself; chinese patent publication No. CN106795283A discloses that a photosensitive resin synthesized using a hexafluoropropyl structure and a dianhydride of an alicyclic structure has high transparency and high photoreaction efficiency of a photosensitizer at an exposed portion, but the alicyclic structure has a relatively high flexibility and causes a problem of a relatively high thermal expansion coefficient of a cured film of the photosensitive resin.

At present, hydroxyl is introduced through a biphenyl structure in the process of synthesizing photosensitive resin, but energy loss is caused due to the absorption of resin on light, and the problem that good photosensitive characteristics are difficult to obtain is solved; the photosensitive resin synthesized by using dianhydride of an alicyclic structure has good photosensitive characteristics, but alicyclic chain links have high flexibility, and the problems of high thermal expansion system and high alkali solubility of a cured film of the photosensitive resin exist. Therefore, in view of the problems in the prior art, it is desired to develop a photosensitive resin composition having a moderate alkali solubility, good photosensitive properties and a low thermal expansion coefficient.

Disclosure of Invention

The problems to be solved by the invention are:

aiming at the defects in the prior art, the invention introduces the structures of general formulas (1) and (2) containing phenolic hydroxyl into the photosensitive resin, and the diamine connected by an amide bond and the dianhydride or the tetraacid with an alicyclic structure (i has weak linear absorption) are connected by the amide bond, so that the photosensitive resin composition has proper alkali solubility, good exposure sensitivity, higher development resolution and high residual film rate, and meanwhile, the main chain structure of the photosensitive resin has an amide bond structure and a benzene ring structure with strong local rigidity, so that the cured film of the photosensitive resin has the characteristics of good photosensitive property and low thermal expansion coefficient.

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

a positive photosensitive resin composition, 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 a structure of formula (1) and/or a tetracarboxylic acid or dianhydride having a structure of formula (2);

wherein R in the structural formula (1) represents 2-4 valent organic group, R₁represents-COOH or-OH;

a polymer general formula (3) in which the main chain of the alkali-soluble resin (a) includes general formulae (a1) and (a2) as main repeating units;

formula (a1), (a2) is:

wherein R is₁₃Represents an organic group having 1 to 20 carbon atoms.

The general formula (3) is:

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

alternatively, the alkali-soluble resin (a) comprises a polymer having the general formulae (4) and (a3) and (a4) as main repeating units;

formula (a3), (a4) is:

wherein R is₂Represents an organic group having 1 to 20 hydrogen atoms and/or carbon atoms,

the general formula (4) is:

wherein in the general formula (4), P and/or Q represents a reaction residue of diamine containing a structure of general formula (1), and X and/or Y represents a reaction residue of tetracarboxylic acid or dianhydride containing a structure of 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 ' -bistrifluoromethyldiphenyl ether.

Further, 20 to 40 mol% of X and/or Y in the repeating units (a1), (a2), (a3), (a4) in the general formula (3) and the general formula (4) are derived from the structural formula (2), and 20 mol% or more and 40 mol% or less of X + Y are derived from the structural formula (2); 10-20 mol% of P and/or Q in the repeating units (a1), (a2), (a3) and (a4) in the general formula (3) and the general formula (4) is derived from the structural formula (1), and 10 mol% to 20 mol% of P + Q is derived 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 formula (5) and/or (6), wherein A is derived from primary monoamine, B is derived from dianhydride, and the molar ratio of the main chain end capping group of the alkali soluble resin (a) to the total amine and/or the total anhydride is 0-50%.

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

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

Preferably, P, Q of the recurring units (a1), (a2), (a3), (a4) comprises one or more of the following reactive residues of diamine compounds: 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4 ' -diaminodiphenyl ether, 2 ' -bis trifluoromethyl-4, 4 ' -diaminodiphenyl ether, 4 ' -diaminotetrafluorodiphenyl ether, 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane, and diamine compounds in the following figures.

X and Y in the repeating units (a1), (a3), (a4) comprise one or more of the reaction residues of the dianhydride compounds: 2,2 ' -bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 3, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride, 2 ', 3, 3 ' -benzophenone tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, 3, 3 ', 4, 4 ' -diphenylether tetracarboxylic dianhydride, and the following structures.

Y in the repeating unit (a2) represents a reaction residue of a dicyanomethylene derivative of dianhydride shown in the following figure.

In a second aspect of the present invention, there is provided a film obtained by curing the positive photosensitive resin composition.

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

i) coating the positive photosensitive resin composition of any one of claims 1 to 8 on a substrate, and drying at 40 to 120 ℃ for 1 to 10min to form a positive photosensitive resin composition coating film;

ii) exposing the envelope under a mask;

iii) removing the exposed portion of the coating film using an alkali developing solution, developing and washing;

iiii) curing and drying the developed coating at the temperature of 100-400 ℃ to obtain a cured coating containing a desired pattern.

The invention has the beneficial effects that: the photosensitive resin composition has appropriate alkali solubility, better exposure sensitivity, higher development resolution and high residual film rate by introducing the structures of general formulas (1) and (2) containing phenolic hydroxyl into the photosensitive resin, and the main chain structure of the photosensitive resin has an amide bond structure and a benzene ring structure with strong local rigidity, so that the cured film of the photosensitive resin also 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 of 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 invention, the alkali soluble resin (a) contains a polymer which is expressed by a structural general formula (3) as a main component, or can be a polymer which is expressed by a structural general formula (4) as a main component, and the alkali soluble resin can obtain a polymer containing a polyimide ring under the action of heating or adding a proper catalyst, so that the heat resistance and the solvent resistance can be greatly improved;

the alkali-soluble resin (a) used in the present invention is represented by the general formula (3) of a polymer having the general formulae (a1) and (a2) as main repeating units, or the general formula (4) of a polymer having the general formulae (a3) and (a4) as main repeating units;

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

wherein, the general formula (a1), (a2), (a3) and (a4) are shown as the following figures:

in the above general formulae (3) and (4), in the repeating units (a1), (a2), (a3) and (a4), X and Y are the reaction residues of dianhydrides, and there may be mentioned: pyromellitic dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 2, 3, 5, 6-pyridinetetracarboxylic dianhydride, bicyclo [3.1.1] hept-2-ene tetracarboxylic dianhydride, 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 3,4, 9, 10-perylenetetracarboxylic dianhydride, bicyclo [2.2.2] octane tetracarboxylic dianhydride, 2, 3, 3 ', 4' -biphenyltetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, N '-bis [5, 5' -hexafluoropropane-2, 2-diyl-bis (2-hydroxyphenyl) ] bis (3, 4-dicarboxyphenyl benzamide), adamantane tetracarboxylic dianhydride, 2,2 ', 3, 3' -biphenyltetracarboxylic dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, cyclobutanetetracarboxylic dianhydride, 3, 3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, 1, 2, 3, 4-cyclopentanetetracarboxylic dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 2 ', 3, 3' -benzophenonetetracarboxylic dianhydride, 3, 3 ', 4, 4' -diphenylethertetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 1, 2, 5, 6-naphthalenetetracarboxylic dianhydride, bicyclo [2.2.1] heptanetetracarboxylic dianhydride, 2, 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, and dianhydrides having the following structures, which can be used alone or in combination of two or more kinds.

Wherein R in the above formula₃represents-O-, -C (CF)₃)₂-、-C(CH₃)₂-, -CO-, -COO-or-SO₂One of (A), (B), (C) and (C), R₄And R₅Respectively represent one of-H, -OH and-SH.

Further, the inventors have found that a tetracarboxylic acid or dianhydride compound having a phenolic hydroxyl structure and an alicyclic structure has a significant effect in adjusting the alkali solubility of the alkali-soluble resin (a) and the thermal expansion coefficient of a cured film of a photosensitive resin composition, and in the prior art, a biphenyl tetracarboxylic acid or dianhydride monomer having a phenolic hydroxyl group is used as a method for introducing a phenolic hydroxyl group into the alkali-soluble resin (a), and although the obtained cured film of a photosensitive resin has a low thermal expansion coefficient, the cured film of a photosensitive resin has a large number of benzene ring structures in the main chain structure, so that the resin itself absorbs light strongly and energy is lost, and thus it is difficult to exhibit excellent photosensitivity, and the cured film of a photosensitive resin synthesized using a biphenyl dianhydride or tetracarboxylic acid having a phenolic hydroxyl group exhibits good transparency and excellent photosensitivity, however, because the main chain molecule is a flexible unit-alicyclic structure, the CTE value of the cured film of the photosensitive resin is often high, so that the cured film of the photosensitive resin cannot show good mechanical strength, in the embodiment of the invention, in order to have good photosensitivity and low thermal expansion coefficient at the same time, the number of phenolic hydroxyl groups in dianhydride or tetracarboxylic acid molecules and the amount of benzene rings and alicyclic structures in the molecules are adjusted through reasonable design, so that the cured film not only has a rigid benzene ring structure but also has an alicyclic structure capable of improving photosensitivity, and a tetracarboxylic acid compound (2) is synthesized in the embodiment of the invention;

the specific synthesis method comprises the following steps:

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

adding a certain amount of nickel powder (15-20mmol), maleic anhydride (25-30mmol) and dimethyl ether (10-30mL) into a three-neck flask, introducing inert gas for protection and stirring for 1h, then dissolving a certain amount of the product (10-20mmol) in the dimethyl ether, then slowly adding the solution into the three-neck flask through an addition funnel, stirring for 1-2h at room temperature, slightly heating the reaction mixture, turning green within 5-10min after the addition starts, continuing to react for 12-36h at room temperature, then pouring the solution into 3% hydrochloric acid (100mL), and then extracting the hydrochloric acid solution by using dichloromethane; the dichloromethane extract was washed with sodium bisulfite solution to remove 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 when a film is developed with an aqueous alkaline solution, the film has appropriate hydrophobicity at the interface, penetration into the interface can be effectively suppressed, and the solubility of the polymer in an organic solvent can be improved, and the following may be mentioned the X or Y structures of some fluorine atom-containing dianhydrides, as shown in the following figure:

by-CF₃and-C (CF)₃)₂Fluorine atom is introduced in a group mode, and the group volume is larger, so that the stacking density of macromolecules can be obviously reduced, the alkali-soluble resin (a) obtains higher organic solvent solubility, and simultaneously, the introduction of the fluorine atom can also reduce the charge transfer effect inside and outside molecules, so that the alkali-soluble resin (a) has lighter color and higher transparency, and moreover, the fluorine atom has low electron polarization rate, often shows lower cohesive energy and surface free energy, so that the alkali-soluble resin (a) has lower cohesive energy and surface free energyIn view of the above advantages, the dianhydride is preferably selected from the group consisting of: 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl]Propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) hexafluoropropane dianhydride, 3, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, cyclobutanetetracarboxylic dianhydride, 2 ', 3, 3 ' -benzophenonetetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, 2-bis (2, 3-dicarboxyphenyl) hexafluoropropane dianhydride, 4, 4 ' -hexafluoroisopropylidene diphthalic dianhydride, 3, 3 ', 4, 4 ' -tetracarboxylic diphenyl ether dianhydride, 3, 3 ', 4, 4 ' -diphenyl ether tetracarboxylic dianhydride and the following structures:

the introduction of fluorine atoms can bring about good solubility of organic solvents, good transparency and excellent hydrophobic and oleophobic performance of interfaces, and good effect of preventing interface penetration and proper dissolution speed are obtained, but excessive fluorine atoms can increase the thermal expansion coefficient of the alkali-soluble resin (a) and have poor adhesion with other materials, so that the fluorine atoms in the embodiment of the invention preferably account for 5-25% of the mass of the alkali-soluble resin (a).

Among the dianhydrides mentioned above, further preferred are: 2,2 ' -bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 3, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride, 2 ', 3, 3 ' -benzophenone tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, 3, 3 ', 4, 4 ' -diphenyl ether tetracarboxylic dianhydride, and dianhydride compounds in the following figures.

Preferably, for the above formula (3), 20 to 40 mol% of X or Y in the recurring units (a1), (a2) is derived from formula (2), and 20 mol% or more and X + Y or less are derived from formula (2).

Preferably, for the above formula (4), 20 to 40 mol% of X or Y in the recurring units (a3), (a4) is derived from formula (2), and 20 mol% or more and 40 mol% or less of X + Y is derived from formula (2).

For the above general formula (3), wherein Y in the repeating unit (a2) can also be obtained by reacting a dicyanomethylene derivative of dianhydride as a monomer component with a diamine compound, wherein Y is preferably selected from the dicyanomethylene derivatives of dianhydride of the following structure, as shown in the structural formula (a5), (a5) wherein the dicyanomethylene derivatives of two dianhydrides are isomers, often present as a mixture during synthesis, but have the same structure in the product that reacts with diamine to form imide, and thus the following structures can be used alone or in combination of two or more;

wherein R in the structural formula (a5)₁₃Represents a compound containing-O-, -C (CF)₃)₂-、-C(CH₃)₂-, -CO-, -COO-or-SO₂-an organic group of one of the groups having 1 to 20 carbon atoms;

in the present example, dianhydride (0.01-0.05mol) and dicyanomethane (0.01-0.05mol) were added to a three-necked flask and dissolved in 500mL of Tetrahydrofuran (THF) at 200-. Dropwise adding diisopropylamine (0.010-0.100mol) within 1-3h, continuously stirring at room temperature for 20-24h after dropwise adding is finished to obtain yellow precipitate, filtering, washing a filter cake with THF, and then vacuum-drying at 100 ℃ for 2-3 days;

taking 3-5mol of the dried filter cake, dissolving the filter cake in 50mL of dichloromethane, introducing nitrogen, and then adding 1.0-2.0mL of phosphorus oxychloride (POCl)₃) Then stirring and reacting for 20-24h at room temperature under nitrogen, filtering, washing a filter cake with dried dichloromethane to obtain a crude product, recrystallizing the crude product in acetic anhydride,and then dried to give the dicyanomethylene derivative of dianhydride (the mixture of the two isomers, when reacted with diamine, gives the imide product the same structure and therefore does not require isolation).

Further, the dicyanomethylene derivative of dianhydride of formula (a5) synthesized by the above synthesis method is preferably of the structure shown in the following figure.

Wherein R is₃Indicates the selection of-O-, -C (CF)₃)₂-、-C(CH₃)₂-, -CO-, -COO-or-SO₂-one of the groups;

R₄and R₅Respectively represents one of-H, -OH and-SH groups; when the resin is synthesized, the ratio (m/n) of the repeating units (a1) and (a2) in the alkali-soluble resin (a) can be obtained quantitatively by quantitatively controlling the amounts of the dicyanomethylene derivative of the dianhydride with the structural formula (a5) in (a2) and the dianhydride in (a1), and further the amounts of the phenolic hydroxyl, amido bond and alicyclic structure in the repeating units (a1) and (a2) are controlled, so that the purposes of adjusting the alkali solubility, photosensitive property and thermal expansion coefficient of the resin composition are achieved.

In the general formula (1), R₀Preferably one of p-phenylenediamine, 2 ' -bistrifluoromethyl-4, 4 ' -diaminobiphenyl (TFMB), 2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF), 4 ' -diamino-2, 2 ' -bistrifluoromethyldiphenyl ether:

when R is₀Selected from p-phenylenediamine, R₁When — OH, the structure of formula (1) is:

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

stirring 0.5-1.0 mol of 2, 5-dihydroxy-1, 4-dibenzoic acid in a certain amount of thionyl chloride at room temperature for 2-4h, filtering, and drying the filtrate under reduced pressure to obtain 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 freshly obtained dark-brown solid in 100mL of acetone, reacting at room temperature for 4-6h after dropwise adding, filtering out precipitated white solid, and drying at 50 ℃ in vacuum to obtain the diamine.

When R is₀Selectively represents 2,2 '-bis-trifluoromethyl-4, 4' -diaminobiphenyl (TFMB), R₁When — OH, the structure of formula (1) is:

when R is₀Selectively represents 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF), R₁When — OH, the structure of formula (1) is:

when R is₀Selected from 4, 4 '-diamino-2, 2' -ditrifluoromethyl diphenyl ether, R₁When — OH, the structure of formula (1) is:

when R is₀Preparation method and R for selecting 2,2 ' -bis (trifluoromethyl) -4, 4 ' -diaminobiphenyl (TFMB), 2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) and 4, 4 ' -diamino-2, 2 ' -bistrifluoromethyl diphenyl ether₀The same applies to the selection of p-phenylenediamine, except that p-phenylenediamine is replaced with the above three diamines.

P and/or Q in the repeating units (a1), (a2), (a3), (a4) in the general formulae (3) and (4) of the alkali-soluble resin (a) further contains 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, 2, 6-naphthalenediamine, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) fluorene, Aromatic diamines such as 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 and 2,2 ' -bis (trifluoromethyl) -4, 4 ' -diaminobiphenyl, 2 ' -bis (trifluoromethyl) -5, 5 ' -dihydroxybenzidine, 3,4 ' -diaminodiphenyl ether, 3,4 ' -diaminodiphenylmethane, 4, 4 ' -diaminodiphenylmethane, 3,4 ' -diaminodiphenylsulfone, 4, 4 ' -diaminodiphenylsulfone, and mixtures thereof, 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, diamines of the following structures, and the like. These may be used alone or in combination of two or more.

In the above diamine compound, R₄～R₁₂In addition toR₆And each independently represents one or more combinations selected from-H, -OH and-SH groups, R₆Indicates the selection of-O-, -C (CF)₃)₂-、-C(CH₃)₂-, -CO-, -COO-or-SO₂-one of the groups;

by adjusting R₄～R₁₂The type and ratio of the group can be adjusted to adjust the dissolution rate of the alkali water of the structural formula (3) to obtain a photosensitive resin composition having an appropriate dissolution rate, and in order to obtain an appropriate dissolution rate of the alkali water, among the diamine compounds: 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, 2,2 '-bistrifluoromethyl-4, 4' -diaminobiphenyl, 4 '-diamino-2, 2' -bistrifluoromethyldiphenyl ether, 2,2 '-bistrifluoromethyl-4, 4' -diaminodiphenyl ether, 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4' -diaminotetrafluorodiphenyl ether, and diamines having the structures shown below, and the like.

In the above diamine compound, R₄～R₁₂In addition to R₆And each independently represents one or more combinations selected from-H, -OH and-SH groups, R₆Indicates the selection of-O-, -C (CF)₃)₂-、-C(CH₃)₂-, -CO-, -COO-or-SO₂-one of the groups;

among the above diamines, further preferred are: 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4 ' -diaminodiphenyl ether, 2 ' -bis trifluoromethyl-4, 4 ' -diaminodiphenyl ether, 4 ' -diaminotetrafluorodiphenyl ether, and a diamine compound in the following figures.

Wherein, for the general formula (3), 10 to 20 mol% of P or Q in the repeating units (a1), (a2) is derived from the structural formula (1), and 10 mol% or more and 20 mol% or less of P + Q is derived from the structural formula (1).

Wherein, for the general formula (4), 10 to 20 mol% of P or Q in the repeating units (a3), (a4) is derived from the structural formula (1), and 10 mol% or more and 20 mol% or less of P + Q is derived from the structural formula (1).

Further, since fluorine atoms are introduced in the examples of the present invention, the adhesion of the resin composition to the substrate is reduced to some extent, and in order to neutralize this adverse effect and improve the adhesion of the resin composition to the substrate, in the embodiment of the present invention, P and/or Q in the alkali-soluble resin (a) further contains a diamine having a siloxane structure, wherein the molar percentage of the diamine having a siloxane structure in P and/or Q in the general formula (3) and the general formula (4) is 0 to 10 mol%, within a range in which the heat resistance is not reduced; specifically, as the diamine component, there can be mentioned: diamines such as 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane (SiDA) and bis (p-aminophenyl) octamethylpentasiloxane (SiDA), and 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane (SiDA) is preferable.

In the terminal structure of the polymer having the structural unit represented by the general formula (5), A in the general formula (5) is derived from a primary monoamine which is an end-capping agent; preferred examples of the primary monoamine as the end-capping agent include 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, and 6-aminosalicylic acid. The primary monoamines may be used singly or in combination of two or more, and the monoprimary amine as the end-capping agent accounts for 0 to 50 mol%, particularly preferably 5 to 30 mol%, of the total amine components

In the terminal structure of the polymer having the structural unit represented by the general formula (6), B is derived from dianhydride of a capping agent; the end-capping agent may be phthalic anhydride, maleic anhydride, nadic anhydride, or cyclohexane anhydride, and these dianhydrides may be used alone or in combination of two or more. The dianhydride as the end-capping agent accounts for 0 to 50 mol%, particularly preferably 5 to 30 mol%, of the total anhydride components.

Photoacid generators (b)

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

Specific examples of the phenolic hydroxyl compound which may be mentioned are the structures shown in the following figures:

as the quinonediazide compound, any one or a combination of plural kinds of naphthoquinonediazidosulfonate structures are preferably used in the molecular structure. Specific examples thereof include the following commercial photoacid generators PAC-1 to PAC-20, and the following may be used in any one or a combination of plural kinds.

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

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 undergo 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 an epoxy compound (c1) and an alkoxy/methylol compound (c 2); among them, the (c1) Epoxy compound is preferably a compound having two or more Epoxy groups in one molecule, and examples thereof include, but are not limited to, bisphenol a type Epoxy resins, bisphenol a type oxetane resins, bisphenol F type Epoxy resins, bisphenol F type oxetane resins, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Epoxy group-containing silicones such as polymethyl (glycidyloxypropyl) siloxane, and the like, and specific examples thereof include, but are not limited to, products of systems such as EPICLON and EXA in the japanese ink chemical industry, bisphenol a type Epoxy compounds of Epikote series by Yuka Shell Epoxy co. (c2) The alkoxy/hydroxymethyl compound preferably contains two or more alkoxy and/or hydroxymethyl functional groups in one molecule of 2-8, and can be exemplified by DML, TriML, DMOM, HMOM, TMOM, etc., and MX, MW series of Sanhe chemical. The positive photosensitive resin composition of the present invention contains at least one of the thermal crosslinkers.

The amount of the thermal crosslinking agent (c) added is 15 to 100 parts by weight, preferably 20 to 60 parts by weight, based on 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 organic solvent that can be used 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, amyl alcohol, γ -butyrolactone, N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, and dimethyl sulfoxide, 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 provided by the present invention.

< Pattern processing method >

The following describes in detail a pattern processing method for forming a resin pattern using the positive photosensitive resin composition of the present invention.

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 coat the coating so that the film thickness after drying is 0.5 to 50 μm; drying with oven, heating plate, infrared oven, etc. at 40-120 deg.C for 1-10min or stage programmed heating for drying to volatilize 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 on which constituent materials of circuits are disposed.

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

After exposure, the exposed portion of the film is removed using a developer, preferably an aqueous solution of an alkaline compound such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, dimethylamine, dimethylaminoethanol, cyclohexylamine, ethylenediamine, etc.; in addition, one or more combinations 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; the conditions such as development time, development temperature, and development step may be conditions under which the exposed portion is removed; after the development, the film is preferably rinsed with water, more preferably rinsed with an aqueous solution of an alcohol or ester of ethanol, isopropanol, or ethyl lactate; before developing, if necessary, baking the envelope at 60-150 deg.C, preferably 60-120 deg.C for 5 s-60 min; after rinsing, the coating is dried by heating at 60-200 deg.C for 1-60 min.

After exposure, development and rinsing, the positive photosensitive resin composition is subjected to staged temperature programmed/constant temperature heat treatment at the temperature of 100-400 ℃ and is cured to form a cured film; examples of the temperature-raising/constant-temperature heat treatment method include a method in which the temperature is raised from room temperature at a rate of 5 ℃/min, then constant-temperature heat treatment is carried out at 120 ℃ and 180 ℃ for 30min, and then constant-temperature heat treatment is carried out at 250 ℃ for 2 hours; or heating from room temperature to 250 ℃ within 2h at the heating rate of 5 ℃/min, and then carrying out constant-temperature heat treatment at 250 ℃ for 2 h; the heating/constant temperature heat treatment is carried out under normal pressure, nitrogen or vacuum; curing to obtain a cured film with a desired pattern and having heat resistance.

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

Examples

The present invention will be described below by way of examples, but the present invention is not limited to these examples. First, the evaluation methods in the synthesis examples and comparative examples will be described; for the evaluation, a resin composition (hereinafter referred to as a varnish) which had been filtered with a1 μm polytetrafluoroethylene filter in advance was used.

Imidization ratio of synthetic resin

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

Production of developing film

A positive photosensitive resin composition (varnish) was applied onto a 6-inch silicon wafer so that the prebaked film thickness was 10 μm, and then prebaked at 120 ℃ for 4min using a hot plate (SCW-636; Dainippon Screen production Co., Ltd.) to obtain a prebaked film of a photosensitive polyimide; using a small developing device (AC3000) for lithography to form a line of 0-1000 mJ/cm in i (365nm), h (405nm) and g (436nm)²Exposure dose of (2) at 10mJ/cm²Step pitch of to the filmCarrying out exposure; after exposure, the prebaked film of the photosensitive polyimide was developed in a 2.38 mass% aqueous solution of tetramethylammonium (hereinafter referred to as TMAH, manufactured by the multi-mole chemical industry) for 90 seconds, and then rinsed with water to obtain a developed film having an isolated pattern of 10 μm.

Calculation of residual film rate

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

Sensitivity of the device

A varnish was applied to a 6-inch silicon wafer by a spin coating method using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Limited) and prebaked at 120 ℃ for 3 min; exposure was performed using an i-line stepper NSR-2005i9C (manufactured by Nikon); after exposure, development was repeated 2 times by spin immersion (10 s for the discharge time of the developer and 40s for the spin immersion time) using a developing apparatus of ACT-8 using 2.38 wt% TMAH, and then the substrate was washed with pure water and spun, and the minimum exposure amount when the exposed portion was completely dissolved was used as the sensitivity.

Resolution ratio

A cured film of the composition was prepared by the method described in example 1, using a double-side alignment single-side exposure apparatus (mask aligner PEM-6M; manufactured by Union Optical Co., Ltd.) and a gray scale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; manufactured by Optoline International Co., Ltd.) through pattern exposure using i (365nm), h (405nm) and g (436nm) lines of an ultra-high pressure mercury lamp, followed by development using a photolithography small-sized developing apparatus (AD-2000; manufactured by Gekko industries Co., Ltd.), and then using a high temperature inert oven (INH-9 CD-S; manufactured by Koyo Thermo Systems Co., Ltd.); the pattern of the cured film thus produced was observed using an FPD/LSI inspection microscope (OPTIPHOT-330; manufactured by UNION Co., Ltd.); the minimum pattern size of the line-and-space pattern obtained without residue was defined as the resolution.

Evaluation of pattern of developed film

With respect to the photosensitive resin composition film formed by development, the viscosity of an unexposed portion and the residue of an exposed portion were visually observed; the development film was judged to be good when no pattern was found to be defective, and was judged to be bad when the unexposed area was sticky or the exposed area was left free.

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 for 3min with a 120 ℃ hot plate (Tokyo Electron Limited, manufactured by coating and developing apparatus Act-8) to obtain a resin film.

Heating the pre-baked coating film to 300 ℃ at a rate of 3.5 ℃/min under a nitrogen stream (oxygen concentration of 20ppm or less), maintaining the temperature for 30min, and cooling the coating film to 50 ℃ at a rate of 5 ℃/min to produce a resin laminate; next, a notch was cut into the periphery of the obtained resin laminate, and the resin laminate was immersed in hot water at 65 ℃ for 1 to 4 minutes, and then physically pulled to peel the resin laminate from the substrate, followed by air drying.

The glass resin laminate was measured under a nitrogen stream using a thermomechanical analyzer (EXSTAR 6000TMA/SS6000, manufactured by SII Nano Technology Co., Ltd.); the temperature raising method is carried out under the following conditions: in the 1 st stage, raising the temperature to 150 ℃ at the temperature raising rate of 5 ℃/min, removing the adsorbed water of the sample, and in the 2 nd stage, air-cooling to room temperature at the temperature lowering rate of 5 ℃/min; in stage 3, the measurement is carried out at a temperature rise rate of 5 ℃/min, and the coefficient of linear expansion (CTE) is determined from the average value of the coefficients of linear expansion at 50 to 200 ℃. The evaluation was carried out by the following evaluation method.

Good (A): 35 ppm/DEG C or less

Good (B): more than 35 ppm/DEG C and less than 40 ppm/DEG C

Failure (C): above 40 ppm/deg.C

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

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

THF: tetrahydrofuran (THF)

DIPA: diisopropylamine

TFMB: 2,2 '-bis-trifluoromethyl-4, 4' -diaminobiphenyl

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

ODA: 4, 4' -diaminodiphenyl ether

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

NMP: n-methyl pyrrolidone

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

ODPA: 3, 3 ', 4, 4' -Diphenyl Ether Tetraformic dianhydride

Synthesis example 1

Synthesis of dicyanomethylene derivative Y1 of dianhydride of aromatic tetracarboxylic acid

Inventive example A three-necked flask was charged with 6FDA (0.0245mol) and dicyanomethane (0.049mol) dissolved in 300mL of THF. DIPA (0.099mol) was added dropwise over 1h, and after addition, 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 under vacuum at 100 ℃ for 2 days.

3.36mol of the above-mentioned dried cake are taken, dissolved in 50mL of dichloromethane, purged with nitrogen and then 1.2mL of POCl are added₃Then the reaction is stirred at room temperature for 20h under nitrogen, filtered, the filter cake is washed with dry dichloromethane to obtain a crude product, which is recrystallized from acetic anhydride and then dried to obtain the dicyanomethylene derivative Y1 of 6FDA (the mixture of the two isomers has the same structure in the reaction with diamine to give imide, so no separation is required).

Synthesis example 2

Synthesis of aminophenol Compound Y2

Stirring 0.6mol of 2, 5-dihydroxy-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; dissolving 0.11mol of p-phenylenediamine in 200mL of acetone and 0.3mol of propylene oxide; a solution prepared by dissolving 0.05mol of the brown solid obtained just in 100mL of acetone is dropwise added into the solution; 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 differs from that of Y2 in that p-phenylenediamine is replaced with TFMB, and the aminophenol compound Y3 is obtained without changing other conditions.

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 not changed to obtain the aminophenol compound Y4.

Synthesis example 5

Synthesis of aminophenol Compound Y5

The synthesis method of the aminophenol compound Y5 is different from that of Y2 in that p-phenylenediamine is replaced by 4, 4 '-diamino-2, 2' -ditrifluoromethyldiphenyl ether, and the aminophenol compound Y5 is obtained without changing other conditions.

Synthesis example 6

Synthesis of alicyclic structure-containing tetracarboxylic acid Compound chloro product Y6

Adding a polyhydroxy compound (36.20mmol) and 300mL of diethyl ether in the following figure into a three-necked bottle, cooling to 0 ℃ in an ice bath, then dropwise adding phosphorus tribromide (434mmol) into the three-necked bottle, slowly heating to room temperature after dropwise adding, stirring for reacting for 12 hours, pouring a product into ice water, repeatedly washing with brine and extracting with diethyl ether twice, drying an diethyl ether extraction phase with magnesium sulfate, and then removing the diethyl ether in vacuum to obtain a brominated product.

Nickel powder (17.90mmol), maleic anhydride (28.64mmol) and dimethyl ether (20mL) were added to a three-necked flask, argon was turned on and stirred for 1h, then the above brominated product (14.21mmol) was dissolved in dimethyl ether (20mL) and slowly added to the three-necked flask through an addition funnel, stirred at room temperature for 1h, the reaction mixture started to warm slightly and turned green within 5-10min after starting the addition, continued to react at room temperature for 24h, 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 sodium bisulfite solution to remove residual iodine, then dried over anhydrous disodium sulfate, and dichloromethane was removed in vacuo to give the tetracarboxylic acid compound in the lower graph.

0.1mol of the above tetracarboxylic acid was stirred in 110mL of thionyl chloride at room temperature for 2 hours, and after filtration, the filtrate was dried under reduced pressure to obtain Y6 as a yellow solid.

Synthesis example 7

Synthesis of alkali-soluble resin (a) A1

Under a dry nitrogen flow, ODA (0.008mol), SiDA (0.002mol,), Y2(0.010mol), 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (0.018mol), NMP (100g) and pyridine (9.5g) are added into a three-neck flask together, the temperature is reduced to-15 ℃, Y6(0.010mol) is dropwise dissolved in NMP (10g), the reaction is completed for 0.5h, then the temperature is increased to 0 ℃, Y1(0.030mol) is dissolved in NMP (30g) and added, the reaction is performed for 2h at 25 ℃, then 3-aminophenol (0.004mol) is added, the reaction is continued for 24h at 25 ℃, then the temperature is increased to 40 ℃ for 2h, and then the temperature is increased to 60 ℃ for 2 h. In 2L ethanol: water was precipitated in 2:1 (volume ratio) solvent to give a white precipitate, which was filtered and the filter cake was purified with ethanol: washing with 2:1 (volume ratio) of water for several times, and then vacuum drying at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A1, and measuring an infrared absorption spectrum, the imide rate was 85.0%.

Synthesis example 8

Synthesis of alkali-soluble resin A2

Under a dry nitrogen flow, ODA (0.008mol), SiDA (0.002mol), Y2(0.010mol), bis (3-amino-4-hydroxyphenyl) hexafluoropropane (0.018mol), NMP (100g) and pyridine (28.5g) are added into a three-neck flask together, the temperature is reduced to-15 ℃, Y6(0.030mol) is dropwise dissolved in NMP (20g), the reaction is completed by 0.5h, the temperature is raised to 0 ℃, 6FDA (0.010mol) is dissolved in NMP (10g) is added, the reaction is carried out for 2h at 25 ℃, 3-aminophenol (0.004mol) is added, the reaction is continued for 24h at 25 ℃, the reaction is further raised to 40 ℃ for 2h, and the reaction is carried out for 2h at 60 ℃. In 2L ethanol: water was precipitated in 2:1 (volume ratio) solvent to give a white precipitate, which was filtered and the filter cake was purified with ethanol: washing with 2:1 (volume ratio) water several times, then vacuum drying at 50 ℃ for 72h to obtain a powder of alkali-soluble resin A2, and measuring the infrared absorption spectrum, the imide rate is 72.0%.

Synthesis example 9

Synthesis of alkali-soluble resin A3

Under a dry nitrogen flow, the amine derivative of bis (3-amino-4-hydroxyphenyl) hexafluoropropane (0.025mol), Y3(0.010mol), SiDA (0.002mol), dissolved in NMP (100g), and pyridine (19g) in the following figure were added together to a three-necked flask, and cooled to-15 ℃, Y6(0.020mol) dissolved in NMP (20g) was added dropwise, the reaction was completed by 0.5h, and then heated to 0 ℃, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride (0.020mol) and NMP (20g) were added thereto, reacted at 25 ℃ for 2h, then 3-aminophenol (0.006mol) was added, reacted at 25 ℃ for 48h, and then heated to 40 ℃ for 2 h. In 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a ratio of 1:3 (volume ratio) for several times, and then vacuum-drying at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A3, and measuring an infrared absorption spectrum, the imide rate was 52.0%.

Synthesis example 10

Synthesis of alkali-soluble resin A4

Y4(0.015mol), ODA (0.020mol), SiDA (0.002mol) and NMP (100g) are dissolved in a dry nitrogen flow, pyridine (19g) is added into a three-neck flask together, the temperature is reduced to-15 ℃, Y6(0.025mol) is dropwise added and dissolved in NMP (20g), the reaction is completed for 0.5h, then the temperature is raised to 0 ℃,2 ', 3, 3' -benzophenone tetracarboxylic dianhydride (0.015mol) and NMP (20g) are added together, the reaction is carried out for 2h at the temperature of 25 ℃, then 3-aminobenzoic acid (0.006mol) and 25 ℃ are added for 48h, and then the reaction is carried out for 6h at the temperature of 40 ℃. In 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a ratio of 1:3 (volume ratio) for several times, and then vacuum-drying at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A4, and measuring an infrared absorption spectrum, the imide rate was 61.6%.

Synthesis example 11

Synthesis of alkali-soluble resin A5

Under a dry nitrogen flow, 2 '-bis (trifluoromethyl) -4, 4' -diaminodiphenyl ether (0.010mol), 6FAP (0.017mol), Y3(0.010mol), SiDA (0.002mol), dissolved in NMP (100g), pyridine (14.8g) was added, the temperature was reduced to-15 ℃, Y6(0.015mol) was dropwise dissolved in N-methylpyrrolidone NMP (20g), the reaction was completed for 0.5h, then the temperature was increased to 0 ℃, cyclobutane tetracarboxylic dianhydride (0.015mol), 3 ', 4, 4' -tetracarboxylic acid diphenyl ether dianhydride (0.015mol), and NMP (20g) were added thereto together, the reaction was performed for 2h at 25 ℃, 4-aminophenol (0.002mol) was then added, the reaction was performed for 48h at 25 ℃, and then the reaction was performed for 4h at 40 ℃. In 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a volume ratio of 1:3 for several times, and then vacuum-drying at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A5, and measuring an infrared absorption spectrum, the imide rate was 36.9%.

Synthesis example 12

Synthesis of alkali-soluble resin A6

Under a dry nitrogen flow, 4' -diamino tetrafluoro diphenyl ether (0.018mol), Y4(0.015mol), SiDA (0.003mol), dissolved in NMP (100g) and pyridine (28.5g) in the following figure are added into a three-neck flask together, the temperature is reduced to-15 ℃, Y6(0.030mol) dissolved in NMP (20g) is added dropwise, the reaction is completed for 0.5h, then the temperature is increased to 0 ℃, dianhydride (0.010mol) and NMP (20g) in the following figure are added together, the reaction is carried out for 2h at the temperature of 25 ℃, 4-aminophenol (0.008mol) and the reaction is carried out for 48h at the temperature of 25 ℃, and the reaction is carried out for 6h at the temperature of 60 ℃. In 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a volume ratio of 1:3 for several times, and then vacuum-drying at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A6, and measuring an infrared absorption spectrum, the imide rate was 49.5%.

Synthesis example 13

Synthesis of alkali-soluble resin A7

Under a dry nitrogen flow, Y5(0.034mol), SiDA (0.003mol), dissolved in NMP (100g), and pyridine (9.5g) are added together into a three-neck flask, the temperature is reduced to-15 ℃, Y6(0.015mol) dissolved in NMP (10g) is added dropwise, the reaction is completed by 0.5h dropwise, then the temperature is increased to 0 ℃, 6 FAP-derived dianhydride (0.025mol) in the following figure and NMP (30g) are added together, the reaction is carried out for 2h at 25 ℃, then 3-aminophenol (0.006mol) is added, the reaction is carried out for 48h at 25 ℃, and then the reaction is carried out for 6h at 60 ℃. In 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a ratio of 1:3 (volume ratio) for several times, and then vacuum-drying at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A7, and measuring an infrared absorption spectrum, the imide rate was 37.1%.

Synthesis example 14

Synthesis of alkali-soluble resin A8

Under a dry nitrogen flow, fluorine-containing arylamine (0.008mol), Y5(0.010mol), 6FAP (0.014mol), SiDA (0.002mol), dissolved in NMP (100g) and pyridine (28.5g) in the following figures are added into a three-neck flask together, cooled to-15 ℃, dropwise added with Y6(0.030mol) dissolved in NMP (30g), reacted for 0.5h, heated to 0 ℃, added with 6FAP derived dianhydride (0.010mol) and NMP (10g) in the following figures, reacted for 2h at 25 ℃, added with 3-aminobenzoic acid (0.012mol), reacted for 48h at 25 ℃, and then heated to 60 ℃ for 6 h. In 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a ratio of 1:3 (volume ratio) for several times, and then vacuum-drying at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A8, and measuring an infrared absorption spectrum, the imide rate was 74.1%.

Synthesis example 15

Synthesis of alkali-soluble resin A9

Under a dry nitrogen flow, Y4(0.038mol), SiDA (0.002mol), dissolved in NMP (100g) and pyridine (8.5g) are added into a three-neck flask together, the temperature is reduced to-15 ℃, Y6(0.010mol) dissolved in NMP (30g) is dripped, the reaction is finished for 0.5h, then the temperature is increased to 0 ℃, 6FDA (0.031mol) and NMP (40g) are added together, the reaction is carried out for 2h at 25 ℃, the reaction is carried out for 48h at 25 ℃, the temperature is increased to 40 ℃ for 2h, then xylene (10mL) is added for azeotropy, and the temperature is increased to 150 ℃ for 5 h. In 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a ratio of 1:3 (volume ratio) for several times, and then vacuum-drying at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A9, and measuring an infrared absorption spectrum, the imide ratio was 91.0%.

Synthesis example 16

Synthesis of alkali-soluble resin A10

In the following figure, a diamine compound (0.024mol), Y5(0.014mol), SiDA (0.002mol), dissolved in NMP (100g), and pyridine (23.5g) were added together to a three-necked flask, the temperature was lowered to-15 ℃ and Y6(0.025mol) dissolved in NMP (20g) was added dropwise, the reaction was completed by 0.5h, then the temperature was raised to 0 ℃ and 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride (0.015mol) and NMP (20g) were added together, the reaction was performed at 25 ℃ for 2h and at 25 ℃ for 48h, then xylene (10mL) was added thereto for azeotropy, and the reaction was performed at 150 ℃ for 5h under a dry nitrogen stream. In 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a ratio of 1:3 (volume ratio) for several times, and then vacuum-drying at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A10, and measuring an infrared absorption spectrum, the imide rate was 92%.

Synthesis example 17

Synthesis of alkali-soluble resin A11

In the following figure, diamine compound (0.012mol), Y5(0.022mol), SiDA (0.002mol), dissolved in NMP (100g), and pyridine (23.5g) were added together to a three-necked flask, the temperature was reduced to-15 deg.C, Y6(0.035mol) dissolved in NMP (20g) was added dropwise, the reaction was completed by dropping for 0.5h, then the temperature was increased to 0 deg.C, 6FDA (0.005mol) and 20g (NMP) were added together thereto, the reaction was carried out at 25 deg.C for 2h, then 3-aminophenol (0.008mol) was added thereto, the reaction was carried out at 25 deg.C for 48h, then xylene (10mL) was added thereto for azeotropic distillation, and the temperature was increased to 150 deg.C for 5h under a. In 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a ratio of 1:3 (volume ratio) for several times, and then vacuum-drying at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A11, and measuring an infrared absorption spectrum, the imide ratio was 93.4%.

Synthesis example 18

Synthesis of alkali-soluble resin A12

Under a dry nitrogen flow, Y3(0.016mol), 6FAP (0.016mol), SiDA (0.004mol), NMP (100g), pyridine (13.5g) are added into a three-neck flask together, the temperature is reduced to-15 ℃, Y6(0.02mol) is dropwise added and dissolved in NMP (20g), the reaction is completed by dropping for 0.5h, then the temperature is increased to 0 ℃, ODPA (0.02mol) and NMP (20g) are added together, the reaction is carried out for 2h at 25 ℃, 4-aminosalicylic acid (0.008mol) and the reaction is carried out for 48h at 25 ℃, then xylene (10mL) is added for azeotropy, and the temperature is increased to 150 ℃ for 5 h. In 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a volume ratio of 1:3 for several times, and then vacuum-drying at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A12, and measuring an infrared absorption spectrum to obtain an imide ratio of 89.0%.

Synthesis example 19

Synthesis of alkali-soluble resin B1

Under a dry nitrogen flow, Y5(0.018mol), 6FAP (0.016mol), SiDA (0.002mol), NMP (100g), pyridine (13.5g) are added into a three-neck flask together, the temperature is reduced to-15 ℃, Y6(0.015mol) is dropwise added and dissolved in NMP (20g), the reaction is completed by dropwise addition for 0.5h, then the temperature is increased to 0 ℃, ODPA (0.025mol) and NMP (20g) are added together, the reaction is performed for 2h at 25 ℃, 4-aminosalicylic acid (0.008mol) and the reaction is completed by 25 ℃ for 48h, the temperature is increased to 50 ℃, N-dimethylformamide dimethyl acetal solution (0.080mol) diluted by NMP (10g) is dropwise added within 10min, and the reaction is completed for 4h at 50 ℃; in 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a ratio of 1:3 (volume ratio) for several times, and then vacuum-drying at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin B1, and measuring an infrared absorption spectrum, the imide rate was 39.0%.

Synthesis example 20

Synthesis of alkali-soluble resin B2

Under a dry nitrogen flow, Y3(0.021mol), ODA (0.014mol), SiDA (0.001mol), dissolved in NMP (100g), pyridine (9g) are added into a three-neck flask together, the temperature is reduced to-15 ℃, Y6(0.010mol) is dropwise dissolved in NMP (10g), the reaction is completed for 0.5h, then the temperature is increased to 0 ℃, the derivative dianhydride (0.030mol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane and NMP (40g) in the following figure are added together, the reaction is completed for 2h at 25 ℃, then 4-aminosalicylic acid (0.008mol) is added, the reaction is completed for 48h at 25 ℃, the temperature is increased to 50 ℃, N-dimethylformamide dimethyl acetal solution (0.060mol) diluted with NMP (10g) is dropwise added within 10min, and the reaction is completed for 4h at 50 ℃. In 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a ratio of 1:3 (volume ratio) for several times, and then vacuum-drying at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin B2, and measuring an infrared absorption spectrum, the imide rate was 25.5%.

Synthesis example 21

Synthesis of alkali-soluble resin B3

Under a dry nitrogen flow, Y3(0.015mol), 6FAP (0.020mol), SiDA (0.002mol), dissolved in NMP (100g), pyridine (9g) are added into a three-neck flask together, the temperature is reduced to-15 ℃, Y6(0.010mol) dissolved in NMP (10g) is dripped, the reaction is finished for 0.5h, then the temperature is raised to 0 ℃, 6FDA (0.015mol), ODPA (0.015mol) and NMP (30g) are added into the three-neck flask together, the reaction is finished for 2h at 25 ℃, 3-aminophenol (0.006mol) and the reaction is finished for 48h at 25 ℃, the temperature is raised to 50 ℃, N-dimethylformamide dimethyl acetal solution (0.060mol) diluted by NMP (10g) is dripped in 10min, and the reaction is finished for 4h at 50 ℃. In 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a ratio of 1:3 (volume ratio) for several times, and then vacuum-drying at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin B3, and measuring an infrared absorption spectrum, the imide rate was 26.1%.

Synthesis example 22

Synthesis of alkali-soluble resin A13

Y3(0.016mol), 6FAP (0.016mol), SiDA (0.004mol) were dissolved in NMP (100g) under a dry nitrogen stream, ODPA (0.020mol), 6FDA (0.020mol), and NMP (40g) were added thereto together, reacted at 25 ℃ for 2 hours, then 4-aminosalicylic acid (0.008mol) was added, reacted at 25 ℃ for 48 hours, then, azeotropic-reacted with xylene (10mL) was added, and the temperature was raised to 150 ℃ for 5 hours. In 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a ratio of 1:3 (volume ratio) for several times, and then vacuum-drying at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A13, and measuring an infrared absorption spectrum, the imide ratio was 91.0%.

Synthesis example 23

Synthesis of alkali-soluble resin A14

Under a dry nitrogen flow, a diamine compound (0.032mol), SiDA (0.002mol), pyridine (23.5g) dissolved in NMP (100g) in the following figure are added into a three-neck flask together, the temperature is reduced to-15 ℃, Y6(0.025mol) dissolved in NMP (20g) is added dropwise, the reaction is completed by 0.5h dropwise, then the temperature is increased to 0 ℃, 6FDA (0.015mol) and NMP (20g) are added together, the reaction is carried out for 2h at the temperature of 25 ℃, then 3-aminophenol (0.008mol) and 25 ℃ are added for 48h, then xylene (10mL) is added for azeotropy, and the temperature is increased to 150 ℃ for 5 h. In 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a ratio of 1:3 (volume ratio) for several times, and then vacuum-drying at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A11, and measuring an infrared absorption spectrum, the imide rate was 94.4%.

Synthesis example 24

Synthesis of alkali-soluble resin B4

In the following figure, 4' -diaminotetrafluorodiphenyl ether (0.018mol), 6FAP (0.016mol) and SiDA (0.003mol) were dissolved in NMP (100g) under a stream of dry nitrogen. ODPA (0.040mol) and NMP (40g) are added together, the mixture is reacted for 2h at 25 ℃, then 3-aminophenol (0.006mol) is added, the mixture is reacted for 2h at 40 ℃, the temperature is raised to 50 ℃, N-dimethylformamide dimethyl acetal solution (0.080mol) diluted by NMP (10g) is added dropwise within 10min, and the mixture is reacted for 4h at 50 ℃. The temperature of the solution was lowered to room temperature, and the solution was precipitated in 2L of water to give a white precipitate, which was filtered, and the filter cake was washed with water several times and then dried under vacuum at 50 ℃ for 72 hours to give a powder of alkali-soluble resin B4, the imide ratio.

Synthesis example 25

Synthesis of alkali-soluble resin A15

Under a dry nitrogen flow, 4 '-diaminotetrafluorodiphenyl ether (0.018mol), 4' -diaminodiphenyl sulfone (0.015mol), SiDA (0.003mol), dissolved in NMP (100g), pyridine (28.5g) in the following figure were added together to a three-necked flask, Y1(0.010mol) was added dropwise at room temperature and dissolved in NMP (20g), and the reaction was completed for 0.5h, then bis (3, 4-dicarboxyphenyl) sulfone dianhydride (0.030mol) and NMP (20g) were added together thereto, and the reaction was performed for 2h at 25 ℃, then 4-aminophenol (0.008mol) and 48h at 25 ℃, followed by heating to 60 ℃ and reacting for 6 h. In 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a ratio of 1:3 (volume ratio) for several times, and then vacuum-drying at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin A15, and measuring an infrared absorption spectrum, the imide rate was 22.0%.

Synthesis example 26

Synthesis of alkali-soluble resin B5

Under a dry nitrogen flow, bis (3-amino-4-hydroxyphenyl) methane (0.018mol), bis (3-amino-4-hydroxyphenyl) ether (0.016mol), SiDA (0.002mol), pyridine (13.5g) dissolved in NMP (100g) are added into a three-neck flask together, the temperature is reduced to-15 ℃, Y6(0.015mol) dissolved in NMP (20g) is dropwise added, the reaction is completed for 0.5h, then the temperature is raised to 0 ℃, ODPA (0.025mol) and NMP (20g) are added together, the reaction is performed for 2h at 25 ℃, 4-aminosalicylic acid (0.008mol) and 25 ℃ are added, the reaction is performed for 48h, the temperature is raised to 50 ℃, N-dimethylformamide dimethyl acetal solution (0.080mol) diluted by NMP (10g) is dropwise added within 10min, and the reaction is completed for 4h at 50 ℃. In 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a ratio of 1:3 (volume ratio) for several times, and then vacuum-drying at 50 ℃ for 72 hours to obtain a powder of alkali-soluble resin B5, and measuring an infrared absorption spectrum, the imide rate was 36.0%.

Example 1

Hereinafter, example 1 will be given as an example to specifically describe the following.

To an alkali-soluble resin A1 solution (10g) of Synthesis example 7 as an alkali-soluble resin (a), quinone diazide compounds PAC-1(0.6g) and PAC-7(0.6g) as photoacid generators (b), HMOM-TPHAP (product of chemical industry, Japan) (1.5g) and EP-4003S (product of ADEKA) (3g) as a thermal crosslinking agent (c), and GBL (10g) as a solvent (d) were added to prepare a varnish, and the varnish was evaluated by the above-described method.

The varnish obtained was coated on a silicon substrate using a spin coater, dried at 80 ℃ for 8min, exposed, and then developed with a small-sized developing apparatus for lithography (AC3000, manufactured by the greens industry) using a 2.38 mass% TMAH aqueous solution for 55 seconds, and rinsed with water for 30 seconds. After the development, the resultant was thermally cured at 230 ℃ using a high-temperature inert gas oven (INH-9 CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) to prepare a cured film having a film thickness of about 1.5 μm; the heat curing condition is heat curing at 230 ℃ for 60min under nitrogen atmosphere.

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

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 by using an alkaline aqueous solution, and has excellent sensitivity and resolution, clear pattern, higher residual film rate of unexposed parts and good thermal expansion coefficient after curing. It is suitably used as a semiconductor element protective film, a planarizing layer, an interlayer insulating film, an insulating film of a display, an insulating layer of an organic field to light emitting element, an insulating layer of a thin film transistor TFT, or the like.

Claims

1. A positive photosensitive resin composition, 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 a structure of formula (1) and a tetracarboxylic acid or dianhydride having a structure of formula (2);

wherein R in the structural formula (1)₀Represents a2 to 4 valent organic group, R₁represents-COOH or-OH;

formula (a1), (a2) is:

the general formula (3) is:

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

wherein R is₁₃Represents an organic group having 1 to 20 carbon atoms.

2. The positive photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (a) comprises a polymer of the general formula (4) having the general formulae (a3) and (a4) as main repeating units;

formula (a3), (a4) is:

the general formula (4) is:

wherein R is₂Represents an organic group having 1 to 20 hydrogen atoms and/or carbon atoms;

wherein in the general formula (4), P and Q represent a reaction residue of a diamine containing a structure of the general formula (1), and X and Y represent a reaction residue of a tetraacid containing a structure of the general formula (2).

3. The positive photosensitive resin composition according to claim 1 or 2, wherein the general formula (1) is obtained 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 ' -bistrifluoromethyldiphenyl ether.

4. A positive photosensitive resin composition according to claim 1 to 3, wherein 20 to 40 mol% of X and/or Y in the repeating units (a1), (a2), (a3), (a4) in the general formula (3) and the general formula (4) is derived from the structural formula (2), and 20 mol% or more and X + Y or less than 40 mol% is derived from the structural formula (2);

10-20 mol% of P and/or Q in the repeating units (a1), (a2), (a3) and (a4) in the general formula (3) and the general formula (4) is derived from the structural formula (1), and 10 mol% to 20 mol% of P + Q is derived from the structural formula (1);

m and n in the general formula (3) and the general formula (4) are integers of 10-50000.

5. The positive photosensitive resin composition according to claim 1 to 4, wherein the main chain end capping group of the alkali-soluble resin (a) has a structure represented by general formula (5) and/or (6), wherein A is derived from a primary monoamine and B is derived from a dianhydride, and the molar ratio of the main chain end capping group of the alkali-soluble resin (a) to the total amine and/or the total anhydride is 0 to 50%.

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

7. The positive photosensitive resin composition according to claim 6, wherein at least one of X, Y, P, and Q groups of the alkali-soluble resin (a) contains a fluorine atom, the fluorine atom accounts for 5 to 25% by mass of the alkali-soluble resin (a), and the at least one of X, Y, P, and Q groups of the alkali-soluble resin (a) contains one or more of a hydroxyl group, a carboxyl group, and a sulfonic group.

8. The positive photosensitive resin composition according to claim 1 or 2, wherein P, Q of the repeating units (a1), (a2), (a3), (a4) comprises one or more of the following reactive residues of diamine compounds: 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4 ' -diaminodiphenyl ether, 2 ' -bis trifluoromethyl-4, 4 ' -diaminodiphenyl ether, 4 ' -diaminotetrafluorodiphenyl ether, 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane, and diamine compounds in the following figures;

x and Y in the repeating units (a1), (a3), (a4) comprise one or more of the reaction residues of the dianhydride compounds: 2,2 ' -bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 3, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride, 2 ', 3, 3 ' -benzophenone tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, 3, 3 ', 4, 4 ' -diphenylether tetracarboxylic dianhydride, and the following structure;

9. A cured film obtained by curing a positive photosensitive resin composition according to any one of claims 1 to 8.

10. A pattern processing method of a cured film, comprising the steps of:

ii) exposing the envelope under a mask;