CN114195688A - Diamine compound, resin, photosensitive resin composition, and cured film - Google Patents

Diamine compound, resin, photosensitive resin composition, and cured film Download PDF

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CN114195688A
CN114195688A CN202111523144.1A CN202111523144A CN114195688A CN 114195688 A CN114195688 A CN 114195688A CN 202111523144 A CN202111523144 A CN 202111523144A CN 114195688 A CN114195688 A CN 114195688A
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diamine compound
formula
photosensitive resin
resin composition
resin
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CN114195688B (en
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周小明
肖桂林
鲁丽平
王元强
朱双全
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Hubei Dinglong Co ltd
Wuhan Rouxian Technology Co ltd
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Hubei Dinglong Co ltd
Wuhan Rouxian Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
    • C07C317/36—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atoms of the amino groups bound to hydrogen atoms or to carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
    • C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/76—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
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    • C07—ORGANIC CHEMISTRY
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    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
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    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
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    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/33—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring
    • C07C323/35—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group
    • C07C323/37—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group the sulfur atom of the sulfide group being further bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials

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Abstract

The invention discloses a diamine compound, resin, a photosensitive resin composition and a cured film, which relate to the technical field of photosensitive resin materials. The diamine compound has a general formula shown in formula (1):
Figure DDA0003397170980000011
in the formula (1), R represents a direct bond, -O-, an organic group with 1-20 carbon atoms; r0Is an organic radical comprising a sulfonic acid, sulfone or sulfide group, R1Represents H or an alkyl group having 1 to 3 carbon atoms; r2Is H, alkyl with 1-20 carbon atoms or organic group containing O, S, N, Si; i is an integer of 1 or more. The diamine compound provided by the invention simultaneously contains crosslinking groups such as alkoxy or hydroxymethyl, and functional groups such as sulfonyl or sulfonic group, and the diamine compound provided by the invention is introduced into photosensitive resin, so that the photosensitive resin has good photosensitive property and excellent mechanical and thermal properties.

Description

Diamine compound, resin, photosensitive resin composition, and cured film
Technical Field
The present invention relates to the technical field of photosensitive resin materials, and specifically relates to a diamine compound, a resin, a photosensitive resin composition and a 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.
In the heat-resistant resin precursor composition which is dissolved and washed by an alkaline developer after exposure, the solubility of carboxyl groups in the polyamic acid is too high, and the addition of the photoacid generator diazide naphthoquinone can make the photosensitive resin composition resistant to alkali to some extent, but an ideal pattern is hardly obtained after exposure. Therefore, in order to adjust the alkali solubility of polyamic acid, polyamic acid/polyimide, polyamic acid ester/polyamic acid resin; the introduction of hydroxyl groups and carboxyl groups into the 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. Therefore, diamines and dianhydrides containing hydroxyl and carboxyl groups are currently commonly used in the synthesis of polyimides.
At present, the introduction mode of using more phenolic hydroxyl groups in the prior art is to use biphenyl monomers containing hydroxyl groups or dianhydride with an alicyclic structure, but the rigid monomer polymer using biphenyl has poor solubility in solvents and alkaline solutions, so that the exposure sensitivity is reduced, and the transmittance is influenced; the alicyclic structure chain link has strong flexibility, which causes the problem of high thermal expansion coefficient of the photosensitive resin curing film.
With the rapid development of display technology, the requirement of the display device for transmittance is higher and higher. Therefore, it is desired to develop a photosensitive resin composition having a moderate alkali solubility, a good photosensitive property, a low thermal expansion coefficient, and a good transmittance.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a diamine compound, a resin, a photosensitive resin composition, and a cured film.
The first aspect of the present invention provides a diamine compound represented by the general formula (1):
Figure BDA0003397170970000021
in the formula (1), R represents a direct bond, -O-, an organic group with 1-20 carbon atoms; r0Is an organic radical comprising a sulfonic acid, sulfone or sulfide group, R1Represents H or an alkyl group having 1 to 3 carbon atoms; r2Is H, alkyl with 1-20 carbon atoms or organic group containing O, S, N, Si; i is an integer of 1 or more.
Further, in the formula (1), R represents a direct bond, -CH2-、-C(CH3)2-、-C(CF3)2-or-C (CH)3)2-Ph-C(CH3)2-；R0represents-Ph-SO2-、-Ph-S-、-Ph-SO3-；R1Represents H or-CH3；R2Represents H or-CH3。
Preferably, the diamine compound is selected from diamines having the structures shown by formulas (1a) to (1 f):
Figure BDA0003397170970000022
in a second aspect of the present invention, there is provided a resin comprising the reaction residue of the diamine compound provided in the first aspect of the present invention, the resin comprising a structure represented by general formula (2) and/or general formula (3):
Figure BDA0003397170970000031
in the formulae (2) and (3), P, Q represents a reactive residue of a diamine, and P and/or Q comprises a reactive residue of a diamine compound represented by the formula (1); x, Y represents the reaction residue of a dianhydride; r3、R4And R5Represents H or an organic group having 1 to 20 carbon atoms, R3、R4And R5The same or different.
Further, in the formulae (2) and (3), m and n represent the degree of polymerization, and m and n are integers of 0 to 50000; further, m + n is 10. ltoreq. m + n. ltoreq.5000, and further, both m and n are integers of 10 to 50000.
Further, in the formulas (2) and (3), the residue of the diamine compound represented by the formula (1) accounts for 5 mol% to 90 mol% of the total amount of P and Q; preferably, the residue of the diamine compound represented by the formula (1) accounts for 5 to 60 mol% of the total amount of P and Q; more preferably, the residue of the diamine compound represented by the formula (1) accounts for 30 to 60 mol% of the total amount of P and Q.
Further, in the formulas (2) and (3), at least one of X, Y, P, Q contains one or more of a phenolic hydroxyl group, a fluorine atom, a siloxane structure and an amide structure, and preferably, P and/or Q contains one or more of a phenolic hydroxyl group, a fluorine atom and a siloxane structure.
The third aspect of the present invention provides a photosensitive resin composition comprising the resin provided by the second aspect of the present invention.
The photosensitive resin composition is a positive photosensitive resin composition, and comprises the resin, a photoacid generator, a thermal crosslinking agent and an organic solvent.
Further, the amount of the thermal crosslinking agent added in the positive photosensitive resin composition is 15 to 100 parts by weight, preferably 20 to 50 parts by weight, relative to 100 parts by weight of the resin; the amount of the photoacid generator added is 5 to 40 parts by weight, preferably 5 to 30 parts by weight.
The fourth aspect of the present invention provides a cured film obtained by curing the photosensitive resin composition provided by the third aspect of the present invention.
Compared with the prior art, the invention has the following beneficial effects: the diamine compound provided by the invention simultaneously contains crosslinking groups such as alkoxy or hydroxymethyl and functional groups such as thioether, sulfone or sulfonic group, and the like, and is introduced into photosensitive resin, so that the photosensitive resin has good photosensitive property, lower thermal expansion coefficient and excellent mechanical property, and the light transmittance, refractive index or air escape property of the photosensitive resin can be improved by introducing the functional groups.
Detailed Description
The present invention provides a diamine compound, a resin, a photosensitive resin composition and a cured film, and will be described below with reference to specific embodiments. It should be noted that the following examples are illustrative of the present invention, and are not intended to limit the present invention. Other combinations and various modifications within the spirit or scope of the present invention may be made without departing from the spirit or scope of the present invention.
< diamine Compound >
The first aspect of the present invention provides a diamine compound used for preparing a polyimide resin that can be used for a photosensitive resin composition.
The diamine compound has a general formula shown in formula (1):
Figure BDA0003397170970000041
in the formula (1), R represents a direct bond, -O-, an organic group with 1-20 carbon atoms; r0Is an organic radical comprising a sulfonic acid, sulfone or sulfide group, R1Represents H or an alkyl group having 1 to 3 carbon atoms; r2Is H, alkyl with 1-20 carbon atoms or organic group containing O, S, N, Si; i is an integer ≧ 1, such as 1,2 or 3.
Preferably, in formula (1), R represents a direct bond, -CH2-、-C(CH3)2-、-C(CF3)2-or-C (CH)3)2-Ph-C(CH3)2-；R0represents-Ph-SO2-, -Ph-S-or-Ph-SO3-；R1Represents H or-CH3；R2Represents H or-CH3. wherein-Ph represents a phenyl group.
Further, the compound represented by the formula (1) is preferably synthesized from a phenol compound represented by the following formula (4).
Figure BDA0003397170970000051
In the formula (4), R represents a direct bond, -O-, an organic group with 1-20 carbon atoms; r1Represents H or an alkyl group having 1 to 3 carbon atoms; r2Is H, alkyl with 1-20 carbon atoms or organic group containing O, S, N, Si; i is an integer of 1 or more. Preferably, R represents a direct bond, -CH2-、-C(CH3)2-、-C(CF3)2-or-C (CH)3)2-Ph-C(CH3)2-；R1Represents H or-CH3；R2Represents H or-CH3. wherein-Ph represents a phenyl group.
As a preferred embodiment, the phenolic compound represented by formula (4) is preferably of the following structure:
Figure BDA0003397170970000052
Figure BDA0003397170970000061
for R0represents-Ph-SO3A diamine compound of (A) R1represents-CH3The preparation method comprises the following steps: mixing a phenolic compound shown as a formula (4) and p-nitrobenzenesulfonyl chloride according to a molar ratio of 1: 2 in a solvent such as DMF, adding potassium carbonate, and reacting to obtain a dinitro compound; the obtained dinitro compound is reduced in Pd-C catalyst/hydrogen atmosphere/ethylene glycol monomethyl ether solvent to obtain diamine compound. The general reaction formula is shown as the following formula (5). For R1Formula (4) representing hydrogen atom, it is necessary to esterify alcoholic hydroxyl group in formula (4) for hydroxyl protection, then react with p-nitrobenzenesulfonyl chloride, and then recover alcoholic hydroxyl group through ester group hydrolysis step.
Figure BDA0003397170970000062
Further, for R0represents-Ph-S-, wherein-Ph represents a phenyl group. Preferably, R represents a direct bond, -CH2-、-C(CH3)2-、-C(CF3)2-or-C (CH)3)2-Ph-C(CH3)2-；R1Represents H or-CH3；R2Represents H or-CH3(ii) a More preferably, R represents a direct bond, -CH2-。R1represents-CH3The preparation method comprises the following steps: reacting a phenolic compound shown as a formula (4) with phosphorus tribromide to obtain a bromide, wherein the obtained bromide and p-nitrobenzothiophenol are mixed according to a molar ratio of 1: 2 reacting to obtain a dinitro compound containing thioether bonds; the obtained dinitro compound is reduced in Pd-C catalyst/hydrogen atmosphere/ethylene glycol monomethyl ether solvent to obtain diamine compound containing thioether bond. The general reaction formula is shown as the following formula (6). R1The preparation method for representing hydrogen atoms comprises the steps of oxidizing alcoholic hydroxyl in a phenolic compound shown as a formula (4) to generate aldehyde, then reacting with phosphorus tribromide according to a formula (6), and reducing the aldehyde group and nitro group into alcoholic hydroxyl and amino through hydrogen under the catalytic action of palladium carbon.
Figure BDA0003397170970000071
For R0represents-Ph-SO2The diamine compound of (a), wherein-Ph represents a phenyl group. The preparation method comprises the following steps: oxidizing the dinitro compound containing the thioether bond obtained in the formula (6) to obtain a dinitro compound containing a sulfone group, and then reducing to obtain a diamine compound containing the sulfone group. Wherein the oxidant is selected from hydrogen peroxide and the like. The general reaction formula is shown as the following formula (7):
Figure BDA0003397170970000072
< resin >
In a second aspect of the present invention, there is provided a resin comprising a residue of the diamine compound provided in the first aspect of the present invention. Further, the resin provided by the second aspect of the present invention is a polyimide resin, specifically, the resin includes a structure represented by general formula (2) and/or general formula (3):
Figure BDA0003397170970000073
Figure BDA0003397170970000081
in the formulae (2) and (3), P, Q represents a reactive residue of a diamine, and P and/or Q comprises a reactive residue of a diamine compound represented by the formula (1); x, Y denotes the reactive residue of the dianhydride. R3、R4And R5Represents H or an organic group having 1 to 20 carbon atoms, R3、R4And R5M and n are, identically or differently, integers from 0 to 50000, preferably from 10 to 50000.
Further, the diamine compound having a structure represented by the formula (1) is preferably R from the viewpoint of improving the light transmittance of the polyimide resin0represents-Ph-SO2-、-Ph-SO3Examples of the diamine compound of (E) include formula (1a), formula (1b), (1e) and formula (1 f). Still further, from the viewpoint of improving the light transmittance of the resin and also improving the alkali solubility of the resin, the diamine compound having a structure represented by the formula (1) is more preferably R0represents-Ph-SO2-、-Ph-SO3-and R1Examples of the diamine compound represented by H include the formulae (1a) and (1 f).
Figure BDA0003397170970000082
Further, the diamine compound having a structure represented by the formula (1) is preferably R from the viewpoint of suppressing outgassing during the high-temperature curing of polyimide and improving the refractive index of the resin0Examples of the diamine compound represented by-Ph-S-include the formula (1c) and the formula (1 d). Further, in order to further improve the alkali solubility of the resin based on the above, the diamine compound having a structure represented by the formula (1) is more preferably R0represents-Ph-S-and R1Represents HThe diamine compound of (1) is exemplified by the formula (1 c).
Figure BDA0003397170970000091
Further, from the viewpoint of increasing the degree of crosslinking of the polyimide resin, in the formulae (2) and (3), the residue of the diamine compound represented by the formula (1) accounts for 5 to 90 mol% of the total amount of P and Q; preferably, the residue of the diamine compound represented by the formula (1) accounts for 5 to 60 mol% of the total amount of P and Q; more preferably, the residue of the diamine compound represented by the formula (1) accounts for 30 to 60 mol% of the total amount of P and Q. When the content is less than 5 mol%, the curing crosslinking density is insufficient, which is not beneficial to the improvement of the light transmittance, the refractive index and the air escape property of the resin and is also not beneficial to the improvement of the thermal property and the mechanical property; when the amount is more than 60 mol%, excessive crosslinking is likely to occur, and the cured film tends to become brittle.
Further, the resin provided by the second aspect of the present invention is used for the photosensitive resin composition, and in formulae (2) and (3), at least one of X, Y, P, Q contains one or more of a phenolic hydroxyl group, a fluorine atom, a siloxane structure and an amide structure, and preferably P and/or Q contains one or more of a phenolic hydroxyl group, a fluorine atom and a siloxane structure. Examples may be mentioned: p and/or Q further comprises the residue of one or more diamine monomers of aromatic diamines such as aromatic diamines containing phenolic hydroxyl groups, fluorine-containing diamines, diamines containing siloxane structures.
From the viewpoint of further improving the heat resistance of the photosensitive resin composition, P and/or Q further includes an aromatic diamine, and preferably includes an aromatic diamine containing a phenolic hydroxyl group. The aromatic diamines include, but are not limited to: 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, 3,3 '-dimethyl-4, 4' -diaminobiphenyl, 3,3 '-diethyl-4, 4' -diaminobiphenyl, 2', 3,3' -tetramethyl-4, 4 '-diaminobiphenyl, 3,3', 4,4 '-tetramethyl-4, 4' -diaminobiphenyl, 2 '-bis (trifluoromethyl) -5, 5' -dihydroxybenzidine, 3,4 '-diaminodiphenyl ether, 3, 4' -diaminodiphenylmethane, 4,4 '-diaminodiphenylmethane, 3, 4' -diaminodiphenylsulfone, 4,4 '-diaminodiphenylsulfone, 3, 4' -diaminodiphenylsulfide, sulfur, and the like, One or more diamines such as 4,4' -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, and 3-carboxy-4, 4' -diaminodiphenyl ether.
From the viewpoint of further improving the transparency and alkali solubility of the photosensitive resin composition, P and/or Q preferably further include fluorine-containing diamines including, but not limited to, one or more of the following structures:
Figure BDA0003397170970000101
it should be noted that, in order to reduce the adverse effect of reducing the adhesion between the resin composition and the substrate to some extent and to improve the adhesion between the resin composition and the substrate, P and/or Q in the general formulae (2) and (3) further contains a diamine having a siloxane structure without reducing the heat resistance, wherein the molar percentage of the diamine having a siloxane structure in P and/or Q in the general formulae (2) and (3) is 0 to 20 mol%; specifically, examples of the diamine component include: 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 general formulae (2) and (3) of the present invention, X and Y represent the residue of a dianhydride including, but not limited to: 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 the like.
For R in the formulae (2) and (3) of the present invention3、R4And R5Group, R3、R4And R5Represents H or an organic group having from 1 to 20 carbon atoms, preferably H or methyl, ethyl or propyl; further, R3、R4And R5The same or different.
M, n, m and n are integers of 0 to 50000 for the degrees of polymerization m, n, m and n in said general formulae (2) and (3), m + n > 1; further, m + n is more than or equal to 10 and less than or equal to 5000.
The resin provided by the second aspect of the present invention is an alkali-soluble polyimide resin, and can be used for a positive photosensitive resin composition.
In order to better regulate the molecular weight of the resin provided by the second aspect of the present invention, a certain end-capping agent may be added during polymerization, and specific examples thereof may be, but are not limited to, one or more combinations of the following exemplified compounds: monofunctional aromatic amine: 3-aminophenol, 2-aminophenol, 4-aminophenol, 3-aminobenzoic acid, 3-amino-o-methylbenzoic acid, 3-amino-m-methylbenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 1-amino-8-hydroxynaphthalene, 1-amino-7-hydroxynaphthalene, 1-amino-6-hydroxynaphthalene, 1-amino-5-hydroxynaphthalene, 1-amino-4-hydroxynaphthalene, 1-amino-3-hydroxynaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 3-aminobenzoic acid, 3-amino-o-methylbenzoic acid, 3-amino-m-methylbenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 1-amino-8-hydroxynaphthalene, 1-amino-7-hydroxynaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 3-aminonaphthalene, and the like, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 3-amino-4, 6-dihydroxypyrimidine, 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline. Monofunctional aromatic anhydrides: maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic anhydride, and cyclohexane dicarboxylic anhydride. Monofunctional aromatic acid: benzoic acid, o-methylbenzoic acid, m-methylbenzoic acid, p-methylbenzoic acid, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, carboxynaphthalene, 2-hydroxy-naphthoic acid, 3-hydroxy-naphthoic acid, 4-hydroxy-naphthoic acid, 5-hydroxy-naphthoic acid, 6-hydroxy-naphthoic acid, 7-hydroxy-naphthoic acid, 8-hydroxy-naphthoic acid, 9-hydroxy-naphthoic acid.
The end-capping agent is introduced in a proportion of 0.005 to 0.5, further 0.01 to 0.4, based on the total molar amount of all the diamine monomers and dianhydride monomers; when the content is within the above range, a resin composition having an appropriate solution viscosity and excellent film properties can be obtained.
< Positive photosensitive resin composition >
A third aspect of the present invention provides a positive photosensitive resin composition comprising the resin, a photoacid generator, a thermal crosslinking agent, and an organic solvent. Wherein the resin is the resin provided by the second aspect of the present invention.
Examples of the photoacid generator in the positive photosensitive resin composition include: one or more of quinone diazide compounds (naphthoquinone diazide sulfonate compounds), sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, and the like; 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. The phenolic hydroxy compound includes the following examples:
Figure BDA0003397170970000121
Figure BDA0003397170970000131
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.
Figure BDA0003397170970000132
Figure BDA0003397170970000141
The amount of the photoacid generator added is 5 to 40 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the alkali-soluble resin (a).
With respect to the thermal crosslinking agent in the photosensitive resin composition, the thermal crosslinking agent reacts with the resin provided by the second aspect of the present invention by heating, thereby improving the chemical resistance of the cured film. The thermal crosslinking agent in the invention is selected from one or more of epoxy compound and alkoxy/hydroxymethyl compound.
Among them, the epoxy compound is preferably a compound having two or more epoxy groups in one molecule, and examples thereof include epoxy group-containing silicones such as bisphenol a type epoxy resin, bisphenol a type oxetane resin, bisphenol F type epoxy resin, bisphenol F type oxetane resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl (glycidyloxypropyl) siloxane, and the like, but are not limited thereto, and examples thereof include: the Dainippon ink chemical industry EPICLON, EXA series products such as EPICLON850-S, EPICLONHP-4032, EPICLON HP-7200, EPICLON HP-820, EPICLON HP-4700, EPICLON EXA-4710, EPICLON HP-4770, EPICLON EXA-4816, EPICLON EXA-4822, and the like, and the ADEKA company EP series products such as EP 4003S, EP-4000S, and the like.
The alkoxy/hydroxymethyl compound is preferably a compound having 2 to 8 or more alkoxy and/or hydroxymethyl functional groups in one molecule, and is, for example, a phenol compound such as (2-hydroxy-5-methyl) -1, 3-benzenedimethanol or 2,2', 6, 6' -tetramethoxymethyl bisphenol A. There may be mentioned the trade names DML, TriML, DMOM, HMOM, TMOM etc. series of the state chemistry, such as DML-PC, DML-PEP, DML-OC, DML-OEP, DMOM-PC, DMOM-PTBP etc., and the MX, MW series of the three-and chemistry, such as MX-270, MW-100LM etc.
The amount of the thermal crosslinking agent of the present invention added is 15 to 100 parts by weight, preferably 20 to 50 parts by weight, relative to 100 parts by weight of the resin.
As the organic solvent in the photosensitive resin composition, the following examples are included, but not limited to: 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, dimethylsulfoxide, and the like.
The positive photosensitive resin composition introduced with the reaction residue of the diamine compound represented by the formula (1) of the present invention has appropriate alkali solubility and exposure sensitivity, and a cured film after development has high development resolution and high residual film ratio. Meanwhile, the cross-linking groups such as alkoxy, hydroxymethyl and the like which are contained in the reaction residue of the diamine compound shown in the formula (1) react with a thermal cross-linking agent during curing, so that the prepared cured film has a low thermal expansion coefficient and excellent chemical corrosion resistance.
< cured film >
The fourth aspect of the present invention provides a cured film obtained from the positive photosensitive resin composition provided by the third aspect of the present invention, specifically, by coating, exposing, developing, and curing.
The coating step is a step of coating the positive photosensitive resin composition on a substrate, and examples of the coating method include spin coating, spray coating, blade coating, screen coating, slit coating, and the like. Preferably, the film thickness after drying is 0.5-50 μm, and drying is carried out by oven, hot plate, infrared oven, etc. at 40-120 deg.C for 1-10 min or stage temperature programmed drying treatment 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.
The exposure step is to expose under a mask with a desired pattern after coating and drying to form a film; the exposure light source is preferably a mercury lamp of i (365nm), h (405nm), g (436nm) radiation; as the exposure apparatus, a reduction projection type exposure apparatus, a mask aligner, a mirror projection type exposure apparatus, or the like is used.
As for the development step, in the method for producing a cured film from the positive photosensitive resin composition, the development step is to remove the exposed portion on the coating film using a developer.
The developer is 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 selected from 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 developed 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; before developing, if the film needs to be baked, baking at 50-150 ℃, preferably 50-120 ℃ for 5 s-60 min; and after rinsing, heating and drying the film at the temperature of 50-200 ℃, wherein the drying time is controlled to be 1-60 min.
In the curing step, the curing temperature is 100-400 ℃, the temperature rising mode is a staged temperature rising program or a constant rate temperature rising, and the temperature rising examples include: heating from room temperature to 120 ℃ at a heating rate of 5 ℃/min, and carrying out constant temperature treatment for 30 min; continuously heating to 180 ℃ at the heating rate of 5 ℃/min, and carrying out constant temperature treatment for 30 min; continuously heating to 250 ℃ at the heating rate of 5 ℃/min, and carrying out constant-temperature heat treatment for 1 h. Or heating from room temperature to 250 ℃ at the heating rate of 5 ℃/min, and then carrying out constant-temperature heat treatment for 1 h. The patterned cured film can be obtained by curing.
The cured film provided by the present invention has a low coefficient of thermal expansion and excellent chemical resistance, and is suitable for use as a surface protective film for a semiconductor device, an interlayer insulating film, an insulating layer for an organic Electroluminescent (EL) device, an insulating layer for a Thin Film Transistor (TFT), and the like, but is not limited thereto.
Examples
The above and other advantages of the present invention will be better understood by the following examples, which are not intended to limit the scope of the present invention.
Description of abbreviations:
ODA: 4,4' -diaminodiphenyl ether
6 FAP: 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane
SiDA: 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane
6 FDA: 2,2' -bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride
ODPA: 3,3', 4,4' -Diphenyl Ether Tetraformic dianhydride
Synthesis example 1
Diamine compound Y1 was synthesized according to the following route:
Figure BDA0003397170970000171
the specific operation is as follows: oxidizing methyl into carboxyl by using 2, 6-dimethyl bromobenzene as a raw material, then carrying out sulfonic group substitution on a benzene ring, converting the sulfonic group into sulfonyl chloride by phosphorus oxychloride, reducing the sulfonyl chloride into thiophenol, then reacting with m-nitrobromobenzene to generate thioether compounds, and then carrying out reaction on bis (pinacolato) diboron (B)2Pin2) Suzuki coupling reaction is carried out under the action to obtain thioether biphenyl compounds, and finally diamine compounds Y1 are obtained through hydrolysis and reduction.
Or selecting the following route to synthesize the diamine compound Y1 derivative:
Figure BDA0003397170970000172
the specific operation is as follows: 3,3',5,5' -tetra-aldehyde-4, 4' -dihydroxydiphenyl is used as a raw material to react with phosphorus tribromide to obtain a bromide, and then Cu is added into a mixed solvent of quinoline and pyridine2O is used as a catalyst, the m-nitrothiophenol reacts to generate a dinitro compound containing a thioether bond, and the dinitro compound is reduced under Pd-C catalyst/hydrogen atmosphere/ethylene glycol monomethyl ether solvent to obtain a diamine compound Y1 containing the thioether bond.
Synthesis example 2
Diamine compound Y2 was synthesized according to the following route:
Figure BDA0003397170970000181
the specific operation is as follows: using 2-amino-5-methyl benzoic acid as raw material in NaNO2Diazotization under the action of HCl, and then neutralization of KS2COCH2CH3Reacting to generate 2-mercapto-5-methylbenzoic acid, or directly taking p-methylthio phenol as a raw material and neutralizing under the action of aluminum trichloride or ferric trichlorideOxalyl chloride generates 2-mercapto-5-methyl benzoic acid; sequentially carrying out esterification reaction, p-nitrobromobenzene reaction and hydrolysis to obtain thioether benzyl alcohol compound, reacting benzyl alcohol group with alkyl halide for etherification, then carrying out bromine substitution, then reacting with carbon dioxide under Grignard reagent n-butyllithium (n-BuLi) to carboxylate bromide, carrying out coupling reaction after esterification, and carrying out triethylsilane (Et)3SiH)/TFA to reduce the hydroxyl group to hydrogen and finally the nitro group to the amine group to give the diamine compound Y2.
Or the diamine compound Y2 is synthesized by adopting the following route:
Figure BDA0003397170970000182
the phenolic compound in the above route is used as a raw material, and is sequentially reacted with phosphorus tribromide and p-nitrothiophenol, and then reduced under Pd-C catalyst/hydrogen atmosphere/ethylene glycol monomethyl ether solvent to obtain a diamine compound Y2 containing thioether bonds.
Synthesis example 3
The dinitro sulfide compound prepared in Synthesis example 1 was reacted with hydrogen peroxide (H)2O2) Under the action, thioether groups are oxidized into sulfone groups, and then the sulfone groups are reduced under the Pd-C catalyst/hydrogen atmosphere/ethylene glycol monomethyl ether solvent to obtain a diamine compound Y3, wherein the synthetic route is as follows:
Figure BDA0003397170970000191
synthesis example 4
Oxidizing thioether groups of the dinitro thioether compounds prepared in the synthesis example 2 into sulfone groups under the action of m-chloroperoxybenzoic acid (m-CPBA), and then reducing the sulfone groups under Pd-C catalyst/hydrogen atmosphere/ethylene glycol monomethyl ether solvent to obtain a diamine compound Y4, wherein the synthesis route is as follows:
Figure BDA0003397170970000192
synthesis example 5
Diamine compound Y5 was synthesized according to the following route:
Figure BDA0003397170970000193
the specific operation is as follows: adding 0.25mol of 2,2 '-dihydroxy-3, 3' -dihydroxymethyl-diphenylmethane and 0.52mol of acetic acid into a three-neck flask, and carrying out esterification reaction under the action of concentrated sulfuric acid; then, 150mL of DMF in which 0.52mol of p-nitrobenzenesulfonyl chloride was dissolved was added, 0.57mol of potassium carbonate was further added, the reaction was stirred at room temperature for 10 hours, and the mixture was poured into 400mL of a solution of ethanol and water at a ratio of 1:1, and the resulting crude product was precipitated and recrystallized in acetic acid to obtain a dinitro compound represented by the above formula. Taking 0.02mol of the obtained dinitro compound, hydrolyzing ester groups under the action of acid, dissolving a hydrolyzed product into 150mL of ethylene glycol monomethyl ether, then adding the ethylene glycol monomethyl ether into a stainless steel autoclave, adding 0.4g of 5% palladium-carbon, then adding hydrogen into the ethylene glycol monomethyl ether, stirring the mixture at room temperature for epoxy reaction for 4 hours, then, not reducing the hydrogen pressure, filtering the mixture to remove the catalyst after the reaction is finished, and rotationally evaporating and concentrating the filtrate to obtain a diamine compound Y5.
Synthesis example 6
Diamine compound Y6 was synthesized according to the following route:
Figure BDA0003397170970000194
the specific operation is as follows: 0.25mol of the phenolic compound having the above structure and 0.52mol of p-nitrobenzenesulfonyl chloride were added to a three-necked flask and dissolved in 150mL of DMF, and potassium carbonate (0.57mol) was added thereto, and the mixture was stirred at room temperature for 10 hours, and then poured into a solution of 400mL of ethanol and water (1: 1), and the resulting crude product was precipitated and recrystallized in acetic acid to obtain a dinitro compound represented by the following formula. Dissolving 0.02mol of the obtained dinitro compound into 150mL of ethylene glycol monomethyl ether, adding the dinitro compound into a stainless steel autoclave, adding 0.4g of 5% palladium-carbon, adding hydrogen into the autoclave, stirring the mixture at room temperature, carrying out epoxy reaction for 4 hours, stopping the reaction until the hydrogen pressure is not reduced, filtering the mixture to remove the catalyst, and carrying out rotary evaporation and concentration on the filtrate to obtain a diamine compound Y6.
< preparation of alkali-soluble resin >
Preparation example 1: synthesis of alkali-soluble resin A1
0.06mol of Y3 and 0.03mol of ODA were dissolved in 100g of NMP under a stream of dry nitrogen, and then 0.1mol of 6FDA and 40g of NMP were added thereto, reacted at 25 ℃ for 2 hours, 0.02mol of 4-aminosalicylic acid and 10g of NMP were added, reacted at 25 ℃ for 2 hours, then heated to 40 ℃ for 2 hours, and further heated to 120 ℃ and 180 ℃ for 2 to 5 hours. 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 for several times. The filter cake was dried under vacuum at 50 ℃ for 72h to give a powder of alkali-soluble resin A1.
Preparation example 2: synthesis of alkali-soluble resin A2
The difference from preparation example 1 is that: diamine monomer used 0.05mol Y3 and 0.04mol ODA, and dianhydride monomer used 0.1mol ODPA. The rest was the same as in preparation example 1, and a powder of alkali-soluble resin A2 was prepared.
Preparation example 3: synthesis of alkali-soluble resin A3
The difference from preparation example 1 is that: diamine monomers used 0.04mol Y3 and 0.05mol ODA. The rest was the same as in preparation example 1, and a powder of alkali-soluble resin A3 was prepared.
Preparation example 4: synthesis of alkali-soluble resin A4
The difference from preparation example 1 is that: diamine monomer used 0.02mol Y3, 0.05mol ODA and 0.02mol6FAP, and dianhydride monomer used 0.1mol ODPA. The rest was the same as in preparation example 1, and a powder of alkali-soluble resin A4 was prepared.
Preparation example 5: synthesis of alkali-soluble resin A5
The difference from preparation example 1 is that: the diamine monomer used was 0.005mol of Y3, 0.065mol of ODA and 0.02mol of 6 FAP. The rest was the same as in preparation example 1, and a powder of alkali-soluble resin A5 was prepared.
Preparation example 6: synthesis of alkali-soluble resin A6
The difference from preparation example 1 is that: diamine monomers used 0.04mol Y1 and 0.05mol ODA. The rest was the same as in preparation example 1, and a powder of alkali-soluble resin A6 was prepared.
Preparation example 7: synthesis of alkali-soluble resin A7
The difference from preparation example 1 is that: the diamine monomer used was 0.04mol of Y3, 0.02mol of SiDA and 0.03mol of ODA. The rest was the same as in preparation example 1, and a powder of alkali-soluble resin A7 was prepared.
Preparation example 8: synthesis of alkali-soluble resin A8
The difference from preparation example 1 is that: diamine monomers used 0.04mol Y5 and 0.05mol ODA. The rest was the same as in preparation example 1, and a powder of alkali-soluble resin A8 was prepared.
Preparation example 9: synthesis of alkali-soluble resin A9
The difference from preparation example 1 is that: the diamine monomer used was 0.04mol of Y2 and 0.05mol of 6 FAP. The rest was the same as in preparation example 1, and a powder of alkali-soluble resin A9 was prepared.
Preparation example 10: synthesis of alkali-soluble resin A10
The difference from preparation example 1 is that: diamine monomer used 0.04mol Y4, 0.01mol SiDA and 0.04mol6FAP, dianhydride monomer used 0.1mol ODPA. The rest was the same as in preparation example 1, and a powder of alkali-soluble resin A10 was prepared.
Preparation example 11: synthesis of alkali-soluble resin A11
The difference from preparation example 1 is that: diamine monomer used 0.04mol Y6, 0.01mol SiDA and 0.04mol ODA, and dianhydride monomer used 0.1mol ODPA. The rest was the same as in preparation example 1, and a powder of alkali-soluble resin A11 was prepared.
Comparative preparation example 1: synthesis of alkali-soluble resin A1-1
The difference from preparation example 1 is that: 0.09mol of ODA was used as the diamine monomer. The rest was the same as in preparation example 1, and a powder of alkali-soluble resin A1-1 was prepared.
Comparative preparation example 2: synthesis of alkali-soluble resin A1-2
The difference from preparation example 1 is that: diamine monomers used were 0.095mol Y3 and 0.005mol ODA. The rest was the same as in preparation example 1, and a powder of alkali-soluble resin A1-2 was prepared.
Comparative preparation example 3: synthesis of alkali-soluble resin A1-3
The difference from preparation example 1 is that: diamine monomer used 0.04mol Y6 and 0.05mol bis (3-amino-4-hydroxyphenyl) ether, and dianhydride monomer used 0.1mol ODPA. The rest was the same as in preparation example 1, and a powder of alkali-soluble resin A1-3 was prepared.
The component lists of the alkali-soluble resins prepared in the above preparation examples 1 to 11 and comparative preparation examples 1 to 3 are shown in Table 1:
TABLE 1 ingredient List of alkali soluble resins prepared in preparation examples 1-11 and comparative preparation examples 1-3
Figure BDA0003397170970000221
Example 1
Provided is a positive photosensitive resin composition, the preparation method of which is: 10g of an alkali-soluble resin A1 was taken, to which was added a photoacid generator: 0.6g PAC-1, solvent addition: 10g of gamma-butyrolactone, to give a positive photosensitive resin composition varnish.
The varnish thus obtained was applied to a silicon substrate using a spin coater, dried at 80 ℃ for 8min to form a coating film, and the coating film was exposed to light using a photolithography small-sized developing apparatus (AC 3000; manufactured by greenling industries, ltd.). After exposure, the resultant was developed with a 2.38 mass% aqueous tetramethylammonium hydroxide solution for 55 seconds and rinsed with water for 30 seconds. After the development and rinsing, the resultant was cured at 250 ℃ for 60 minutes in a nitrogen atmosphere using a high-temperature inert gas oven (INH9 CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) to obtain a cured film having a film thickness of about 1.5. mu.m.
Example 2
Unlike example 1, the alkali-soluble resin was A2, and the photoacid generator was PAC-2.
Example 3
Unlike example 1, the alkali-soluble resin was A3, and the photoacid generator was PAC-3.
Example 4
Unlike example 1, the alkali-soluble resin was A4, and the photoacid generator was PAC-4.
Example 5
Unlike example 1, the alkali-soluble resin was A5, and the photoacid generator was PAC-5.
Example 6
Different from the example 1, the alkali soluble resin is A6, the photoacid generator is PAC-6, and a thermal cross-linking agent is added after the addition of the photoacid generator: 2.0g EPICLON 850-S.
Example 7
Different from the example 1, the alkali soluble resin is A7, the photoacid generator is PAC-7, and a thermal cross-linking agent is added after the addition of the photoacid generator: 2.0g EPICLON EXA-4710.
Example 8
Different from the example 1, the alkali soluble resin is A8, the photoacid generator is PAC-8, and a thermal cross-linking agent is added after the addition of the photoacid generator: 2.0g of polypropylene glycol diglycidyl ether.
Example 9
Different from the example 1, the alkali soluble resin is A9, the photoacid generator is PAC-9, and a thermal cross-linking agent is added after the addition of the photoacid generator: 4.0g EPICLON 850-S.
Example 10
Different from the example 1, the alkali soluble resin is A10, the photoacid generator is PAC-10, and a thermal cross-linking agent is added after the addition of the photoacid generator: 5.0g EPICLON EXA-4710.
Example 11
Different from the example 1, the alkali soluble resin is A11, the photoacid generator is PAC-11, and a thermal cross-linking agent is added after the addition of the photoacid generator: 5.0g of 2,2', 6, 6' -tetramethoxymethyl bisphenol A.
Comparative example 1
Unlike example 1, the alkali-soluble resin was A1-1.
Comparative example 2
Unlike example 1, the alkali-soluble resin was A1-2.
Comparative example 3
Unlike example 11, the alkali-soluble resin was A1-3, and the thermal crosslinking agent was 6g of EPICLON 850-S.
The component lists of the positive photosensitive resin compositions prepared in examples 1 to 11 and comparative examples 1 to 3 are shown in Table 2:
TABLE 2 ingredient List of positive photosensitive resin compositions prepared in examples 1 to 11 and comparative examples 1 to 3
Figure BDA0003397170970000241
The positive photosensitive resin compositions prepared in examples 1 to 11 and comparative examples 1 to 3 were evaluated by the following evaluation methods, and the results shown in Table 3 were obtained.
TABLE 3 evaluation results of Positive photosensitive resin compositions prepared in examples 1 to 11 and comparative examples 1 to 3
Figure BDA0003397170970000242
< method for evaluating Positive photosensitive resin composition >
The positive photosensitive resin compositions prepared in examples 1 to 11 of the present invention and comparative examples 1 to 3 were coated on a 6-inch silicon wafer to give a prebaked film thickness of 10 μm, and then prebaked at 120 ℃ for 4 minutes using a hot plate (SCW-636; Dainippon Screen Ltd.) to give a prebaked film. Using a small developing device (AC3000) for lithography to expose the photoresist at the exposure level of 0-1000 mJ/cm2In the case of (2), at 10mJ/cm2Exposing the coating film at the step pitch of (a); after exposure, the coating film was developed in a 2.38 mass% aqueous TMAH solution for 90 seconds, and then rinsed with water to obtain a developed film having an isolated pattern.
And (3) calculating the residual film rate: the residual film ratio (%). film thickness after development ÷ film thickness after prebaking × 100%
Residue: with respect to the obtained developed film having an isolated pattern, the residue of the exposed portion was observed on the surface. The case where no problem occurred in the developed film pattern was judged to be good, the case where the pattern resolution was good although there was little residue was judged to be normal, and the case where there was residue and the pattern resolution was not good was judged to be bad.
And (3) evaluating the resolution: a coating film obtained by coating a positive photosensitive resin composition varnish was subjected to patterning exposure using an i-line (wavelength 365nm), an h-line (wavelength 405nm) and a g-line (wavelength 436nm) of an ultra-high pressure mercury lamp with a gray scale mask (MDRM MODEL 4000-5-FS; manufactured by Union Optical, Inc.) for sensitivity measurement through a double-side alignment single-side exposure apparatus (mask aligner PEM-6M), and then developed using a small developing apparatus for lithography (AD-2000; manufactured by Kyowa industries, Ltd.), and then the developed coating film was cured using a high temperature inert oven (INH-9 CD-S; manufactured by Koyo Thermo Systems, Ltd.) to obtain a cured film. The pattern of the cured film was observed using an FPD/LSI inspection microscope (OPTIPHOT-330; manufactured by UNION). The minimum pattern size of the line-and-space pattern obtained without residue was defined as the resolution.
And (3) testing light transmittance: a coating film having a thickness of 3.0 μm was formed on the glass substrate. The exposure is performed through a predetermined mask by using an i-ray stepper. After development with an alkaline developer (2.38 mass% aqueous tetramethylammonium hydroxide solution) at 25 ℃, rinsing with deionized water was carried out for 1 minute. Irradiating the developed coating film with 300mJ/cm at 365nm using an ultrahigh pressure mercury lamp2After the light, it was heated in an oven at 250 ℃ for 45 minutes. The transmittance of the cured film was measured three times at a wavelength of 400nm using a spectrophotometer, and the average value was taken.
Evaluation of refractive index: the positive photosensitive resin composition was uniformly applied to a glass substrate using a blade coater, and dried at 100 ℃ for 10 minutes to form a photosensitive resin composition layer having a thickness of 5 μm, which was cut into 5cm × 5 cm. The prepared sample was measured for the refractive index at an arbitrary 4 points in the planar direction of the sample using a refractive index measuring apparatus (manufactured by Metricon corporation) and a 620nm light source, and the refractive index at an arbitrary 4 points in the vertical direction was measured to calculate the average value.
Evaluation of outgassing Properties: the positive photosensitive resin composition was uniformly applied to a glass substrate using a blade coater, and prebaked at 90 ℃ for 120 seconds on a hot plate to volatilize the solvent, thereby forming a photosensitive resin composition layer having a film thickness of 3.0 μm. Then, the obtained photosensitive resin composition layer was exposed to light through a predetermined mask by using MPA 5500CF (high pressure mercury lamp) manufactured by Canon (inc.). Then, the exposed photosensitive resin composition layer was developed with an alkali developer (0.4% tetramethylammonium hydroxide aqueous solution) at 23 ℃ for 60 seconds, and then rinsed with ultrapure water for 20 seconds. Thereafter, baking was performed at 250 ℃ for 30 minutes using an oven. The obtained cured film was scraped off, and the amount of weight loss was analyzed by a thermogravimetric Analyzer (TGA) Analyzer (Q-5000SA, manufactured by TA instruments) under a nitrogen atmosphere at a temperature rising rate of 10 ℃/min, a holding temperature of 250 ℃, a holding time of 60 minutes.
Testing the thermal expansion coefficient: the prebaked coating was cut into short strips of 4mm by 20mm in width, and the strips were used as test pieces by using a TMA tester (TA-Q400) under a nitrogen atmosphere at a temperature rise rate of 10 ℃/min. The sample was warmed once in TMA before testing to remove relaxation effects.
Elongation at break and tensile strength test: the test specimen width was 10mm, the jig interval was 50mm, the test speed was 50mm/min, and the number of test specimens was 10 groups, as measured by a universal material testing machine (Instron 3360).

Claims (10)

1. A diamine compound represented by the general formula (1):
Figure FDA0003397170960000011
in the formula (1), R represents a direct bond, -O-, an organic group with 1-20 carbon atoms; r0Is an organic radical comprising a sulfonic acid, sulfone or sulfide group, R1Represents H or an alkyl group having 1 to 3 carbon atoms; r2Is H, alkyl with 1-20 carbon atoms or organic group containing O, S, N, Si; i is an integer of 1 or more.
2. Diamine compound according to claim 1, characterized in that in formula (1), R represents a direct bond, -CH2-、-C(CH3)2-、-C(CF3)2-or-C (CH)3)2-Ph-C(CH3)2-；R0represents-Ph-SO2-、-Ph-S-、-Ph-SO3-；R1Represents H or-CH3；R2Represents H or-CH3。
3. Diamine compound according to claim 1, characterized in that it is selected from diamines of the structure represented by formula (1a) to formula (1 f):
Figure FDA0003397170960000012
4. a resin comprising the reactive residue of a diamine compound according to any one of claims 1 to 3, wherein the resin comprises a structure represented by general formula (2) and/or general formula (3):
Figure FDA0003397170960000021
in the formulae (2) and (3), P, Q represents a reactive residue of a diamine, and P and/or Q comprises a reactive residue of a diamine compound represented by the formula (1); x, Y represents the reaction residue of a dianhydride; r3、R4And R5Represents H or an organic group having 1 to 20 carbon atoms, R3、R4And R5The same or different, m and n are integers of 0 to 50000.
5. The resin according to claim 4, wherein the residue of the diamine compound represented by the formula (1) accounts for 5 to 90 mol% of the total amount of P and Q; preferably, the residue of the diamine compound represented by the formula (1) accounts for 5 to 60 mol% of the total amount of P and Q; more preferably, the residue of the diamine compound represented by the formula (1) accounts for 30 to 60 mol% of the total amount of P and Q.
6. The resin according to claim 4, wherein in the formulas (2) and (3), at least one of X, Y, P, Q contains one or more of a phenolic hydroxyl group, a fluorine atom, a siloxane structure and an amide structure, and preferably P and/or Q contains one or more of a phenolic hydroxyl group, a fluorine atom and a siloxane structure.
7. A photosensitive resin composition comprising the resin according to any one of claims 4 to 6.
8. A photosensitive resin composition according to claim 7, wherein the photosensitive resin composition is a positive photosensitive resin composition comprising the resin, a photoacid generator, a thermal crosslinking agent, and an organic solvent.
9. A photosensitive resin composition according to claim 8, wherein the amount of the thermal crosslinking agent added in the positive photosensitive resin composition is 15 to 100 parts by weight, preferably 20 to 50 parts by weight, based on 100 parts by weight of the resin; the amount of the photoacid generator added is 5 to 40 parts by weight, preferably 5 to 30 parts by weight.
10. A cured film obtained by curing the photosensitive resin composition according to any one of claims 7 to 9.
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