CN114450318A - Polymer, photosensitive resin composition, resin film, and electronic device - Google Patents

Polymer, photosensitive resin composition, resin film, and electronic device Download PDF

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CN114450318A
CN114450318A CN202080067912.4A CN202080067912A CN114450318A CN 114450318 A CN114450318 A CN 114450318A CN 202080067912 A CN202080067912 A CN 202080067912A CN 114450318 A CN114450318 A CN 114450318A
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polymer
carbon atoms
group
resin composition
photosensitive resin
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池田阳雄
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Sumitomo Bakelite Co Ltd
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Sumitomo Bakelite Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/22—Esters containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • 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
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

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  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
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Abstract

A polymer comprising structural units represented by the following formulae (1) and (2 a). In the formula (1), R1、R2、R3And R4Each independently hydrogen or an organic group having 1 to 30 carbon atoms, n is 0, 1 or 2, R in the formula (2a)5Is an organic group having 1 to 30 carbon atoms, R1、R2、R3、R4And R5At least one of the fluorine-containing organic groups is a fluorine-containing organic group having 1 to 30 carbon atoms.

Description

Polymer, photosensitive resin composition, resin film, and electronic device
Technical Field
The invention relates to a polymer, a photosensitive resin composition, a resin film and an electronic device. More specifically, the present invention relates to a polymer, a photosensitive resin composition containing the polymer, a resin film formed from a cured product of the photosensitive resin composition, and an electronic device including the resin film.
Background
In the field of negative photosensitive resin compositions, various techniques have been developed for the purpose of achieving high resist pattern accuracy with the miniaturization of patterns. As such a technique, for example, a technique described in patent document 1 can be cited. According to this document, a radiation-sensitive resin composition containing [ A ] a polymer and [ B ] an acid generator is described. Further, the following is described: the polymer [ A ] has a structural unit (I) and a structural unit (II), and is excellent in LWR (Line Width Roughness) performance and defect suppression performance, which indicate the magnitude of the deviation of the Line Width (paragraph 0012 of patent document 1). Wherein it is described that the structural unit (I) is a structural unit derived from N- (tert-butoxycarbonylmethyl) maleimide, N- (1-methyl-1-cyclopentyloxycarbonylmethyl) maleimide or N- (2-ethyl-2-adamantyloxycarbonylmethyl) maleimide. Further, it is described that the structural unit (II) is a structural unit derived from 2-norbornene.
Documents of the prior art
Patent literature
Patent document 1: japanese laid-open patent publication No. 2015-184458
Disclosure of Invention
Technical problems to be solved by the invention
The present inventors have studied the durability of a negative photosensitive resin composition. As a result, it is clear that the radiation-sensitive resin composition described in patent document 1 has room for further improvement in durability and low dielectric constant. The invention provides a photosensitive resin composition with excellent balance between durability and low dielectric property and a polymer used in the photosensitive resin composition.
The present inventors have found that a cured product of a photosensitive resin composition containing a polymer having a structural unit with a specific structure has improved heat resistance, improved solvent resistance, and a low dielectric constant, and have completed the present invention.
Means for solving the problems
The present inventors have conducted intensive studies and as a result, have found that the above-mentioned problems can be solved by using a polymer having a specific fluorine-containing organic group.
According to the present invention, there is provided a polymer comprising structural units represented by the following formulae (1) and (2 a).
Figure BDA0003567946470000021
In the formula (1), R1、R2、R3And R4Each independently hydrogen or an organic group having 1 to 30 carbon atoms, n is 0, 1 or 2, R in the formula (2a)5Is an organic group having 1 to 30 carbon atoms, R1、R2、R3、R4And R5At least one of the fluorine-containing organic groups is a fluorine-containing organic group having 1 to 30 carbon atoms.
Further, according to the present invention, there is provided a photosensitive resin composition comprising: a polymer comprising structural units represented by the following formulae (1) and (2 a); a crosslinking agent; and a photosensitizer.
Figure BDA0003567946470000022
In the formula (1), R1、R2、R3And R4Each independently hydrogen or an organic group having 1 to 30 carbon atoms, n is 0, 1 or 2, R in the formula (2a)5Is an organic group having 1 to 30 carbon atoms, R1、R2、R3、R4And R5At least one of the fluorine-containing organic groups is a fluorine-containing organic group having 1 to 30 carbon atoms.
Further, according to the present invention, there is provided a resin film comprising a cured film of the photosensitive resin composition.
Also, according to the present invention, there is provided an electronic device including the resin film described above.
Effects of the invention
According to the present invention, a polymer which is excellent in heat resistance and solvent resistance and which can be suitably used for producing a resin film having a low dielectric constant can be provided.
Detailed Description
Embodiments of the present invention will be described below.
(Polymer P)
The polymer of the present embodiment (hereinafter referred to as "polymer P") includes structural units represented by the following formulae (1) and (2 a).
Figure BDA0003567946470000031
Wherein, in the formula (1), R1、R2、R3And R4Each independently hydrogen or an organic group having 1 to 30 carbon atoms, n is 0, 1 or 2, R in the formula (2a)5Is an organic group having 1 to 30 carbon atoms, R1、R2、R3、R4And R5At least one of the fluorine-containing organic groups is a fluorine-containing organic group having 1 to 30 carbon atoms.
By containing the above structural unit, the polymer P gives a cured product having excellent heat resistance and solvent resistance and low dielectric properties. Therefore, the resin composition can be suitably used as a material for a resin film for manufacturing an electronic device.
The polymer P has a structural unit derived from a norbornene-type monomer represented by formula (1) and a structural unit derived from maleic anhydride represented by formula (2 a).
Figure BDA0003567946470000041
In the formula (1), n is 0, 1 or 2, preferably 0.
R1、R2、R3And R4Each independently hydrogen or an organic group having 1 to 30 carbon atoms.
In the formula (2a), R5Is an organic group having 1 to 30 carbon atoms.
R1、R2、R3、R4And R5At least one of the fluorine-containing organic groups is a fluorine-containing organic group having 1 to 30 carbon atoms.
The proportion of the structural unit represented by formula (1) in all the structural units of the polymer P is preferably from 35 mol% to 70 mol%, more preferably from 40 mol% to 60 mol%.
R in the formula (1) and the formula (2a) can be constituted1、R2、R3And R4And R5Examples of the organic group having 1 to 30 carbon atoms include an alkyl group, an alkenyl group, an alkynyl group, an alkylene group (alkyl group), an aryl group, an aralkyl group, an alkaryl group (alkyl group), a cycloalkyl group, and a heterocyclic group.
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group.
Examples of the alkenyl group include allyl, pentenyl and vinyl. Examples of the alkynyl group include an ethynyl group.
Examples of the alkylene group include a methine (methylene goup) group and an ethylene (ethylene goup) group.
Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.
Examples of the alkylaryl group include tolyl and xylyl. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
Examples of the heterocyclic group include an epoxy group and an oxetanyl group.
The organic group having 1 to 30 carbon atoms may contain at least 1 atom selected from O, N, S, P and Si in its structure.
In one embodiment, the organic group having 1 to 30 carbon atoms is preferably an organic group having 1 to 15 carbon atoms, and more preferably an organic group having 1 to 10 carbon atoms. The organic group having 1 to 30 carbon atoms is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and still more preferably an alkyl group having 1 to 10 carbon atoms.
In the polymer P, R1、R2、R3、R4And R5At least one of the fluorine-containing organic groups is a fluorine-containing organic group having 1 to 30 carbon atoms. Examples of the fluorine-containing organic group having 1 to 30 carbon atoms include fluoroalkyl groups having 1 to 30 carbon atoms and having an etheric oxygen atom. The fluoroalkyl group having 1 to 30 carbon atoms is an organic group in which 1 or more hydrogen atoms in the alkyl group are substituted with fluorine atoms. As such fluoroalkyl groups, fluoroalkyl groups and perfluoroalkyl groups are included.
In one embodiment, R1、R2、R3And R4Any 1 of the fluorine-containing organic groups is a fluorine-containing organic group having 1 to 30 carbon atoms, and the balance is a hydrogen atom. Preferably R1、R2、R3And R4Any 1 of them is a fluoroalkyl group having 1 to 30 carbon atoms, and the rest is a hydrogen atom. More preferably R1、R2、R3And R4Any 1 of them is a perfluoroalkyl group having 1 to 30 carbon atoms, and the rest is a hydrogen atom. By R1、R2、R3And R4Wherein any 1 of the fluorine-containing organic groups has 1 to 30 carbon atoms and the balance is a hydrogen atom, can improve the film-forming property of the photosensitive resin composition containing the polymer P, and can make the obtained cured film have low dielectric property.
In one embodiment, R is preferred5Is a fluoroalkyl group having 1 to 30 carbon atoms or a fluoroalkyl group having 1 to 30 carbon atoms and having an etheric oxygen atom.
In one embodiment, R is preferably formed1、R2、R3And R4The organic group(s) of (a) is an organic group having no acidic functional groupAnd (4) clustering. The acid value of the polymer P can be easily controlled by not having an acidic organic group.
The polymer P of the present embodiment may further include at least one of the structural units represented by formulae (B2) to (B6).
Figure BDA0003567946470000061
Wherein, in the formula (B2), R6And R7Each independently an organic group having 1 to 30 carbon atoms.
In the formula (B6), R8Is an organic group having 1 to 30 carbon atoms.
The definition of the organic group having 1 to 30 carbon atoms is the same as that described above.
R5、R6、R7Any of them preferably has a carbon-carbon double bond crosslinked by a photo radical polymerization initiator. Examples thereof include a vinyl group, a vinylidene group, an allyl group, an acryloyl group, and a methacryloyl group.
Among them, from the viewpoint of improving the heat resistance of the cured film obtained, it is preferable to contain a maleimide-derived structural unit represented by formula (B5) or formula (B6). Preferably form R6～R8None of the organic groups (2) has an acidic functional group such as a carboxyl group. This makes it possible to easily control the acid value of the polymer P.
The polymer P of the present embodiment can be produced by addition polymerization of a norbornene-type monomer (monomer a) represented by the formula (3) and maleic anhydride (monomer B) represented by the formula (4). When the polymer P of the present embodiment further contains a structural unit represented by the formula (B5) and/or the formula (B6), the target polymer can be prepared by addition-polymerizing a norbornene-type monomer (monomer a) with maleic anhydride and maleimide and/or a maleimide derivative represented by the formula (5) (monomer B).
Figure BDA0003567946470000071
In the formula (3), n is 0, 1 or 2, R1、R2、R3And R4Each independently hydrogen or an organic group having 1 to 30 carbon atoms.
In the formula (5), R8The definitions of (a) are the same as those described above.
Examples of norbornene-type monomers that can be used include the following norbornenes.
Figure BDA0003567946470000081
Figure BDA0003567946470000091
Figure BDA0003567946470000101
Figure BDA0003567946470000111
Figure BDA0003567946470000121
Examples of the maleimide derivative represented by the above formula (5) include N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (4-aminophenyl) maleimide, N-benzylmaleimide, N-t-butylmaleimide, N-ethylmaleimide, N- (2-hydroxyethyl) maleimide, N-methoxycarbonylmaleimide, 3-maleimidopropionic acid, 4-maleimidobutyric acid and 6-maleimidocaproic acid. Among them, N-cyclohexylmaleimide is preferably used. This can improve the heat resistance and chemical resistance of the cured product of the polymer P.
The polymer P can be synthesized by addition polymerization of the monomer a and the monomer B.
Further, the monomers A and B are not limited to 1 or 2 or more types of monomers, respectively.
The method of addition polymerization is not particularly limited, but in the present embodiment, a copolymer is synthesized by radical polymerization using a radical polymerization initiator.
By addition polymerization using a radical polymerization initiator, a copolymer having a structural unit derived from the monomer a and a structural unit derived from the monomer B and having a terminal derived from the radical polymerization initiator can be synthesized.
The preferred molar ratio of the monomer A to the monomer B in the copolymer is 1: 0.5-1: 2. In addition, the ratio of 1: 0.5-1: 2 includes 1: 0.5 and 1: 2. Among them, the molar ratio is preferably 1: 1 from the viewpoint of improving controllability of the molecular structure.
The addition polymerization is performed by dissolving the monomer a, the monomer B, and a radical polymerization initiator in a solvent and then heating for a predetermined time. The heating temperature is, for example, 50 ℃ to 80 ℃ and the heating time is 3 hours to 20 hours.
In addition, in addition polymerization, an additive such as a chain transfer agent may be used. It is preferable to introduce a functional group which reacts with the crosslinking agent into the terminal of the copolymer by controlling the terminal structure of the copolymer by adding a chain transfer agent.
The radical polymerization initiator is not limited as long as a functional group capable of reacting with the crosslinking agent is introduced into X, which is one of the terminal ends of the copolymer, and an azo compound or a peroxide can be used. Among them, azo compounds are preferably used.
Specific examples of the azo compound include a radical polymerization initiator having a carboxyl group such as 4, 4 '-azobis (4-cyanovaleric acid) and 2, 2' -azobis [ N- (2-carboxyethyl) -2-methyl ]; radical polymerization initiators having an amino group such as 2, 2 '-azobis (2-methylpropionamidine) and 2, 2' -azobis [2- (2-imidazolin-2-yl) propane ]; a radical polymerization initiator having a hydroxyl group such as 2, 2' -azobis [ 2-methyl-N- (2-hydroxyethyl) propionamide ]. Among them, a radical polymerization initiator having a carboxyl group is preferably used, and among them, 4' -azobis (4-cyanovaleric acid) is more preferably used. This improves the heat resistance and chemical resistance of the obtained polymer P.
The amount (mole number) of the radical polymerization initiator added is preferably 1% to 10% of the total mole number of the monomer A and the monomer B. By appropriately setting the amount of the radical polymerization initiator within the above range, and appropriately setting the reaction temperature and reaction time, the weight average molecular weight (Mw) of the obtained copolymer can be adjusted.
A copolymer obtained by addition polymerization of the monomer a and the monomer B (referred to as a "polymer precursor" or a "polymer before ring opening") is converted into the polymer P through a ring opening step. In the ring-opening step, in the polymer precursor obtained as described above, a part of the repeating units in the structural units derived from maleic anhydride is in a ring-closed state, and the remaining repeating units are ring-opened. Thereby, the amount of carboxyl groups in the copolymer can be adjusted. That is, the acid value of the produced copolymer can be controlled. Further, the alkali solubility of the photosensitive resin composition containing the polymer P can be adjusted by controlling the acid value.
In the present embodiment, of the repeating units derived from maleic anhydride of the polymer precursor, for example, 50% or more of the repeating units are not ring-opened, but the cyclic structure (acid anhydride ring) of the remaining repeating units is ring-opened. That is, the ring-opening ratio of the copolymer is, for example, less than 50%. Among these, it is preferable to ring-open 10% to 30% of the total number of repeating units derived from the cyclic structure of maleic anhydride in the copolymer.
Here, the ring opening ratio of the repeating unit derived from maleic anhydride can be measured as follows.
The IR absorption intensity (Abs1) of (C ═ O) in the acid anhydride structure of the polymer before ring opening (polymer precursor) was measured, and the ring opening ratio was calculated from the IR absorption intensity (Abs2) of (C ═ O) in the acid anhydride structure after ring opening using the following formula.
The ring opening ratio (%) (((Abs1) - (Abs2))/(Abs1)) × 100
Of these, acetonitrile was used as an internal standard.
The polymer precursor is treated with any one of (i) a metal alkoxide as a base, (ii) an alcohol and a hydroxide of an alkali metal as a base, and (iii) an organic base such as an alcohol and a tertiary amine, and becomes a polymer P obtained by ring-opening a maleic anhydride structural unit. Specifically, in the polymerization step, the reagent (i) or (ii) is added to the reaction solution obtained by polymerizing the monomer A, B, and an organic solvent such as Methyl Ethyl Ketone (MEK) is further added thereto, and the mixture is stirred at a temperature of 40 to 50 ℃ for 1 to 5 hours, thereby obtaining a reaction solution L1. In the reaction liquid L1, a part of the anhydride rings of the repeating units derived from maleic anhydride of the copolymer were opened, and a part of the terminals formed by the opening was esterified. In addition, the remaining terminal is not esterified and becomes a metal salt structure.
In the present embodiment, the number of moles of the metal alkoxide or the alkali metal hydroxide is preferably 50% or less of the number of moles of the maleic anhydride used in the polymerization step. Among these, the number of moles of the metal alkoxide or the alkali metal hydroxide is preferably 40% or less and 10% or more, and more preferably 30% or less of the number of moles of maleic anhydride used in the polymerization step. In this way, the amount of the metal alkoxide or the alkali metal hydroxide can be reduced, and the alkali metal concentration in the finally obtained polymer P can be reduced. By reducing the alkali metal concentration in the polymer P, migration of metal ions in a device using a resin composition using the polymer P can be suppressed.
The metal alkoxide is preferably represented by M (OR)5) Metal alkoxide (M is a metal having a valence of 1, R)5An organic group having 1 to 30 carbon atoms). The metal M may be an alkali metal, and among them, sodium is preferable from the viewpoint of workability. As R5For example, R in the above formula (2a) is the same as R5The same organic group.
As the metal alkoxide, 2 or more different metal alkoxides may be used. However, from the viewpoint of production stability, 1 metal alkoxide is preferably used.
On the other hand, as described above, the structure derived from maleic anhydride of the polymer precursor may be opened in the presence of (ii) an alcohol and a hydroxide of an alkali metal as a base.
As the alkali metal hydroxide, sodium hydroxide is preferred from the viewpoint of handling properties.
As the alcohol, a monohydric alcohol (R) is preferred5OH). R as an organic radical5The above-mentioned organic group may be used. In addition, R5The number of carbon atoms is preferably 1 to 30.
As the monohydric alcohol (R) preferably used in the present embodiment5OH), there may be mentioned allyl alcohol, methallyl alcohol, 3-buten-1-ol, 3-methyl-3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, 6-hepten-1-ol, 7-octen-1-ol, 8-nonen-1-ol, 9-decen-1-ol, 10-undecen-1-ol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 1, 4-cyclohexanedimethanol monoacrylate and 1, 4-cyclohexanedimethanol monomethacrylate, ethylene glycol, propylene glycol, ethylene glycol, propylene glycol, ethylene glycol, propylene glycol, ethylene glycol, propylene glycol, ethylene glycol, propylene glycol, ethylene glycol, propylene glycol, ethylene glycol, propylene glycol, ethylene glycol, propylene glycol, ethylene glycol, propylene glycol, ethylene glycol, propylene glycol, ethylene glycol, propylene glycol, ethylene glycol, propylene glycol, ethylene glycol, propylene glycol, ethylene glycol, propylene glycol, ethylene, 1H, 1H-trifluorovinyl alcohol, 1H-pentafluoropropanol, 6- (perfluoroethyl) hexanol, 1H-heptafluorobutanol, 2- (perfluorobutyl) ethanol, 3- (perfluorobutyl) propanol, 6- (perfluorobutyl) hexanol, 2-perfluoropropoxy-2, 2, 3, 3-tetrafluoropropanol, 2- (perfluorohexyl) ethanol, 3- (perfluorohexyl) propanol, 6- (perfluorohexyl) hexanol, 1H-2, 5-bis (trifluoromethyl) 3, 6-dioxaundecafluorononol, 6- (perfluoro-1-methylethyl) hexanol, 1H, 3H-tetrafluoropropanol, 1H, 5H-octafluoropentanol, 1H, 7H-dodecafluoroheptanol, 1H-perfluorohexyl) ethanol, 2- (perfluorohexyl) propanol, 6-dioxa-n-ethyl-ol, 1H, 3H-tetrafluoropropanol, 1H, 5H-octafluoropentanol, 1H, 7H-dodecafluoroheptanol, and mixtures thereof, 2H-hexafluoro-2-propanol, 1H, 3H-hexafluorobutanol, 2-bis (trifluoromethyl) propanol, and the like, but are not limited thereto. These alcohols may be used alone in 1 kind, or 2 or more kinds may be used in combination.
The repeating unit derived from maleic anhydride ring-opened in the ring-opening step has a structure represented by the following formula (5a) and has a structure of a salt moiety having a carboxyl group.
Figure BDA0003567946470000161
(in the formula (5a), R5An organic group having 1 to 30 carbon atoms)
When the copolymer is ring-opened by (i) a metal alkoxide as an alkali or (ii) an alcohol and a hydroxide of an alkali metal as an alkali, a structure represented by the following general formula (B2) or the following formula (5B) may be formed, although in a small amount. In the general formula (B2), R6、R7May be reacted with the above R5The same is true.
Figure BDA0003567946470000162
(in the formula (B2), R6And R7Each independently an organic group having 1 to 30 carbon atoms)
Figure BDA0003567946470000163
After the ring-opening reaction, a monomer having an epoxy group and a double bond group is further reacted, whereby a polymer P having a group containing a crosslinkable double bond introduced therein can be obtained. In the present embodiment, as the monomer having an epoxy group and a double bond group, glycidyl acrylate, glycidyl methacrylate, or 3, 4-epoxycyclohexylmethyl methacrylate is preferably used in view of easy availability. In addition, the fluorine functional group can also be introduced by reacting a monomer having an epoxy group and a fluorine functional group in the same manner. For example, 3-perfluorobutyl-1, 2-epoxypropane, 3-perfluorohexyl-1, 2-epoxypropane, 3-perfluorooctyl-1, 2-epoxypropane and the like can be used. The polymer P containing a group having a double bond can improve the crosslinkability by the photo radical polymerization initiator, and as a result, the sensitivity of the polymer P can be improved.
Next, an acidic aqueous solution such as hydrochloric acid or formic acid is added to the reaction solution L1 to subject the copolymer to an acid treatment, thereby removing metal ions (Na)+) Substitution by protons (H)+)。
The structural unit represented by the above formula (6) is a structural unit represented by the following (2a) and (B4) by proton substitution, respectively.
Figure BDA0003567946470000171
(in the formula (2a), R5An organic group having 1 to 30 carbon atoms)
Figure BDA0003567946470000172
In the ring-opening step (S3), it is preferable that 50% or more of the repeating units derived from maleic anhydride in the polymer precursor are not ring-opened. As described above, in the polymer P, a metal such as Na is bonded to one end formed by ring opening of maleic anhydride, but the amount of the metal contained in the polymer P as a product can be reduced by not ring opening 50% or more of the repeating units. This can reduce the amount of alkali metal in the polymer P finally obtained in the present embodiment, and can exhibit desired characteristics in the photosensitive resin composition containing the polymer P.
After the ring-opening step, the solution containing the obtained polymer P may be washed with a mixed solution of water and an organic solvent (for example, methyl ethyl ketone) to remove the remaining metal components. Further, the washing step is preferably performed so that the alkali metal concentration in the polymer P becomes 10ppm or less, preferably 5ppm or less.
From the viewpoint of forming an appropriate crosslinked structure, the weight average molecular weight (Mw) of the polymer P of the present embodiment is preferably in the range of 1000 to 20000, more preferably 1500 to 15000, and still more preferably 2000 to 10000. From the viewpoint of forming an appropriate crosslinked structure, the number average molecular weight (Mn) of the polymer P of the present embodiment is preferably 500 to 10000, more preferably 1000 to 8000. The molecular weight distribution (Mw/Mn) of the polymer P is preferably 1.0 to 2.5, and more preferably 1.2 to 2.0, from the viewpoint of making the physical properties of each molecular chain of the polymer P uniform and making the shape of the resin film obtained by curing good. The molecular weight of the polymer P can be controlled by adjusting the kind of the above-mentioned monomer used for producing the polymer P, the amount of the monomer to be blended, the adjustment conditions, and the like.
The double bond equivalent weight of the polymer P of the present embodiment is preferably 500g/mol or more and 2500g/mol or less, and more preferably 500g/mol or more and 2000g/mol or less. When the double bond equivalent is within the above range, the polymer P can be suitably used for a photosensitive resin composition for exposure development treatment.
The fluorine content of the polymer P of the present embodiment is preferably 25 wt% or more and 45 wt% or less, and more preferably 30 wt% or more and 40 wt% or less. When the fluorine content is within the above range, a cured product of the polymer P has excellent heat resistance and solvent resistance. The fluorine content of the polymer P can be controlled by adjusting the kind and the amount of the above-mentioned monomer used for producing the polymer P.
The polymer P of the present embodiment has excellent alkali solubility, and therefore, has excellent processability in an exposure development treatment using an alkali aqueous solution as a developer. The rate of alkaline dissolution of the polymer P may be, for example
Figure BDA0003567946470000181
The above
Figure BDA0003567946470000182
Hereinafter, more preferably, the compound may be
Figure BDA0003567946470000184
The above
Figure BDA0003567946470000183
The following. The alkali dissolution rate was calculated by immersing a polymer film, which was coated on a silicon wafer by spin coating with a propylene glycol monomethyl ether acetate solution of polymer P (35 mass% as a solid content) and softened at 100 ℃, in a 2.38% aqueous tetramethylammonium hydroxide solution at 23 ℃ and measuring the time until the polymer film visually disappearedBaking for 120 seconds.
The polymer P of the present embodiment has a refractive index of, for example, 1.38 to 1.48, and more preferably 1.40 to 1.46. The polymer P having a refractive index within the above range is excellent in processability at the time of exposure and development, and a cured product thereof has desired properties as a permanent film of an electronic device.
(photosensitive resin composition)
The polymer P of the present embodiment can be used in a photosensitive resin composition for forming a resin film of an electronic device.
The photosensitive resin composition of the present embodiment includes: the above-mentioned polymer P; a crosslinking agent; and a photosensitizer.
The photosensitive resin composition of the present embodiment contains the polymer P, and thus a cured product thereof has excellent heat resistance and solvent resistance and low dielectric properties. Therefore, the photosensitive resin composition of the present embodiment can be suitably used as a material for producing a permanent film of an electronic device.
The components used in the photosensitive resin composition will be described in detail below. As regards the polymer P, this is as described above.
(crosslinking agent)
The photosensitive resin composition of the present embodiment contains a crosslinking agent. The crosslinking agent is not limited as long as it is a compound containing a functional group capable of reacting with an active hydrogen of the polymer P. Examples of such a crosslinking agent include compounds having at least 1 functional group selected from the group consisting of an epoxypropyl group, an oxetanyl group and a blocked isocyanate group. The crosslinking agent is preferably a compound having an epoxypropyl group or an oxetanyl group, and more preferably a compound having an epoxypropyl group. By using such a crosslinking agent, an appropriate crosslinked structure can be formed. Further, as the crosslinking agent, 1 or 2 or more selected from a compound having a blocked isocyanate group, an epoxy compound and an oxetane compound can be used at the same time.
Examples of the compound having a glycidyl group which can be used as a crosslinking agent include allyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyoxypropylene ether, sorbitol polyoxypropylene ether, glycidyl ethers such as glycidyl ether of bisphenol a (or F), glycidyl esters such as diglycidyl adipate and diglycidyl phthalate, 3, 4-epoxycyclohexylmethyl (3, 4-epoxycyclohexane) carboxylate, 3, 4-epoxy-6-methylcyclohexylmethyl (3, 4-epoxy-6-methylcyclohexane) carboxylate, bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentadiene oxide, bis (2, 3-epoxycyclopentyl ether, alicyclic epoxy compounds such as CELLOXIDE 2021, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, CELLOXIDE 8000, EPOLED GT401, etc., 2' - ((((((1- (4- (epoxyethane-2-ylmethoxy) phenyl) propan-2-yl) phenyl) ethane-1, 1-diyl) bis (4, 1-phenylene)) bis (oxy)) bis (methylene)) bis (ethylene oxide) (e.g., Techmore VG 310310 3101L (Printec Corporation)), Epolite 100MF (Keisha Co., Ltd.), EPTMP (NOF Corporation), 1-bis (cyclopropyl-O Co., Ltd.)), NEYOPROXYL CO Co., Ltd.) (NOC Co., Ltd., N.N.P., N.P.), EPTMP (NOF Corporation ), 1-cyclopropyl-cyclohexane dimethanol (NEYNOC Co., Ltd.), ltd.), aliphatic glycidyl ether such as Showa Denko co., Ltd.), aromatic glycidyl ether such as 3, 3 ', 5, 5' -tetramethyl-4, 4 '-bis (glycidoxy) -1, 1' -biphenyl, and epoxy resin such as 1,1, 3, 3, 5, 5-hexamethyl-1, 5-bis (3- (oxiran-2-ylmethoxy) propyl) trisiloxane (e.g., DMS-E09 (manufactured by Gelest, inc.).
Further, for example, a bisphenol A type epoxy resin such as LX-01 (manufactured by Daiso Co., Ltd.), JeR1001, JeR1002, JeR1003, JeR1004, JeR1007, JeR1009, JeR1010, JeR828, and JeR825 (trade name; manufactured by Mitsubishi Chemical Corporation), a bisphenol F type epoxy resin such as JeR807 (manufactured by Mitsubishi Chemical Corporation), a phenol novolac type epoxy resin such as JeR152, JeR154 (trade name; manufactured by Mitsubishi Chemical Corporation), EPPN201, EPPN202 (trade name; manufactured by Nippon Kayaku Co., Ltd.), a phenol novolac type epoxy resin such as JeR152, JeR154 (trade name; manufactured by Mitsubishi Chemical Corporation), EOCN102, EOCN103S, EOCN104S, 1020, 1021025, 1025 (trade name; manufactured by Nippon Kayaku Co., Ltd.), a JER 184 (manufactured by CY Chemical Corporation), a phenol novolac type epoxy resin such as Arvatic 184, a phenol novolac type epoxy resin (manufactured by Arvata Co., Ltd., manufactured by Arthron Honda 179, Sanshi Chemical Corporation), a phenol novolac type epoxy material, and so on 179, manufactured by Arthron Chemical Corporation, a phenol novolac type novolak type epoxy resin, and so on, ERL-4206, 4221, 4234, 4299 (trade name; manufactured by The Dow Chemical Company), EPICLON 200, EPICLON 400 (trade name; manufactured by DIC Corporation), jER871, jER872 (trade name; manufactured by Mitsubishi Chemical Corporation), etc., a polyfunctional alicyclic epoxy resin such as poly [ (2-epoxyethyl) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propanediol ether (3: 1), etc., and EHPE-3150 (manufactured by Daiiol Co., Ltd.).
Examples of the compound having an oxetanyl group which can be used as a crosslinking agent include 1, 4-bis { [ (3-ethyl-3-oxetanyl) methoxy ] methyl } benzene, bis [ 1-ethyl (3-oxetanyl) ] methyl ether, 4 '-bis [ (3-ethyl-3-oxetanyl) methoxymethyl ] biphenyl, 4' -bis (3-ethyl-3-oxetanylmethoxy) biphenyl, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) diphenol, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, Oxetane compounds such as pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, poly [ [3- [ (3-ethyl-3-oxetanyl) methoxy ] propyl ] silsesquioxane ] derivative, oxetanyl silicate, phenol novolak-type oxetane, and 1, 3-bis [ (3-ethyloxetan-3-yl) methoxy ] benzene.
The compound having a blocked isocyanate group which can be used as a crosslinking agent is not limited, and examples thereof include compounds obtained by protecting an isocyanate group of a polyfunctional isocyanate with a blocking agent.
The polyfunctional isocyanate is an organic compound having a plurality of isocyanate groups in one molecule. Examples of the polyfunctional isocyanate include diisocyanate compounds selected from the group consisting of 1, 4-tetramethylene diisocyanate, 1, 5-pentamethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 2, 4-trimethyl-1, 6-hexamethylene diisocyanate, lysine diisocyanate, 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1, 3-bis (isocyanatomethyl) -cyclohexane, 4 '-dicyclohexylmethane diisocyanate, toluene diisocyanate, 4' -diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, triazine diisocyanate, xylylene diisocyanate, and the like; and 1 or 2 or more of the above diisocyanate compound derivatives such as isocyanurate-modified polyfunctional isocyanate, biuret-modified polyfunctional isocyanate and urethane-modified polyfunctional isocyanate.
Examples of the blocking agent include one or more selected from alcohol compounds, phenol compounds, active methylene compounds, thiol compounds, acid amide compounds, acid imide compounds, imidazole compounds, urea compounds, oxime compounds, amine compounds, imine compounds, bisulfite, and pyridine compounds.
Specific examples of the blocking agent include alcohol compounds such as methanol, ethanol, propanol, butanol, 2-ethylhexanol, methylcellosolve, butylcellosolve, methylcarbitol, benzyl alcohol, and cyclohexanol; phenol compounds such as phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, and hydroxybenzoates; active methylene compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone; mercaptan compounds such as butyl mercaptan and dodecyl mercaptan; acid amide compounds such as acetanilide, acetic acid amide, epsilon-caprolactam, delta-valerolactam and gamma-butyrolactam; acid imide compounds such as succinimide and maleimide; imidazole compounds such as imidazole and 2-methylimidazole; urea compounds such as urea, thiourea and ethylene urea; oxime compounds such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanone oxime; amine compounds such as diphenylamine, aniline, and carbazole; imine compounds such as ethyleneimine and polyethyleneimine; bisulfite such as sodium bisulfite; pyridine compounds such as 2-hydroxypyridine and 2-hydroxyquinoline.
Specific examples of the compound having a blocked isocyanate group which can be used as such a crosslinking agent include BURNOCK D-500 (blocked toluene diisocyanate), BURNOCK D-550 (blocked 1, 6-hexamethylene diisocyanate), BURNOCK D-980K (blocked 1, 6-hexamethylene diisocyanate), manufactured by Dainippon Ink and Chemicals, Inc.; TAKENATE B-830 (tolylene diisocyanate terminated product), TAKENATE B-815N (4, 4' -methylenebis (cyclohexylisocyanate) terminated product), TAKENATE B-842N (1, 3-bis (isocyanotomethyl) cyclohexane terminated product), TAKENATE B-846N (1, 3-bis (isocyanotomethyl) cyclohexane terminated product), TAKENATE B-874N (isophorone diisocyanate terminated product), TAKENATE B-882N (1, 6-hexamethylene diisocyanate terminated product), and TAKENATE B-890 (xylylene diisocyanate terminated product), manufactured by Mitsui martial chemical corporation (MITSUI TAKEDA CHEMICALS, INC); TAKENATE B-820NP (1, 3-bis (isocyanatomethyl) cyclohexane terminated compound), TAKENATE B-885N (1, 6-hexamethylene diisocyanate terminated compound); DURANATE MF-B60X (1, 6-hexamethylene diisocyanate-terminated product), DURANATE MF-K60X (1, 6-hexamethylene diisocyanate-terminated product), and the like, manufactured by Asahi Kasei CORPORATION (ASAHI KASEI CORPORATION).
(photosensitizers)
When the photosensitive resin composition is a positive type, a photoactive compound, for example, a diazoquinone (diazoquinone) compound, can be used as the photosensitizer.
For example, any of the following 1 or more compounds may be used.
Figure BDA0003567946470000231
Figure BDA0003567946470000241
Figure BDA0003567946470000251
(n2 represents an integer of 1 to 5.)
Figure BDA0003567946470000261
Figure BDA0003567946470000271
Figure BDA0003567946470000281
In each of the above compounds, Q is a hydrogen atom or any one of the structures shown below. However, at least 1 of Q in each compound is any of the following.
Among them, the o-naphthoquinone diazide sulfonic acid derivative in which Q is (a) or (b) is preferable from the viewpoint of transparency and dielectric constant of the photosensitive resin composition.
Figure BDA0003567946470000282
In addition, the positive photosensitive resin composition may contain an acid generator capable of generating an acid by light or heat, in addition to the above-described photoactive compound. By including such an acid generator, the crosslinking reaction of the crosslinking agent can be promoted by irradiation with light or heating after the photosensitive resin composition is exposed and developed.
In this case, the acid generator is preferably 3 parts by mass or less with respect to 100 parts by mass of the crosslinking agent.
As the photoacid generator capable of generating an acid by using light, a photoacid generator described later can be used.
As the thermal acid generator capable of generating an acid by heat, aromatic sulfonium salts such as SI-45L, SI-60L, SI-80L, SI-100L, SI-110L, SI-150L (manufactured by Sanxin chemical Co., Ltd. (SANSHIN CHEMICAL INDUSTRY CO., LTD.) can be used.
For example, when the total solid content of the photosensitive resin composition is 100 mass%, the content of the thermal acid generator is preferably 0.1 mass% or more and 5 mass% or less.
In the present embodiment, all solid components of the photosensitive resin composition represent components other than the solvent.
In addition, when the photosensitive resin composition is a negative type, a photoacid generator can be used as the photosensitizer. The photoacid generator may be any one as long as it can absorb energy of light to generate brensted acid or lewis acid, and examples thereof include sulfonium salts such as triphenylsulfonium trifluoromethanesulfonate and tris (4-tert-butylphenyl) sulfonium-trifluoromethanesulfonate; diazonium salts such as p-nitrophenyl diazonium hexafluorophosphate; ammonium salts; phosphonium salts; iodonium salts such as iodonium trifluoromethane sulfonate and (triisopropylphenyl) iodonium-tetrakis (pentafluorophenyl) borate; diazomethanes such as quinonediazide and bis (phenylsulfonyl) diazomethane; sulfonic acid esters such as 1-phenyl-1- (4-methylphenyl) sulfonyloxy-1-benzoylmethane and N-hydroxynaphthalimide-trifluoromethanesulfonate; disulfones such as diphenyl disulfone; and triazines such as tris (2, 4, 6-trichloromethyl) -s-triazine and 2- (3, 4-methylenedioxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine. These photoacid generators may be used alone or in combination of two or more.
When the photosensitive resin composition is a negative type, the second crosslinking agent may include a compound that crosslinks the copolymer by the action of an acid. The second crosslinking agent is a compound that crosslinks the copolymer using an acid generated by the photoacid generator as a catalyst, and is a compound different from the compound used in the crosslinking agent.
Examples thereof include melamine-based crosslinking agents and urea-based crosslinking agents.
Examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutylmelamine, and the like, and hexamethoxymethylmelamine is preferable among them.
Examples of the urea-based crosslinking agent include methylated urea resin, bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, and bisbutoxymethyl urea, and among them, methylated urea resin is preferable.
Examples of commercially available methylated urea resins include MX-270, MX-280, and MX-290 (manufactured by Kabushiki Kaisha, Kagaku Kogyo (SANWA CHEMICAL CO., LTD.)).
The proportion of the second crosslinking agent in the negative photosensitive resin composition is preferably 5 mass% or more and 40 mass% or less, more preferably 5 mass% or more and 30 mass% or less, and even more preferably 10 to 25 mass%, from the viewpoint of resolution, assuming that the total solid content of the resin composition is 100 mass%.
In the above photosensitive resin composition, when the photosensitive resin composition is a positive type, the proportions of the respective components are, for example, as follows.
When the total solid content of the photosensitive resin composition is 100 mass%, the copolymer is preferably contained in an amount of, for example, 30 to 70 mass%, and more preferably 40 to 60 mass%.
When the total solid content of the photosensitive resin composition is 100 mass%, the crosslinking agent is preferably contained in an amount of, for example, 15 mass% or more and 50 mass% or less, and particularly preferably 20 mass% or more and 50 mass% or less.
Further, when the total solid content of the photosensitive resin composition is 100 mass%, for example, the photoactive compound as the photosensitizer is preferably contained in an amount of 5 to 40 mass%, and more preferably 10 to 30 mass%.
When the photosensitive resin composition is a negative type, the proportions of the respective components are, for example, as follows.
When the total solid content of the photosensitive resin composition is 100 mass%, the copolymer is preferably contained in an amount of, for example, 30 to 70 mass%, and more preferably 40 to 60 mass%.
When the total solid content of the photosensitive resin composition is 100 mass%, the content of the crosslinking agent (excluding the second crosslinking agent) is preferably 15 mass% or more and 50 mass% or less, and more preferably 20 mass% or more and 50 mass% or less (excluding the second crosslinking agent), for example.
When the total solid content of the photosensitive resin composition is 100 mass%, the amount of the photoacid generator is, for example, 0.1 mass% or more and 40 mass% or less, and more preferably 1 mass% or more and 30 mass% or less, from the viewpoint of forming a high-resolution pattern film.
The photosensitive resin composition may further contain additives such as a solvent, an antioxidant, a surfactant, an adhesion promoter, a dissolution accelerator, a filler, a sensitizer, and a polyphenol.
(resin film)
The resin film of the present embodiment is composed of a cured product of the photosensitive resin composition. The resin film has excellent heat resistance and can be used as a resist or a permanent film in an electronic device.
When the resin film of the present embodiment is used as a resist, the resist can be produced by applying the photosensitive resin composition of the present embodiment by a method such as spin coating, roll coating, flow coating, dip coating, spray coating, or knife coating (sector coat) to obtain a coating film and removing the solvent.
When the resin film of the present embodiment is used as a permanent film, it can be obtained by: the coating film of the photosensitive resin composition obtained as described above is exposed to light and developed to be patterned into a desired shape, and then cured by heat treatment or the like. The permanent film can be used, for example, as a protective film, an interlayer film, or the like of an electronic device.
The electronic device of the present embodiment includes the resin film described above.
The electronic device of the present embodiment includes the resin film described above.
For example, when the electronic device is a semiconductor chip, a passivation film or an insulating layer constituting the semiconductor chip is formed from a cured product of the photosensitive resin composition of the present embodiment.
While the embodiments of the present invention have been described above, these are merely illustrative of the present invention, and various configurations other than the above-described configurations may be adopted.
[ examples ]
The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples.
(Synthesis example 1: Synthesis of precursor Polymer A)
5-Nononafluorobutylbicyclo [2.2.1] hept-2-ene (NBC4F9, 22.9g, 72.8mmol), maleic anhydride (MAN, 7.1g, 72.8mmol), dimethyl 2, 2' -azobis (2-methylpropionate) as an initiator (product name: V-601, 3.4g, 14.6mmol, manufactured by Wako Pure Chemical Industries, Ltd.) and 9.5g of Methyl Ethyl Ketone (MEK) were charged into an appropriate reaction vessel and dissolved by stirring. Then, dissolved oxygen in the system was removed by nitrogen bubbling, and the mixture was heated and reacted at an internal temperature of 60 ℃ for 16 hours. Subsequently, the reaction mixture was cooled to room temperature, and diluted by adding 32.1g of MEK. The diluted solution was poured into a large amount of methanol to precipitate a polymer. Subsequently, the polymer was collected by filtration, washed with methanol, and dried under vacuum at 120 ℃ for 16 hours. The yield of the polymer was 25.0g, which was 83%. The polymer had a weight average molecular weight Mw of 2,400 and a dispersity (weight average molecular weight Mw/number average molecular weight Mn) of 1.69.
(Synthesis example 2 Synthesis of precursor Polymer B)
NBC4F9(22.9g, 72.8mmol), MAN (7.1g, 72.8mmol), V-601(1.7g, 7.3mmol) and MEK11.2g were charged into an appropriate reaction vessel and dissolved by stirring. Then, dissolved oxygen in the system was removed by nitrogen bubbling, and the mixture was heated and reacted at an internal temperature of 60 ℃ for 5 hours. Subsequently, the internal temperature was raised to 80 ℃ and the reaction was further allowed to proceed for 3 hours. The reaction mixture was cooled to room temperature and poured into a large amount of methanol to precipitate a polymer. Subsequently, the polymer was collected by filtration, washed with methanol, and dried under vacuum at 120 ℃ for 16 hours. The yield of the polymer was 14.9g, which was 50%. Also, the Mw of the polymer was 4,000 and the Mw/Mn was 1.50.
(Synthesis example 3 Synthesis of precursor Polymer C)
Maleic anhydride (24.3 g, 247.8mmol, manufactured by NIPPON SHOKUBAI co., LTD.), bicyclo [2.2.1] hept-5-ene-2-carboxylic acid-3, 3, 4, 4, 5, 5, 6, 6, 7, 7,8, 8, 8-tridecafluorooctyl ester (NBCOOC2H4C6F13, 120.0g, 247.8mmol) and dimethyl 2, 2' -azobis (2-methylpropionate) (V-601, fuji film and Wako Pure Chemical Corporation, 7.61g, 30.6mmol) were metered into a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube, and dissolved in methyl ethyl ketone (MEK, 28.5 g). After nitrogen gas was introduced into the solution for 10 minutes to remove oxygen, the temperature was raised to 60 ℃ with stirring and held for 2 hours. Then, after heating to 80 ℃ and holding for 3 hours, V-601(3.81g, 15.3mmol) was added thereto and the mixture was reacted for 3 hours. After the reaction mixture was diluted with MEK, it was added dropwise to a large amount of methanol to precipitate a polymer. After filtration using a suction filter, the solid was further washed with methanol and vacuum-dried. The obtained polymer had a weight average molecular weight (Mw) of 5,400 and a dispersity (Mw/Mn) of 1.72.
(Synthesis example 4 Synthesis of precursor Polymer D)
Maleic anhydride (4.76g, 48.5mmol), 5-tridecafluorohexyl-2-norbornene (NBC6F13, 20.0g, 48.5mmol) and V-601(1.5g, 6.0mmol) were metered into an appropriately sized reaction vessel equipped with a stirrer and cooling tube and dissolved in MEK (4.7 g). After nitrogen gas was introduced into the solution for 10 minutes to remove oxygen, the temperature was raised to 60 ℃ with stirring and held for 2 hours. Then, after raising the temperature to 80 ℃ and holding the temperature for 3 hours, V-601(0.74g, 3.0mmol) was added thereto and the mixture was reacted for 3 hours. After the reaction mixture was diluted with MEK, it was added dropwise to a large amount of methanol to precipitate a polymer. After filtration using a suction filter, the solid was further washed with methanol and vacuum-dried. The obtained polymer had a weight average molecular weight (Mw) of 3,700 and a dispersity (Mw/Mn) of 1.64.
The amounts of the components used in synthesis examples 1 to 4 and the weight average molecular weights and the degrees of dispersion of the precursor polymers obtained are shown in table 1.
Figure BDA0003567946470000341
(Synthesis example 5 Synthesis of fluoropolymer A-1)
15.0g of the precursor polymer synthesized in Synthesis example 1 was dissolved in MEK27.9g. Further, 3.0g of 2-hydroxyethyl methacrylate (HEMA) and 1.5g of Triethylamine (TEA) were added thereto, and the mixture was heated to 70 ℃ and reacted for 6 hours. Subsequently, 1.6g of Glycidyl Methacrylate (GMA) was added thereto, and the mixture was allowed to react for 4 hours. The reaction mixture was cooled to room temperature and neutralized with formic acid. The solution was poured into a large amount of pure water to precipitate the polymer. The obtained polymer was collected by filtration, washed with pure water, dissolved in Propylene Glycol Monomethyl Ether Acetate (PGMEA), and concentrated under reduced pressure to obtain a polymer solution having a solid content of about 35%.
The polymer thus obtained had a weight average molecular weight (Mw) of 2,100 and a molecular weight distribution of 1.55. And the double bond equivalent was 1,700 g/mol. The fluorine content in the solid content of the polymer was 30% by weight.
(Synthesis example 6 Synthesis of fluoropolymer B-1)
The precursor polymer B5.0g synthesized in Synthesis example 2 was dissolved in MEK27.9g. Further, 1.0g of 2-hydroxyethyl methacrylate (HEMA) and 0.75g of Triethylamine (TEA) were added thereto, and the mixture was heated to 70 ℃ and reacted for 6 hours. Subsequently, 0.5g of Glycidyl Methacrylate (GMA) and 1.0g of 3-perfluorobutyl-1, 2-epoxypropane (PFBEp) were added, and the mixture was reacted at 70 ℃ for 4 hours. The reaction mixture was cooled to room temperature and neutralized with formic acid. The solution was poured into a large amount of pure water to precipitate the polymer. The obtained polymer was collected by filtration, washed with pure water, dissolved in PGMEA, and concentrated under reduced pressure to obtain a polymer solution having a solid content of about 35%.
The polymer thus obtained had a weight average molecular weight (Mw) of 4,000 and a molecular weight distribution of 1.50. And the double bond equivalent was 1,100 g/mol. The fluorine content in the solid content of the polymer was 33% by weight.
(Synthesis example 7 Synthesis of fluoropolymer C-1)
The precursor polymer C (10.0g) synthesized in synthesis example 3 was metered into a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube, and dissolved in MEK (10 g). Further, 4-hydroxybutyl acrylate (4HBA, 2.48g, 17.2 mmol; Mitsubishi chemical corporation) and triethylamine (2.0g) were added thereto, and the mixture was heated at 70 ℃ for 6 hours. After formic acid was added to the reaction solution to carry out acid treatment, the mixture was added dropwise to a large amount of pure water to precipitate a polymer. PGMEA was added to the filtered solid and concentrated to obtain a PGMEA solution of polymer. Mw was 4,900, Mw/Mn was 1.81, and the double bond equivalent weight was 1,600 g/mol. And the fluorine content in the polymer was 34 wt%.
(Synthesis example 8 Synthesis of fluoropolymer D-1)
The precursor polymer D (10.0g) synthesized in synthesis example 4 was measured in a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube, and dissolved in MEK (10 g). Further, 4HBA (2.83g, 17.2mmol) and triethylamine (2.0g) were added thereto, and the mixture was heated at 70 ℃ for 6 hours. After formic acid was added to the reaction solution to carry out acid treatment, the reaction solution was added dropwise to a large amount of purified water to precipitate a polymer. PGMEA was added to the filtered solid and concentrated to obtain a PGMEA solution of polymer. Mw was 3,900, Mw/Mn was 1.60, and the double bond equivalent weight was 1,400 g/mol. And the fluorine content in the polymer was 39 wt%.
Synthesis example 9 Synthesis of Polymer 1
2-norbornene (75 wt% toluene solution, produced by Maruzen Petrochemical Co., Ltd., 125.5g, 1.00mol) and dimethyl 2, 2' -azobis (2-methylpropionate) (V-601, produced by Wako pure chemical industries, Ltd., 9.2g, 40mmol) were measured in a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube, and dissolved in methyl ethyl ketone (MEK, 196.1 g). After nitrogen gas was introduced into the solution for 10 minutes to remove oxygen, the solution was heated to 80 ℃ with stirring. While the solution was kept at 80 ℃, a solution prepared by dissolving maleic anhydride (98.1 g, 1.00mol, manufactured by Nippon catalyst Co., Ltd.) in MEK119.9g was added dropwise over 1.5 hours, and the reaction was further carried out at that temperature for 8 hours. The reaction mixture was added dropwise to a large amount of methanol to precipitate a polymer. After filtration using a suction filter, the solid was further washed with methanol and vacuum-dried at 70 ℃. The obtained polymer had a weight average molecular weight (Mw) of 6,900 and a dispersity (Mw/Mn) of 1.76.
The precursor polymer (50.0g) was metered into a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube, and dissolved in MEK (90 g). Further, 2-hydroxyethyl methacrylate (HEMA, manufactured by Nippon catalyst Co., Ltd., 21.2g, 163mmol) and triethylamine (5.0g) were added thereto, and the mixture was heated at 70 ℃ for 6 hours. To the reaction solution, glycidyl methacrylate (GMA, 11.1g, 78mmol) was added, and the mixture was stirred at 70 ℃ for 4 hours. After formic acid was added to the reaction solution to carry out acid treatment, the reaction solution was added dropwise to a large amount of purified water to precipitate a polymer. The filtered solid was dried at 40 ℃ for 16 hours with a vacuum drier to obtain a polymer. Mw was 7,800 and Mw/Mn was 1.70. The double bond equivalent weight was 540 g/mol.
(weight average molecular weight/molecular weight distribution)
In the present specification, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) are polystyrene converted values obtained from a calibration curve of standard Polystyrene (PS) obtained by GPC measurement. The measurement conditions were as follows.
Gel permeation chromatography device HLC-8320GPC manufactured by Tosoh CORPORATION (TOSOH CORPORATION)
Column: TSK-GEL Superporous HZ-M manufactured by Tosoh corporation
A detector: RI detector for liquid chromatogram
Measuring the temperature: 40 deg.C
Solvent: THF (tetrahydrofuran)
Sample concentration: 2.0 mg/ml
(double bond equivalent)
The double bond equivalent weight of the fluoropolymers A-1 to D-1 was measured by the following method. First, about 50mg of the polymer after drying under reduced pressure to remove the solvent and about 5mg of dimethyl terephthalate as an internal standard were measured and dissolved in DMSO-d 6. This solution was subjected to 1H-NMR measurement using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL Ltd.). The polymer weight per 1 mole of double bonds (g/mol, double bond equivalent) was calculated from the integrated ratio of the signal derived from the (meth) acrylic group (5-7ppm) to the signal derived from the phenyl group of the internal standard (4H, 8.1ppm) of the obtained spectrogram.
(measurement of fluorine content)
The fluorine content of the fluoropolymers A-1 to D-1 was measured by the following method. First, about 10mg of the polymer after the solvent was removed by drying under reduced pressure was completely burned in a flask of a sealed system replaced with oxygen. The generated gas was trapped in a previously added alkali hydrogen peroxide absorbent solution and a volume (constant volume) of 50mL was determined as a sample solution. The sample solution and the standard solution were introduced into an ion chromatography apparatus (ICS-3000 type chromatograph manufactured by dean (Dionex)) and the concentration of fluoride ions was determined by a calibration curve method to calculate the amount of fluorine contained in the sample.
(measurement of refractive index)
The refractive index of the fluoropolymers A-1 to D-1 was measured by the following method. The polymer was dissolved in PGMEA at a concentration of 35 wt%. The obtained polymer solution was applied to a 3-inch silicon wafer by spin coating, and heat treatment was performed at 100 ℃ for 120 seconds, thereby obtaining a film of 1.0 to 1.5 μm. The refractive index at a wavelength of 632.8nm was measured using a prism coupler (prism coupler) (MODEL 2010M manufactured by Metricon corporation).
(alkali dissolution rate)
For the fluoropolymers A-1 to D-1, the alkali dissolution rate was measured as follows. The polymer was dissolved in PGMEA to prepare a solution having a solid content concentration of 35%. The polymer solution was applied to a silicon wafer by spin coating and soft-baked at 100 ℃ for 120 seconds to form a polymer film having a thickness H of about 2.0. mu.m. The silicon wafer on which the polymer film was formed was immersed in a 2.38% aqueous tetramethylammonium hydroxide solution at 23 ℃ to measure the time T until the polymer film was visually disappeared. From H and T, the alkali dissolution rate was calculated from the following formula.
Figure BDA0003567946470000381
The amounts of the components used in synthesis examples 5 to 8, the weight average molecular weight distribution of the obtained fluoropolymer, the double bond equivalent weight, the fluorine content, the refractive index, and the alkali dissolution rate are shown in table 2.
Figure BDA0003567946470000391
(preparation of photosensitive resin composition)
In each of examples and comparative examples, the polymer, photosensitizer, crosslinking agent, adhesion improver, and surfactant prepared in synthesis examples 5 to 9 were dissolved in PGMEA and cyclohexanone in the blending amounts shown in table 3, and stirred. After stirring, the mixture was filtered through a 0.2 μm filter to prepare a negative photosensitive resin composition.
The following compounds were used for each component shown in table 3.
(fluorine-containing Polymer)
Polymer A-1: fluoropolymer A-1 prepared in Synthesis example 5
Polymer B-1: fluoropolymer B-1 prepared in Synthesis example 6
Polymer C-1: fluoropolymer C-1 prepared in Synthesis example 7
Polymer D-1: fluoropolymer D-1 prepared in Synthesis example 8
(other Polymer)
Polymer 1: polymer 1 prepared in Synthesis example 9
(crosslinking agent)
Crosslinker 1: an acrylic crosslinking agent represented by the following formula (12) (DPHA manufactured by Daicel-Cytec Company, Ltd.).
Figure BDA0003567946470000401
(photosensitizers)
Photosensitizer 1: a photo radical polymerization initiator represented by the following formula (11) (Irgacure OXE02 manufactured by BASF corporation) was used.
Figure BDA0003567946470000402
(Advance adjuvant)
Adhesion promoter 1: 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.)
(surfactant)
Surfactant 1: MEGAFACE F-556(DIC corporation)
(solvent)
Solvent 1: propylene Glycol Monomethyl Ether Acetate (PGMEA)
Solvent 2: cyclohexanone
The negative photosensitive resin composition obtained as described above was evaluated for the following items.
(evaluation of sensitivity)
The prepared negative photosensitive resin compositions were applied to 3-inch silicon wafers using a spin coater, respectively. After coating, the coating film was prebaked on a hot plate at 100 ℃ for 2 minutes to obtain a coating film (film A) having a film thickness of about 3.0. mu.m.
The film is subjected to a g + h + i-ray mask manufactured by Canon Inc., having a gray scale of 1 to 100% transmittanceAlign the Exposure machine (PLA-501F) at 100mJ/cm2The exposure amount of (2) is an exposure to g + h + i rays.
After exposure, the unexposed portions are dissolved and removed by development for 60 seconds at 23 ℃ using 2.38% tetramethylammonium hydroxide as a developer to obtain a resist pattern of 1 to 100mJ/cm2The film exposed to each exposure amount (film B).
The residual film ratio was calculated from the film thicknesses of the thin films a and B obtained by the above method by the following equation.
After development, residual film ratio (%) { (film thickness (μm) of thin film B at each exposure amount)/(film thickness (μm) of thin film a) } × 100
The minimum exposure amount at which the residual film ratio after development obtained by the above calculation formula becomes 95% or more is used as the sensitivity of the resist.
(measurement of dielectric constant)
After coating a photosensitive resin composition on a low-resistance silicon wafer (Ω <), the solvent is removed by heat treatment at 100 ℃ for 120 seconds. Next, the exposure apparatus was aligned with a g + h + i-ray mask (PLA-501F) made by Canon corporation at 100mJ/cm2The exposure amount of (2) makes a blanket exposure of g + h + i rays. The obtained film was heat-treated in an oven at 230 ℃ for 60 minutes in the air to cure the photosensitive resin composition. Thus, cured films were obtained for each example and each comparative example. A gold electrode was formed on the thin film, and the dielectric constant was calculated from the electrostatic capacity obtained under the conditions of room temperature and 100kHz using an LCR meter (4282A) manufactured by Hewlett Packard co.
(evaluation of chemical resistance)
After coating the photosensitive resin composition on a 3-inch silicon wafer, the solvent was removed by heat treatment at 100 ℃ for 120 seconds. Next, the exposure was aligned with a g + h + i-ray mask aligner (PLA-501F) made by Canon corporation at 100mJ/cm2The exposure amount of (2) makes a blanket exposure of g + h + i rays. The obtained film was heat-treated in an oven at 230 ℃ for 60 minutes in the air to cure the photosensitive resin composition. Thus, the results were obtained for each example and each comparative example, respectivelyAnd curing the film. The silicon wafer with the obtained cured film was immersed in TOK106 (manufactured by TOKYO OHKA KOGYO co., LTD.) at room temperature for 5 minutes, and then rinsed with pure water for 30 seconds. At this time, the film thickness change rate defined by the following expression was obtained and used as an index of chemical resistance. The smaller the rate of change in film thickness, the more excellent the chemical resistance.
Film thickness change rate (%) [ { (film thickness after chemical solution immersion) - (film thickness before chemical solution immersion) }/(film thickness before chemical solution immersion) ] × 100
(evaluation of light transmittance)
A photosensitive resin composition was applied to a 1737 glass substrate manufactured by corning Incorporated (Corning corporation) having a length of 100mm and a width of 100mm, and then subjected to heat treatment at 100 ℃ for 120 seconds to remove the solvent. Next, the exposure was aligned with a g + h + i-ray mask aligner (PLA-501F) made by Canon corporation at 100mJ/cm2The exposure amount of (2) makes a blanket exposure of g + h + i rays. The obtained film was heat-treated in an oven at 230 ℃ for 60 minutes in the air to cure the photosensitive resin composition. Thus, cured films were obtained for each example and each comparative example. The transmittance (%) of the cured film at a light wavelength of 400nm was measured using an ultraviolet-visible spectrophotometer, and the transmittance was determined as a value converted to a film thickness of 3 μm.
(evaluation of Heat resistance)
For each example, the weight reduction rate of the cured film was evaluated by using the obtained photosensitive resin composition as follows.
First, a photosensitive resin composition was applied to a 3-inch wafer, and then, heat treatment was performed at 100 ℃ for 120 seconds to remove the solvent. Next, the exposure was aligned with a g + h + i-ray mask aligner (PLA-501F) made by Canon corporation at 100mJ/cm2The exposure amount of (2) makes a blanket exposure of g + h + i rays. The obtained film was heat-treated in an oven at 230 ℃ for 60 minutes in the air to cure the photosensitive resin composition. Thus, cured films were obtained for each example and each comparative example.
Then, measureThe weight loss rate of the above samples was measured. In the measurement, a sample obtained by weighing 5mg of the cured film was measured by using a thermogravimetry/differential thermal measurement apparatus (TG/DTA) at a starting temperature of 30 ℃ and a temperature rise rate of 10 ℃/min, N2The temperature was raised to 250 ℃ at a flow rate of 200mL/min and maintained at 250 ℃ for 60 minutes. The weight change rate from the weight at the time of arrival at 250 ℃ to the time of elapse of 60 minutes was defined as the weight loss rate.
The evaluation results of the above items are shown in table 3.
[ Table 3]
Figure BDA0003567946470000441
The cured product of the photosensitive resin composition of the example was low in dielectric constant, and excellent in heat resistance and chemical resistance.
The present application claims priority based on japanese application laid-open application No. 2019-175111, filed on 26.9.2019, and the entire disclosure of which is incorporated herein by reference.

Claims (16)

1. A polymer characterized by:
comprising structural units represented by the following formulae (1) and (2a),
Figure FDA0003567946460000011
in the formula (1), the reaction mixture is,
R1、R2、R3and R4Each independently hydrogen or an organic group having 1 to 30 carbon atoms, n is 0, 1 or 2,
in the formula (2a), the compound (A),
R5an organic group having 1 to 30 carbon atoms,
R1、R2、R3、R4and R5At least one of the fluorine-containing organic groups is a fluorine-containing organic group having 1 to 30 carbon atoms.
2. The polymer of claim 1, wherein:
the fluorine-containing organic group having 1 to 30 carbon atoms is a fluoroalkyl group having 1 to 30 carbon atoms or a fluoroalkyl group having 1 to 30 carbon atoms and having an etheric oxygen atom.
3. The polymer of claim 1 or 2, characterized in that:
the R is1、R2、R3And R4At least one of the fluorine-containing organic groups is a fluorine-containing organic group having 1 to 30 carbon atoms.
4. The polymer of claim 3, wherein:
the R is1、R2、R3And R4At least one of them is a fluoroalkyl group having 1 to 30 carbon atoms.
5. The polymer of claim 4, wherein:
the fluoroalkyl group having 1-30 carbon atoms is a perfluoroalkyl group.
6. The polymer according to any one of claims 1 to 5, characterized in that:
the polymer further contains at least one of structural units represented by formulae (B2) to (B6),
Figure FDA0003567946460000021
in the formula (B2), R6And R7Each independently an organic group having 1 to 30 carbon atoms,
Figure FDA0003567946460000022
in the formula (B6), R8Is an organic group having 1 to 30 carbon atoms.
7. The polymer according to any one of claims 1 to 6, characterized in that:
the weight average molecular weight of the polymer is 1500-30000.
8. A photosensitive resin composition, comprising:
a polymer comprising structural units represented by the following formulae (1) and (2 a);
a crosslinking agent; and
a photosensitizer is added to the mixture of the two or more photosensitizers,
Figure FDA0003567946460000031
in the formula (1), the reaction mixture is,
R1、R2、R3and R4Each independently hydrogen or an organic group having 1 to 30 carbon atoms, n is 0, 1 or 2,
in the formula (2a), the compound (A),
R5an organic group having 1 to 30 carbon atoms,
R1、R2、R3、R4and R5At least one of the fluorine-containing organic groups is a fluorine-containing organic group having 1 to 30 carbon atoms.
9. The photosensitive resin composition according to claim 8, wherein:
the fluorine-containing organic group having 1 to 30 carbon atoms is a fluoroalkyl group having 1 to 30 carbon atoms or a fluoroalkyl group having 1 to 30 carbon atoms and having an etheric oxygen atom.
10. The photosensitive resin composition according to claim 8 or 9, wherein:
the R is1、R2、R3And R4At least one of the fluorine-containing organic groups is a fluorine-containing organic group having 1 to 30 carbon atoms.
11. The photosensitive resin composition according to claim 10, wherein:
the R is1、R2、R3And R4At least one of them is a fluoroalkyl group having 1 to 30 carbon atoms.
12. The photosensitive resin composition according to claim 11, wherein:
the fluoroalkyl group having 1-30 carbon atoms is a perfluoroalkyl group.
13. The photosensitive resin composition according to any one of claims 8 to 12, wherein:
the polymer further contains at least one of structural units represented by formulas (B2) to (B6),
Figure FDA0003567946460000041
in the formula (B2), R6And R7 are each independently an organic group having 1 to 30 carbon atoms,
Figure FDA0003567946460000042
Figure FDA0003567946460000051
in the formula (B6), R8Is an organic group having 1 to 30 carbon atoms.
14. The photosensitive resin composition according to any one of claims 8 to 13, wherein:
the weight average molecular weight of the polymer is 1500-30000.
15. A resin film characterized in that:
the cured film of the photosensitive resin composition according to any one of claims 8 to 14.
16. An electronic device, characterized in that:
comprising the resin film of claim 15.
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