CN113515011A - Photosensitive composition, method for producing patterned cured film, and patterned cured film - Google Patents

Photosensitive composition, method for producing patterned cured film, and patterned cured film Download PDF

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CN113515011A
CN113515011A CN202110390190.2A CN202110390190A CN113515011A CN 113515011 A CN113515011 A CN 113515011A CN 202110390190 A CN202110390190 A CN 202110390190A CN 113515011 A CN113515011 A CN 113515011A
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加藤广树
染谷和也
引田二郎
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Tokyo Ohka Kogyo Co Ltd
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    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • 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
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • 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
    • G03F7/20—Exposure; Apparatus therefor

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  • Physics & Mathematics (AREA)
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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
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Abstract

The invention relates to a photosensitive composition, a method for producing a patterned cured film, and a patterned cured film. Provided are a photosensitive composition which can form a cured product having a low relative dielectric constant and can form a coating film having good shape retention on a substrate having a level difference, a cured product of the photosensitive composition, and a method for producing a cured product using the photosensitive composition. In a photosensitive composition containing an alkali-soluble resin (A), a photopolymerizable compound (B) and a photopolymerization initiator (C), an acrylic resin containing a specific amount of a structural unit (A-1) derived from a polycycloalkyl (meth) acrylate and having a weight average molecular weight of 9,000 or more is used as the alkali-soluble resin (A).

Description

Photosensitive composition, method for producing patterned cured film, and patterned cured film
Technical Field
The present invention relates to a photosensitive composition, a cured product of the photosensitive composition, and a method for producing a cured product using the photosensitive composition.
Background
In a display device such as a liquid crystal display device, a material such as an insulating film is required to efficiently transmit light emitted from a light source such as a backlight. Therefore, in order to form an insulating film, a material capable of forming a film having excellent transparency is required.
Such a transparent insulating film is usually patterned on a substrate. As a method of forming a patterned transparent insulating film, for example, a method of using a negative photosensitive composition containing an alkali-soluble resin having an oxetane ring, a polymerizable polyfunctional compound, and an α -aminoalkylbenzophenone-based photopolymerization initiator (see patent document 1) is known.
On the other hand, in recent years, as the number of production stages of liquid crystal displays has increased, the production amount of color filters has also increased, and from the viewpoint of further improving productivity, a highly sensitive photosensitive composition capable of forming a pattern with a low exposure amount has been desired.
However, when various functional films included in a color filter contain a colorant, and when a photosensitive composition contains a colorant, it is difficult to obtain sufficiently high sensitivity by using the α -aminoalkylphenone-based photopolymerization initiator described in patent document 1.
Under such circumstances, the inventors of the present application have proposed a highly sensitive photosensitive composition containing an oxime ester compound having a specific structure as a photopolymerization initiator as a highly sensitive photosensitive composition (see patent documents 2 and 3).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2012-173678
Patent document 2: japanese laid-open patent publication No. 2012-189996
Patent document 3: japanese laid-open patent publication No. 2012-189997
Disclosure of Invention
Problems to be solved by the invention
However, the photosensitive composition containing an oxime ester compound as a photopolymerization initiator has a problem that it is difficult to form a cured product having a low relative dielectric constant, although it has good sensitivity.
In addition, the integration of semiconductor devices has been advanced, and structures such as patterns are often formed in advance on a substrate coated with a photoresist composition. The structure itself may have a step. Therefore, even if there is a level difference on the surface to be coated, it is desirable that the film thickness of the coating film can be made to be the same level following the level difference. In view of the above circumstances, it is desirable that the photosensitive composition be capable of forming a conformal film (conformal film).
The present invention has been made in view of the above problems, and an object of the present invention is to provide a photosensitive composition capable of forming a cured product having a low relative dielectric constant and capable of forming a coating film having good shape retention on a substrate having a level difference, a cured product of the photosensitive composition, and a method for producing a cured product using the photosensitive composition.
Means for solving the problems
The inventors of the present invention have found that the above-mentioned problems can be solved by using, as an alkali-soluble resin (a), an acrylic resin having a weight-average molecular weight of 9,000 or more, which contains a specific amount of a structural unit (a-1) derived from a polycycloalkyl (meth) acrylate, in a photosensitive composition containing the alkali-soluble resin (a), a photopolymerizable compound (B), and a photopolymerization initiator (C), and have completed the present invention. More specifically, the present invention provides the following.
The invention of the 1 st mode is a photosensitive composition, which contains alkali soluble resin (A), photopolymerization compound (B), and photopolymerization initiator (C),
the alkali-soluble resin (A) contains an acrylic resin containing a structural unit (A-1) derived from a polycycloalkyl (meth) acrylate in an amount of 20 mass% or more relative to the amount of the total structural units,
the weight average molecular weight of the acrylic resin is 9,000 or more.
The 2 nd embodiment of the present invention is a cured product of the photosensitive composition according to the 1 st embodiment.
The 3 rd aspect of the present invention is a method for producing a cured product, comprising the steps of:
a step of molding the photosensitive composition according to claim 1 in accordance with the shape of a cured product to be formed; and
and exposing the molded photosensitive composition.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a photosensitive composition capable of forming a cured product having a low relative dielectric constant and forming a coating film having good shape retention on a substrate having a level difference, a cured product of the photosensitive composition, and a method for producing a cured product using the photosensitive composition can be provided.
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FIG. 1 is a view showing the shape retention property evaluated in the examples of the present invention.
Detailed Description
Photosensitive composition
The photosensitive composition comprises an alkali-soluble resin (A), a photopolymerizable compound (B), and a photopolymerization initiator (C). The alkali-soluble resin (A) contains an acrylic resin containing 20 mass% or more of a structural unit (A-1) derived from a polycycloalkyl (meth) acrylate. The weight average molecular weight of the acrylic resin is 9,000 or more. By adding the alkali-soluble resin (a) to the photosensitive composition, a photosensitive composition can be obtained which can form a cured product having a low relative dielectric constant and can form a coating film having good shape retention on a substrate having a level difference.
Hereinafter, essential or optional components contained in the photosensitive composition and a method for producing the photosensitive composition will be described in order.
< alkali soluble resin (A) >)
The photosensitive composition includes an alkali-soluble resin (a). As described above, the alkali-soluble resin (a) contains an acrylic resin containing 20 mass% or more of the structural unit (a-1) derived from a polycycloalkyl (meth) acrylate. The weight average molecular weight of the acrylic resin is 9,000 or more. In the specification and claims of the present application, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography.
In the present specification, the alkali-soluble resin (a) is a resin having an alkali-soluble functional group (for example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, or the like) in a molecule.
The alkali-soluble resin (a) may contain the above-mentioned specific acrylic resin and other resins than the above-mentioned specific acrylic resin within a range not impairing the object of the present invention. Hereinafter, an acrylic resin containing 20 mass% or more of a structural unit (a-1) derived from a polycycloalkyl (meth) acrylate and having a weight average molecular weight of 9,000 or more will be referred to as "acrylic resin (a-I)".
Typically, the ratio of the mass of the acrylic resin (a-I) to the total mass of the alkali-soluble resin (a) is preferably 70 mass% or more, more preferably 80 mass% or more, further preferably 90 mass% or more, further preferably 95 mass% or more, and particularly preferably 100 mass%.
As the acrylic resin (a-I), a resin containing a structural unit derived from (meth) acrylic acid and/or a structural unit derived from another monomer such as (meth) acrylate can be used. The (meth) acrylic acid is acrylic acid, or methacrylic acid. As the other monomer, typically, a compound represented by the following formula (a-I-1) is preferably used.
Figure BDA0003016372270000041
In the above formula (a-I-1), RA1Is a hydrogen atom or a methyl group. RA2Is a monovalent organic group. The organic group may contain a bond or a substituent other than the hydrocarbon group, such as a heteroatom. The organic group may be linear, branched, or cyclic. RA3is-O-, or-NRA4-a group represented by (a). RA4Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
As RA2The substituent other than the hydrocarbon group in the organic group(s) is not particularly limited as long as the effect of the present invention is not impaired, and examples thereof includeHalogen atom, hydroxyl group, mercapto group, thioether group, cyano group, isocyano group, cyanate group, isocyanate group, thiocyanate group, isothiocyanate group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphonyl group, phosphonate group, hydroxyimino group, alkylether group, arylether group, arylthioether group, amino group (-NH-)2-NHR, -NRR': r and R' each independently represents a hydrocarbon group), and the like. The hydrogen atoms contained in the above substituents may be substituted with hydrocarbon groups. The hydrocarbon group included in the substituent may be linear, branched, or cyclic.
In addition, as RA2The organic group (C) may have a reactive functional group such as acryloyloxy group, methacryloyloxy group, epoxy group, oxetanyl group and the like.
An acyl group having an unsaturated double bond or the like such as an acryloyloxy group or a methacryloyloxy group can be produced, for example, by: an unsaturated carboxylic acid such as acrylic acid or methacrylic acid is reacted with at least a part of the epoxy groups in the acrylic resin (a-I) containing a structural unit having an epoxy group.
After the unsaturated carboxylic acid is reacted with at least a part of the epoxy groups, the polybasic acid anhydride may be reacted with a group generated by the reaction.
Specific examples of the polybasic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, and 4-ethyltetrahydrophthalic anhydride.
Specifically, when acrylic acid is reacted with a structural unit derived from glycidyl methacrylate, a structural unit having a hydroxyl group shown in the following reaction formula is produced. By reacting a polybasic acid anhydride such as tetrahydrophthalic acid with the above-mentioned structural unit having a hydroxyl group, a structural unit having a carboxyl group and an unsaturated double bond and imparting alkali solubility to the resin is produced.
Figure BDA0003016372270000061
In addition, the unsaturated double bond can be introduced into the acrylic resin (a-I) by reacting a compound having an epoxy group and an unsaturated double bond with a structural unit derived from an unsaturated carboxylic acid such as acrylic acid or methacrylic acid which the acrylic resin (a-I) has. Examples of the compound having an epoxy group and an unsaturated double bond include glycidyl (meth) acrylate and compounds represented by the following formulae (a-I-1a) to (a-I-1 o).
As RA2Preferably, the epoxy group is an alkyl group, an aryl group, a cycloalkyl group, a polycycloalkyl group (polycycloalkyl group), a cycloalkylalkyl group, a polycycloalkylalkyl group, an aralkyl group, or a heterocyclic group, and these groups may be substituted with a halogen atom, a hydroxyl group, an alkyl group, or a heterocyclic group, or an oxygen atom may be bonded to these groups to form an epoxy group. In addition, when these groups contain an alkylene moiety, the alkylene moiety may be interrupted by an ether bond, a thioether bond, or an ester bond.
When the alkyl group is linear or branched, the number of carbon atoms is preferably 1 or more and 20 or less, more preferably 1 or more and 15 or less, and particularly preferably 1 or more and 10 or less. Examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl.
Among cycloalkyl groups, polycycloalkyl groups, cycloalkylalkyl groups, polycycloalkylalkyl groups, and alicyclic group-containing groups other than these groups, preferable examples of the alicyclic group contained in these groups include monocyclic alicyclic groups such as cyclopentyl and cyclohexyl groups, adamantyl, norbornyl, isobornyl, tricyclonyl, tricyclodecyl, tetracyclododecyl, bicyclo- [2.1.1] -hexyl, bicyclo- [2.2.1] -heptyl, bicyclo- [2.2.2] -octyl, bicyclo- [3.3.0] -octyl, bicyclo- [4.3.0] -nonyl, and bicyclo- [4.4.0] -decyl groups.
R is a group represented by the formula (a-I-1) and having a cycloalkyl group, a polycycloalkyl group, a cycloalkylalkyl group, a polycycloalkylalkyl group, or an alicyclic group other than these groupsA2Preferable examples of the compound (b) include compounds represented by the following formulae (a-I-1a) to (a-I-1 h). Among these, compounds represented by the following formulae (a-I-1c) to (a-I-1h) are preferable for adequate developability, and compounds represented by the following formulae (a-I-1c) and (a-I-1d) are more preferable.
Figure BDA0003016372270000071
In the above formula, Ra20Represents a hydrogen atom or a methyl group, Ra21Represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, Ra22Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As Ra21The alkylene group is preferably a single bond, a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a1, 4-butylene group, an ethylethylene group, a1, 5-pentylene group, or a1, 6-hexylene group. As Ra22For example, methyl and ethyl are preferable.
The alkali-soluble resin (A) contains an acrylic resin containing a structural unit (A-1) derived from a polycycloalkyl (meth) acrylate. The amount of the structural unit (A-1) in the acrylic resin is 20% by mass or more relative to the amount of the whole structural units. Thus, a photosensitive composition which can form a cured product having a low relative dielectric constant and can form a coating film having good shape retention on a substrate having a level difference can be obtained.
That is, the acrylic resin preferably contains a structural unit derived from a compound represented by any one of the above formulae (a-I-1c) to (a-I-1h) and having a single bond as Ra21. From the viewpoint of particularly facilitating the formation of a cured product having a low dielectric constant, the acrylic resin more preferably contains, as the structural unit (A-1), a structural unit derived from a compound represented by the formula (a-I-1c), the formula (a-I-1d) or the formula (a-I-1g) and having a single bond as Ra21。
As described above, the amount of the structural unit (a-1) in the acrylic resin is 20 mass% or more, more preferably 20 mass% or more and 40 mass% or less, and still more preferably 22 mass% or more and 35 mass% or less, with respect to the amount of the whole structural units.
The compound represented by the formula (a-I-1) has a chain group having an epoxy group as RA2Specific examples of the compound represented by the formula (a-I-1) include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, 6, 7-epoxyheptyl (meth) acrylate and other epoxyalkyl (meth) acrylates.
The compound represented by the formula (a-I-1) may be an alicyclic epoxy group-containing (meth) acrylate. The alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include cycloalkyl groups such as cyclopentyl and cyclohexyl. Examples of the polycyclic alicyclic group include polycyclic alkyl groups such as norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl groups.
The alkali-soluble resin (a) preferably contains a structural unit (a-2) derived from an alicyclic epoxy group-containing (meth) acrylate, from the viewpoint of ease of formation of a low dielectric constant cured product.
Specific examples of the case where the compound represented by the formula (a-I-1) is an alicyclic epoxy group-containing (meth) acrylate include compounds represented by the following formulas (a-I-1I) to (a-I-1 w). Among these, compounds represented by the following formulae (a-I-1I) to (a-I-1m) are preferable, and compounds represented by the following formulae (a-I-1I) to (a-I-1k) are more preferable, in order to achieve appropriate developability.
Figure BDA0003016372270000091
Figure BDA0003016372270000101
In the above formula, Ra23Represents a hydrogen atom or a methyl group, Ra24Represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, Ra25Represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and t represents an integer of 0 to 10 inclusive. As Ra24Preferred is a linear or branched alkylene group, such as methylene, ethylene, propylene, 1, 4-butylene, ethylethylene, 1, 5-pentylene, and 1, 6-hexylene. As Ra25For example, methylene, ethylene, propylene, 1, 4-butylene, ethylethylene, 1, 5-pentylene, 1, 6-hexylene, phenylene, cyclohexylene, -CH are preferable2-Ph-CH2- (Ph represents phenylene).
The amount of the structural unit (a-2) derived from the alicyclic epoxy group-containing (meth) acrylate in the acrylic resin (a-I) is not particularly limited within a range not impairing the object of the present invention, and is preferably 30% by mass or more and 70% by mass or less. When such a resin is used, a carboxyl group contained in the resin may react with an alicyclic epoxy group. Therefore, when a photosensitive composition containing such a resin is used, the mechanical properties such as hardness of the formed film can be improved by causing a self-reaction between the carboxyl group and the alicyclic epoxy group by a method of heating the film, or the like.
The acrylic resin (a-I) may be obtained by polymerizing a monomer other than (meth) acrylic acid ester. Examples of such monomers include (meth) acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These monomers may be used alone or in combination of two or more.
Examples of the (meth) acrylamide include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N-dialkyl (meth) acrylamide, N-aryl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide, and the like.
Examples of the unsaturated carboxylic acids include monocarboxylic acids such as crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; anhydrides of these dicarboxylic acids; and so on.
Examples of the allyl compound include: allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyloxyethanol; and so on.
Examples of the vinyl ethers include: alkyl vinyl ethers such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2, 2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, and tetrahydrofurfuryl vinyl ether; vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2, 4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthracenyl ether; and so on.
Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl diethylacetate, vinyl valerate, vinyl hexanoate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl β -phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.
Examples of the styrenes include: styrene; alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene and acetoxymethylstyrene; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; halogenated styrenes such as chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene; and so on.
The amount of the structural unit derived from (meth) acrylic acid and the amount of the structural unit derived from another monomer in the acrylic resin (a-I) are not particularly limited within a range not impairing the object of the present invention. The amount of the structural unit derived from (meth) acrylic acid in the acrylic resin (a-I) is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 30% by mass or less, with respect to the total structural units of the acrylic resin (a-I).
When the acrylic resin (a-I) includes a structural unit having an unsaturated double bond, the amount of the structural unit having an unsaturated double bond in the acrylic resin (a-I) is preferably 1% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 30% by mass or less, and particularly preferably 1% by mass or more and 20% by mass or less, relative to the number of moles of the entire structural units of the acrylic resin (a-I).
When the acrylic resin (a-I) contains the structural unit having an unsaturated double bond in an amount within the above range, the acrylic resin can be introduced into a crosslinking reaction in the resist film to achieve homogenization, and therefore, it is effective for improving the heat resistance and mechanical properties of the cured film.
The weight average molecular weight of the acrylic resin (a-I) is 9000 or more, more preferably 9000 or more and 50000 or less, still more preferably 9100 or more and 30000 or less, still more preferably 9200 or more and 20000 or less, and particularly preferably 9500 or more and 15000 or less. By using the acrylic resin (a-I) having a weight average molecular weight within the above range, a photosensitive composition can be obtained which can form a cured product having a low relative dielectric constant and can form a coating film having good shape retention on a substrate having a level difference
The alkali-soluble resin (a) may contain acrylic resins other than the above-mentioned acrylic resins (a to I) and resins other than acrylic resins within a range not impairing the object of the present invention.
Examples of suitable resins that the alkali-soluble resin (a) may contain include resins (a-II) having a Cardo structure (hereinafter, also referred to as "Cardo resins (a-II)").
When the resin (a-II) having a Cardo structure is used as the alkali-soluble resin (a), a photosensitive composition having excellent resolution can be easily obtained, and a cured film which is less likely to excessively flow by heating can be easily formed using the photosensitive composition. Therefore, a cured film having a good shape is easily formed.
[ resin (a-II) having Cardo Structure ]
As the resin (a-II) having a Cardo skeleton, a resin having a Cardo skeleton in its structure and having a predetermined alkali solubility can be used. The Cardo skeleton is a skeleton in which the 2 nd and 3 rd cyclic structures are bonded to 1 ring carbon atom constituting the 1 st cyclic structure. The 2 nd ring structure and the 3 rd ring structure may be the same structure or different structures.
As a typical example of the Cardo skeleton, there is a skeleton in which two aromatic rings (for example, benzene rings) are bonded to the carbon atom at the 9-position of the fluorene ring.
The Cardo resin (a-II) is not particularly limited, and conventionally known resins can be used. Among them, resins represented by the following formula (a-II) are preferable.
Figure BDA0003016372270000131
In the formula (a-1), XaRepresents a group represented by the following formula (a-2). m1 represents an integer of 0 to 20 inclusive.
Figure BDA0003016372270000132
In the above formula (a-2), Ra1Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, Ra2Each independently represents a hydrogen atom or a methyl group, Ra3Each independently represents a linear or branched alkylene group, m2 represents 0 or 1, WaRepresents a group represented by the following formula (a-3).
Figure BDA0003016372270000141
In the formula (a-2), as Ra3The alkylene group has preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and most preferably ethane-1, 2-diyl, propane-1, 2-diyl, and propane-1, 3-diyl.
The ring A in the formula (a-3) represents an aliphatic ring which may have a substituent and may be fused with an aromatic ring. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring.
Examples of the alicyclic ring include monocycloalkane, bicycloalkane, tricycloalkane and tetracycloalkane.
Specific examples thereof include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane.
The aromatic ring which may be condensed with the aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and is preferably an aromatic hydrocarbon ring. Specifically, preferred are benzene ring and naphthalene ring.
Preferred examples of the divalent group represented by the formula (a-3) include the following groups.
Figure BDA0003016372270000142
A divalent group X in the formula (a-1)aBy providing a residue ZaThe tetracarboxylic dianhydride (a) is introduced into the Cardo resin (a-II) by reacting with a diol compound represented by the following formula (a-2 a).
Figure BDA0003016372270000151
In the formula (a-2a), Ra1、Ra2、Ra3And m2 are as described for formula (a-2). The ring A in the formula (a-2a) is as described for the formula (a-3).
The diol compound represented by the formula (a-2a) can be produced, for example, by the following method.
First, according to the conventional method, the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) is replaced with-Ra3A group represented by-OH, followed by glycidylation using epichlorohydrin or the like to obtain an epoxy compound represented by the following formula (a-2 c).
Then, the epoxy compound represented by the formula (a-2c) is reacted with acrylic acid or methacrylic acid to obtain the diol compound represented by the formula (a-2 a).
In the formulae (a-2b) and (a-2c), Ra1、Ra3And m2 are as described for formula (a-2). The ring A in the formulae (a-2b) and (a-2c) is as described for the formula (a-3).
The method for producing the diol compound represented by the formula (a-2a) is not limited to the above-described method.
Figure BDA0003016372270000161
Preferable examples of the diol compound represented by the formula (a-2b) include the following diol compounds.
Figure BDA0003016372270000162
In the above formula (a-1), Ra0Is a hydrogen atom or-CO-Ya-COOH, or a group represented by the formula. Here, YaThe residue is obtained by removing an acid anhydride group (-CO-O-CO-) from a dicarboxylic anhydride. Examples of the dicarboxylic anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, and the like.
In the above formula (a-1), ZaThe residue is obtained by removing two acid anhydride groups from a tetracarboxylic dianhydride. Examples of the tetracarboxylic acid dianhydride include tetracarboxylic acid dianhydrides represented by the following formula (a-4), pyromellitic acid dianhydride, benzophenone tetracarboxylic acid dianhydride, biphenyl tetracarboxylic acid dianhydride, diphenyl ether tetracarboxylic acid dianhydride, and the like.
In the formula (a-1), m represents an integer of 0 to 20 inclusive.
Figure BDA0003016372270000171
(in the formula (a-4), Ra4、Ra5And Ra6Each independently represents 1 selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and m3 represents an integer of 0 to 12. )
Can be selected as R in the formula (a-4)a4The alkyl group of (b) is an alkyl group having 1 to 10 carbon atoms. By setting the number of carbon atoms of the alkyl group within this range, the heat resistance of the obtained carboxylic ester can be further improved. Ra4In the case of an alkyl group, the number of carbon atoms is preferably 1 to 6, more preferably 1 to 5, and still more preferably 1, from the viewpoint of easily obtaining a Cardo resin having excellent heat resistanceThe content is preferably from 1 to 4, more preferably from 1 to 3.
Ra4In the case of an alkyl group, the alkyl group may be linear or branched.
As R in the formula (a-4)a4In view of easily obtaining a Cardo resin having excellent heat resistance, each of them is more preferably independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R in the formula (a-4)a4More preferred is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and particularly preferred is a hydrogen atom or a methyl group.
The plurality of R in the formula (a-4) is preferred in view of easy preparation of a tetracarboxylic dianhydride with high puritya4Preferably the same groups.
M3 in the formula (a-4) represents an integer of 0 to 12 inclusive. When the value of m3 is 12 or less, the tetracarboxylic dianhydride can be easily purified.
The upper limit of m3 is preferably 5, more preferably 3, from the viewpoint of ease of purification of tetracarboxylic dianhydride.
The lower limit of m3 is preferably 1, more preferably 2, from the viewpoint of chemical stability of the tetracarboxylic dianhydride.
M3 in formula (a-4) is particularly preferably 2 or 3.
Can be selected as R in the formula (a-4)a5And Ra6And an alkyl group having 1 to 10 carbon atoms and which may be selected as Ra4The same applies to the alkyl group having 1 to 10 carbon atoms.
R is easy to purify the tetracarboxylic dianhydridea5And Ra6A hydrogen atom or an alkyl group having 1 to 10 (preferably 1 to 6, more preferably 1 to 5, further preferably 1 to 4, and particularly preferably 1 to 3) carbon atoms is preferable, and a hydrogen atom or a methyl group is particularly preferable.
Examples of the tetracarboxylic dianhydride represented by the formula (a-4) include norbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 ″ -norbornane-5, 5 ″,6,6 ″ -tetracarboxylic dianhydride (the alias "norbornane-2-spiro-2 ' -cyclopentanone-5 ' -spiro-2 ″ -norbornane-5, 5 ″,6,6 ″ -tetracarboxylic dianhydride"), methylnorbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 ″ - (methylnorbornane) -5,5 ″,6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro- α -cyclohexanone- α ' -spiro-2 ″ -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride (the alias "norbornane-2-spiro-2 ' -cyclohexanone-6 ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride"), methylnorbornane-2-spiro-alpha-cyclohexanone-alpha ' -spiro-2 ' - (methylnorbornane) -5,5 ', 6,6 ' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclopropanone-alpha ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclobutanone-alpha ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cycloheptanone-alpha ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclooctanone-alpha ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclononanone-alpha ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclodecanone-alpha ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cycloundecanone-alpha ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclododecanone-alpha ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclotridecanone-alpha ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclotetradecanone-alpha ' -spiro-2 ' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclopentadecanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha- (methylcyclopentanone) -alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha- (methylcyclohexanone) -alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride, and the like.
The weight average molecular weight of the Cardo resin (a-II) is preferably 1000 or more and 40000 or less, more preferably 1500 or more and 30000 or less, and further preferably 2000 or more and 10000 or less. By setting the range as described above, good developability can be obtained, and sufficient heat resistance and mechanical strength can be obtained for a cured film formed using the photosensitive composition.
[ Novolac resin (a-III) ]
From the viewpoint of easy formation of a cured product that is not likely to excessively flow by heating, it is also preferable that the alkali-soluble resin (a) contains the Novolac resin (a-III).
As the Novolac resin (a-III), various Novolac resins conventionally blended in photosensitive compositions can be used. The Novolac resin (a-III) is preferably obtained by addition-condensing an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenol") with an aldehyde under acid catalysis.
(phenols)
Examples of the phenols that can be used for producing the Novolac resin (a-III) include phenol; cresols such as o-cresol, m-cresol and p-cresol; xylenols such as 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 2, 6-xylenol, 3, 4-xylenol, and 3, 5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol and p-ethylphenol; alkylphenols such as 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol; trialkylphenols such as 2,3, 5-trimethylphenol and 3,4, 5-trimethylphenol; polyhydric phenols such as resorcinol, catechol, hydroquinone monomethyl ether, pyrogallol, and phloroglucinol; alkyl polyphenols such as alkylresorcinol, alkylcatechol, and alkylhydroquinone (all of alkyl groups have 1 to 4 carbon atoms); alpha-naphthol; beta-naphthol; hydroxybiphenyl (hydroxydiphenylyl); and bisphenol A and the like. These phenols may be used alone or in combination of two or more.
Of these phenols, m-cresol and p-cresol are preferable, and m-cresol and p-cresol are more preferable in combination. In this case, various properties such as heat resistance of a cured film formed using the photosensitive composition can be adjusted by adjusting the mixing ratio of the two.
The mixing ratio of m-cresol and p-cresol is not particularly limited, and is preferably 3/7 or more and 8/2 or less in terms of a molar ratio of m-cresol/p-cresol. By using m-cresol and p-cresol in the above-mentioned ratio, a photosensitive composition capable of forming a cured film having excellent heat resistance can be easily obtained.
In addition, a Novolac resin produced by using m-cresol and 2,3, 5-trimethylphenol in combination is also preferable. When the Novolac resin is used, a photosensitive composition capable of forming a cured film having excellent heat resistance is particularly easily obtained.
The mixing ratio of m-cresol and 2,3, 5-trimethylphenol is not particularly limited, and is preferably 70/30 or more and 95/5 or less in terms of a molar ratio of m-cresol/2, 3, 5-trimethylphenol.
(aldehydes)
Examples of aldehydes that can be used in the production of the Novolac resin (a-III) include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone, or two or more of them may be used in combination.
(acid catalyst)
Examples of the acid catalyst that can be used for producing the Novolac resin (a-III) include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethyl sulfate, and p-toluenesulfonic acid; and metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more.
(molecular weight)
The weight average molecular weight (Mw; hereinafter, also simply referred to as "weight average molecular weight") of the Novolac resin (a-III) in terms of polystyrene is preferably 2000, more preferably 5000, particularly preferably 10000, further preferably 15000, most preferably 20000, and the upper limit is preferably 50000, more preferably 45000, further preferably 40000, most preferably 35000, from the viewpoint of the heat resistance of a cured film formed using the photosensitive composition.
As the Novolac resin (a-III), at least two Novolac resins having different weight average molecular weights in terms of polystyrene can be used in combination. By using a combination of Novolac resins having different weight average molecular weights, the developability of the photosensitive composition and the heat resistance of a cured film formed using the photosensitive composition can be balanced.
[ modified epoxy resin (a-IV) ]
The alkali-soluble resin (A) may comprise a polybasic acid anhydride (a-3c) adduct as a reaction product of an epoxy compound (a-3a) and an unsaturated group-containing carboxylic acid (a-3 b). This adduct is also described as "modified epoxy resin (a-3)".
In the specification and claims of the present application, a compound that satisfies the above definition but does not belong to the above resin (a-II) having a Cardo structure is used as the modified epoxy resin (a-IV).
The epoxy compound (a-3a), the unsaturated group-containing carboxylic acid (a-3b), and the polybasic acid anhydride (a-3c) will be described below.
< epoxy Compound (a-3a) >)
The epoxy compound (a-3a) is not particularly limited as long as it is a compound having an epoxy group, and may be an aromatic epoxy compound having an aromatic group, or an aliphatic epoxy compound containing no aromatic group, and is preferably an aromatic epoxy compound having an aromatic group.
The epoxy compound (a-3a) may be a monofunctional epoxy compound, or may be a polyfunctional epoxy compound having 2 or more functions, and is preferably a polyfunctional epoxy compound.
Specific examples of the epoxy compound (a-3a) include 2-functional epoxy resins such as bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin; glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; glycidyl amine type epoxy resins such as tetraglycidyl aminodiphenylmethane, triglycidyl p-aminophenol, tetraglycidyl m-xylylenediamine, and tetraglycidyl bisaminomethylcyclohexane; heterocyclic epoxy resins such as triglycidyl isocyanurate; 3-functional epoxy resins such as phloroglucinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerol triglycidyl ether, 2- [4- (2, 3-epoxypropoxy) phenyl ] -2- [4- [1, 1-bis [4- (2, 3-epoxypropoxy) phenyl ] ethyl ] phenyl ] propane, and 1, 3-bis [4- [1- [4- (2, 3-epoxypropoxy) phenyl ] -1-methylethyl ] phenyl ] ethyl ] phenoxy ] -2-propanol; 4-functional epoxy resins such as tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether and tetracyclooxypropoxybiphenyl.
The epoxy compound (a-3a) is preferably an epoxy compound having a biphenyl skeleton.
The epoxy compound having a biphenyl skeleton preferably has at least one biphenyl skeleton represented by the following formula (a-3a-1) in the main chain.
The epoxy compound having a biphenyl skeleton is preferably a polyfunctional epoxy compound having two or more epoxy groups.
By using an epoxy compound having a biphenyl skeleton, a photosensitive composition which is excellent in balance between sensitivity and developability and which can form a cured film excellent in adhesion to a substrate can be easily obtained.
Figure BDA0003016372270000221
(in the formula (a-3a-1), Ra7Each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group which may have a substituent, and j is an integer of 1 to 4. )
Ra7In the case of an alkyl group having 1 to 12 carbon atoms, specific 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, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, an n-decyl group, an isodecyl group, an n-undecyl group, and an n-dodecyl group.
Ra7In the case of a halogen atom, specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, andan iodine atom.
Ra7In the case of a phenyl group which may have a substituent, the number of substituents on the phenyl group is not particularly limited. The number of substituents on the phenyl group is 0 or more and 5 or less, preferably 0 or 1.
Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aliphatic acyl group having 2 to 4 carbon atoms, a halogen atom, a cyano group, and a nitro group.
The epoxy compound (a-3a) having a biphenyl skeleton represented by the above formula (a-3a-1) is not particularly limited, and examples thereof include epoxy compounds represented by the following formula (a-3 a-2).
Figure BDA0003016372270000231
(in the formula (a-3a-2), Ra7And j is the same as formula (a-3a-1), k is the average number of repetitions of the structural unit in parentheses, and is 0 to 10 inclusive. )
Among the epoxy compounds represented by the formula (a-3a-2), compounds represented by the following formula (a-3a-3) are preferable in terms of particularly easy availability of a photosensitive composition having an excellent balance between sensitivity and developability.
Figure BDA0003016372270000232
(in the formula (a-3a-3), k is the same as in the formula (a-3 a-2))
(unsaturated group-containing Carboxylic acid (a-3b))
In the preparation of the modified epoxy compound (a-IV), the epoxy compound (a-3a) is reacted with the unsaturated group-containing carboxylic acid (a-3 b).
The unsaturated group-containing carboxylic acid (a-3b) is preferably a monocarboxylic acid having a reactive unsaturated double bond such as an acrylic group (acryl group) or a methacrylic group (methacryl group) in the molecule. Examples of such unsaturated group-containing carboxylic acids include acrylic acid, methacrylic acid, β -styrylacrylic acid, β -furfurylacrylic acid, α -cyanocinnamic acid, cinnamic acid, and the like. The unsaturated group-containing carboxylic acid (a-3b) may be used alone or in combination of two or more.
The epoxy compound (a-3a) can be reacted with the unsaturated group-containing carboxylic acid (a-3b) by a known method. Examples of a preferable reaction method include the following methods: the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) are reacted in an organic solvent at a reaction temperature of 50 ℃ to 150 ℃ in the presence of a tertiary amine such as triethylamine or benzylethylamine, a quaternary ammonium salt such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride or benzyltriethylammonium chloride, pyridine, or triphenylphosphine as a catalyst for several hours to several tens of hours.
The ratio of the amounts of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) used in the reaction is preferably 1: 0.5-1: 2, more preferably 1: 0.8-1: 1.25, particularly preferably 1: 0.9-1: 1.1.
the ratio of the amount of the epoxy compound (a-3a) to the amount of the unsaturated group-containing carboxylic acid (a-3b) used is 1: 0.5-1: 2, the crosslinking efficiency tends to be improved, and is preferable.
(polybasic acid anhydride (a-3c))
The polybasic acid anhydride (a-3c) is an anhydride of a carboxylic acid having two or more carboxyl groups.
The polybasic acid anhydride (a-3c) is not particularly limited, and examples thereof include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride, compounds represented by the following formula (a-3c-1), and mixtures thereof, And a compound represented by the following formula (a-3 c-2). The polybasic add anhydrides (a-3c) may be used alone or in combination of two or more.
Figure BDA0003016372270000251
(in the formula (a-3c-2), Ra8Represents an alkylene group which may have a substituent and has 1 to 10 carbon atoms. )
The polybasic add anhydride (a-3c) is preferably a compound having two or more benzene rings, because it is easy to obtain a photosensitive composition having an excellent balance between sensitivity and developability. The polybasic acid anhydride (a-3c) more preferably contains at least one of the compound represented by the formula (a-3c-1) and the compound represented by the formula (a-3 c-2).
The method of reacting the epoxy compound (a-3a) with the unsaturated group-containing carboxylic acid (a-3b) and then reacting with the polybasic acid anhydride (a-3c) can be appropriately selected from known methods.
The amount of the epoxy compound (a-3a) to be used is usually 1:1 to 1:0.1, preferably 1:0.8 to 1:0.2, in terms of the molar number of OH groups in the component after the reaction with the unsaturated group-containing carboxylic acid (a-3b) and the equivalent ratio of acid anhydride groups of the polybasic acid anhydride (a-3 c). When the amount is within the above range, a photosensitive composition having good developability can be easily obtained.
The acid value of the modified epoxy resins (a to IV) is preferably not less than 10mgKOH/g and not more than 150mgKOH/g, more preferably not less than 70mgKOH/g and not more than 110mgKOH/g, in terms of the solid resin component. By setting the acid value of the resin to 10mgKOH/g or more, sufficient solubility in a developer can be obtained, and by setting the acid value to 150mgKOH/g or less, sufficient curability can be obtained, and surface properties can be improved.
The weight average molecular weight of the modified epoxy resin (a-IV) is preferably 1000 or more and 40000 or less, and more preferably 2000 or more and 30000 or less. By setting the weight average molecular weight to 1000 or more, a cured film excellent in heat resistance and strength is easily formed. Further, by setting the weight average molecular weight to 40000 or less, a photosensitive composition exhibiting sufficient solubility in a developer can be easily obtained.
The content of the alkali-soluble resin (a) is preferably 20 mass% or more and 85 mass% or less, and more preferably 25 mass% or more and 75 mass% or less, with respect to the mass (the whole solid content) of the photosensitive composition excluding the mass of the organic solvent (S) described later. By setting the above range, a photosensitive composition having excellent developability can be easily obtained.
< photopolymerizable Compound (B) >)
As the photopolymerizable compound (B), a monomer having an ethylenically unsaturated group can be preferably used.
The kind of the photopolymerizable compound (B) is not particularly limited as long as the object of the present invention is not impaired.
In the photopolymerizable compound, the monomer having an ethylenically unsaturated group preferably contains a polyfunctional compound having 3 or more (meth) acryloyl groups, and more preferably contains a polyfunctional compound having 3 or 4 (meth) acryloyl groups, from the viewpoint of facilitating formation of a cured product having a low relative dielectric constant. When the polyfunctional compound is used as the photopolymerizable compound (B), a photosensitive composition capable of forming a cured product having a low relative dielectric constant and forming a coating film having good shape retention on a substrate having a level difference can be easily obtained.
The polyfunctional compound having 3 or more (meth) acryloyl groups may be used in combination with other photopolymerizable compounds. The other photopolymerizable compound may be a monofunctional compound or a 2-functional compound. The ratio of the mass of the polyfunctional compound having 3 or more (meth) acryloyl groups to the mass of the photopolymerizable compound (B) is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 100% by mass.
Specific examples of the polyfunctional compound having 3 or 4 (meth) acryloyl groups include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and glycerol tri (meth) acrylate. These polyfunctional monomers may be used alone or in combination of two or more.
The polyfunctional compound having 3 or 4 (meth) acryloyl groups preferably contains a compound having a partial skeleton represented by the following formula (B1), from the viewpoint of ease of forming a low dielectric constant cured product. Typically, the partial skeleton represented by formula (B1) is derived from trimethylolpropane.
Figure BDA0003016372270000271
The photopolymerizable compound (B) preferably contains a compound represented by the following formula (B2) as the polyfunctional compound having a partial skeleton represented by the formula (B1).
Figure BDA0003016372270000272
(in the formula (B2), Rb1Each independently being a hydrogen atom or a methyl group, Rb2Is a divalent linking group, a1 is 0 or 1, a2 is 0 or 1. )
In the formula (B2), when a1 is 0, the compound represented by the formula (B2) is a 3-functional compound. When a1 is 1, the compound represented by the formula (B2) is a 4-functional compound.
R in the formula (B2)b2Is a divalent linking group. The linking group may be a hydrocarbon group or an organic group containing a hetero atom. Examples of the hetero atom that may be contained in the linking group include O, N, S, Se, P, Si, B, and a halogen atom.
Preferred examples of the divalent linking group include-CO-, -Rb3-、-CO-Rb3-CO-、-Rb3-CO-、-Rb4-O-Rb4-、-Rb4-S-Rb4-, and-Rb4-CO-Rb4-a group represented by (a). Rb3Is a divalent hydrocarbon group having 1 to 10 carbon atoms. Rb4Is a compound of two or more carbon atoms of 1 to 6 carbon atomsA hydrocarbyl group.
Among the above-described groups, -CO-, -R ] is preferred in view of ease of synthesis and availability of the compound represented by the formula (B2)b3-, and-CO-Rb3-CO-。
Preferred examples of the linking group include-CO-, -CH2-、-CH2CH2-、-CH＝CH-、-CH2CH2CH2-、-CH2C(CH3)H-、-CO-CH2-CO-、--CO-CH2CH2-CO-、-CO-CH＝CH-CO-、-CO-CH2CH2CH2-CO-、-CO-CH2CH2-and groups of the following structure.
Figure BDA0003016372270000281
Specific preferable examples of the polyfunctional compound having 3 or 4 (meth) acryloyl groups include the following compounds. In the following formula, Rb1Each independently is a hydrogen atom or a methyl group.
Figure BDA0003016372270000291
When the photopolymerizable compound (B) contains another photopolymerizable compound other than the polyfunctional compound having 3 or 4 (meth) acryloyl groups, the other photopolymerizable compound is not particularly limited within a range not to impair the object of the present invention. The other photopolymerizable compound may be a monofunctional compound, or may be a 2-functional or 5-or more-functional polyfunctional compound.
Examples of the monofunctional compound include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, t-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2, 2-trifluoroethyl (meth) acrylate, 2,2,3, 3-tetrafluoropropyl (meth) acrylate, half-esters of (meth) acrylic acid of phthalic acid derivatives, and the like. These monofunctional compounds may be used alone or in combination of two or more.
Examples of the polyfunctional compound having two or more members selected from the group consisting of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, glycerol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, and mixtures thereof, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, urethane (meth) acrylate (i.e., a reaction product of toluene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, or the like with 2-hydroxyethyl (meth) acrylate), polyfunctional compounds such as methylenebis (meth) acrylamide, (meth) acrylamidomethylene ether, and condensates of polyhydric alcohols and N-methylol (meth) acrylamide, and 1,3, 5-triacryloylhexahydro-1, 3, 5-triazine (triacrylformal). These polyfunctional compounds may be used alone or in combination of two or more.
Among other photopolymerizable compounds other than the polyfunctional compound having 3 or 4 (meth) acryloyl groups, a polyfunctional monomer having 5 or more functional groups is preferable in terms of the tendency to improve the adhesion between the photosensitive composition and the substrate and the strength of the photosensitive composition after curing.
The content of the photopolymerizable compound (B) in the photosensitive composition is preferably 1 mass% or more and 50 mass% or less, and more preferably 5 mass% or more and 40 mass% or less, with respect to the mass of the photosensitive composition (the whole solid content) excluding the mass of the organic solvent (S) described later. By setting the range as described above, it is easy to obtain a balance among sensitivity, developability, and resolution.
< photopolymerization initiator (C) >
The photopolymerization initiator (C) is not particularly limited as long as it can cure the photopolymerizable compound (B) by exposure to light. As the photopolymerization initiator (C), an oxime ester compound is typically preferably used in view of the sensitivity of the photosensitive composition.
From the viewpoint of easy formation of a cured product having a low dielectric constant, a compound represented by the following formula (1) is preferably used as the oxime ester compound.
Figure BDA0003016372270000311
(in the formula (1), Rc1Is a hydrogen atom, a nitro group or a monovalent organic group, Rc2And Rc3Each is a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, Rc2And Rc3May be bonded to each other to form a ring, Rc4Is a monovalent organic radical, Rc5A hydrogen atom, an optionally substituted carbon atom number 1 or moreAn alkyl group which is at most 11 or less, or an aryl group which may have a substituent, n1 is an integer of at least 0 and at most 4, and n2 is 0 or 1. )
In the formula (1), Rc1Is a hydrogen atom, a nitro group or a monovalent organic group. Rc1To the fluorene ring in formula (1) with- (CO)n2-a group represented by (a) is bonded to a six-membered aromatic ring different from the six-membered aromatic ring to which the group represented by (b) is bonded. In the formula (1), Rc1The bonding position to the fluorene ring is not particularly limited. The compound represented by the formula (1) has 1 or more Rc1In the case (2), from the viewpoint of easy synthesis of the compound represented by the formula (1), etc., 1 or more R is preferredc11 of which is bonded to the 2-position in the fluorene ring. Rc1In the case of plural, plural Rc1May be the same or different.
Rc1When it is an organic group, Rc1The organic group is not particularly limited as long as the object of the present invention is not impaired, and may be appropriately selected from various organic groups. As Rc1Preferable examples of the organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, an optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted benzoyloxy group, phenylalkyl which may have a substituent, naphthyl which may have a substituent, naphthyloxy which may have a substituent, naphthoyl which may have a substituent, naphthyloxycarbonyl which may have a substituent, naphthoyloxy which may have a substituent, naphthylalkyl which may have a substituent, heterocyclic group which may have a substituent, heterocyclic carbonyl which may have a substituent, amino substituted with 1 or 2 organic groups, morpholin-1-yl, piperazin-1-yl and the like.
Rc1In the case of an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 6. In addition, Rc1When the alkyl group is used, it may be a straight chain or a branched chain. As Rc1Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butylN-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl groups, and the like. In addition, Rc1In the case of alkyl groups, the alkyl groups may contain ether linkages (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.
Rc1In the case of an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 6. In addition, Rc1When the alkoxy group is used, it may be a straight chain or a branched chain. As Rc1Specific examples of the alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, isopentyloxy, sec-pentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy. In addition, Rc1In the case of an alkoxy group, the alkoxy group may contain an ether linkage (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxyethoxy, and methoxypropyloxy.
Rc1In the case of a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms in the cycloalkyl group or the cycloalkoxy group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. As Rc1Specific examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. As Rc1Specific examples of the cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.
Rc1Is a saturated aliphatic acyl group or a saturated aliphatic acyl oxy groupIn the case of the group, the carbon number of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, and more preferably 2 or more and 7 or less. As Rc1Specific examples of the saturated aliphatic acyl group include acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentanoyl, 2-dimethylpropanoyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecanoyl, and n-hexadecanoyl. As Rc1Specific examples of the saturated aliphatic acyloxy group include an acetyloxy group, a propionyloxy group, a n-butyryloxy group, a 2-methylpropionyloxy group, a n-pentanoyloxy group, a2, 2-dimethylpropionyloxy group, a n-hexanoyloxy group, a n-heptanoyloxy group, a n-octanoyloxy group, a n-nonanoyloxy group, a n-decanoyloxy group, a n-undecanoyloxy group, a n-dodecanoyloxy group, a n-tridecanoyloxy group, a n-tetradecanoyloxy group, a n-pentadecanoyloxy group, and a n-hexadecanoyloxy group.
Rc1In the case of an alkoxycarbonyl group, the number of carbon atoms in the alkoxycarbonyl group is preferably 2 or more and 20 or less, and more preferably 2 or more and 7 or less. As Rc1Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, a sec-butyloxycarbonyl group, a tert-butyloxycarbonyl group, an n-pentyloxycarbonyl group, an isopentyloxycarbonyl group, a sec-pentyloxycarbonyl group, a tert-pentyloxycarbonyl group, an n-hexyloxycarbonyl group, an n-heptyloxycarbonyl group, an n-octyloxycarbonyl group, an isooctyloxycarbonyl group, a sec-octyloxycarbonyl group, a tert-octyloxycarbonyl group, an n-nonyloxycarbonyl group, an isononyloxycarbonyl group, an n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.
Rc1In the case of a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. In addition, Rc1In the case of a naphthylalkyl group, the number of carbon atoms in the naphthylalkyl group is preferably 11 or more and 20 or less, and more preferably 11 or more and 14 or less. As Rc1Specific examples of phenylalkyl groups include benzyl, 2-phenylethyl, 3-phenylpropyl and 4-phenylbutyl. As Rc1Specific examples of the naphthylalkyl group include an α -naphthylmethyl group, a β -naphthylmethyl group, a 2- (. alpha. -naphthyl) ethyl group, and a 2- (. beta. -naphthyl) ethyl group. Rc1When it is phenylalkyl or naphthylalkyl, Rc1May further have a substituent on the phenyl group or the naphthyl group.
Rc1In the case of a heterocyclic group, the heterocyclic group is a five-or six-membered monocyclic ring containing at least 1 ring N, S, O, or a heterocyclic group in which the monocyclic rings are condensed with each other or the monocyclic ring is condensed with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings in a single ring constituting the condensed ring is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran, and the like. Rc1When it is a heterocyclic group, the heterocyclic group may further have a substituent.
Rc1When it is a heterocyclylcarbonyl group, the heterocyclyl group and R contained in the heterocyclylcarbonyl groupc1The same applies to heterocyclic groups.
Rc1In the case of an amino group substituted with 1 or 2 organic groups, preferable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 21 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group and the like. These preferred organic radicals haveExamples of the compounds and Rc1 are the same. Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, phenylamino, naphthylamino, acetylamino, propionylamino, n-butyrylamino, n-valerylamino, n-hexanoylamino, n-heptanoylamino, n-octanoylamino, n-decanoylamino, benzoylamino, α -naphthoylamino, β -naphthoylamino and the like.
As Rc1The substituents in the case where the phenyl group, naphthyl group and heterocyclic group contained in (1) further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, a cyano group and the like. Rc1When the phenyl group, naphthyl group and heterocyclic group contained in (1) further have a substituent, the number of the substituent is not limited within a range not interfering with the object of the present invention, and is preferably 1 to 4. Rc1When the phenyl group, naphthyl group and heterocyclic group included in (1) have a plurality of substituents, the plurality of substituents may be the same or different.
In the groups specified hereinbefore, as Rc1Is nitro or Rc10The group represented by-CO-is preferred because it tends to increase sensitivity. Rc10The organic group is not particularly limited as long as the object of the present invention is not impaired, and may be selected from various organic groups. With respect to preference as Rc10Examples of the group (b) include an alkyl group having 1 to 20 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group, and an optionally substituted heterocyclic group. This is achieved byIn these groups, as Rc10Particularly preferred are 2-methylphenyl, thiophen-2-yl and α -naphthyl.
In addition, Rc1In the case of a hydrogen atom, the transparency tends to be good, and it is preferable. In addition, R isc1Is a hydrogen atom and Rc4In the case of the group represented by the formula (1a) or (1b) described later, the transparency tends to be further improved.
In the formula (1), Rc2And Rc3Each is a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. Rc2And Rc3May be bonded to each other to form a ring. Of these groups, as Rc2And Rc3A chain alkyl group which may have a substituent is preferable. Rc2And Rc3When the alkyl group is a linear alkyl group which may have a substituent, the linear alkyl group may be a linear alkyl group or a branched alkyl group.
Rc2And Rc3In the case of a chain alkyl group having no substituent, the number of carbon atoms in the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. As Rc2And Rc3Specific examples of the chain alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl groups. In addition, Rc2And Rc3In the case of alkyl groups, the alkyl groups may contain ether linkages (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.
Rc2And Rc3In the case of a chain alkyl group having a substituent, the number of carbon atoms in the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. In this case, the number of carbon atoms of the chain alkyl group does not include the number of carbon atoms of the substituent. The chain alkyl group having a substituent is preferably straight.
The substituent which the alkyl group may have is not particularly limited within a range not interfering with the object of the present invention. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, fluorine atom, chlorine atom and bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclic group. As specific examples of cycloalkyl, with Rc1The same applies to the preferred cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, and the like. As specific examples of heterocyclic groups, with Rc1The same applies to the preferred examples of heterocyclic groups. Rc1In the case of an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.
When the chain alkyl group has a substituent, the number of the substituent is not particularly limited. The number of the preferable substituents varies depending on the number of carbon atoms of the chain alkyl group. The number of the substituents is typically 1 or more and 20 or less, preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.
Rc2And Rc3In the case of a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group. Rc2And Rc3When it is a cyclic organic group, the substituent which the cyclic organic group may have and Rc2And Rc3The same applies to a chain alkyl group.
Rc2And Rc3In the case of an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably: a phenyl group, a group in which a plurality of benzene rings are bonded via a carbon-carbon bond, or a group in which a plurality of benzene rings are condensed. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or fusing a plurality of benzene rings, the aromatic hydrocarbon group is aromaticThe number of rings of the benzene ring contained in the group hydrocarbon group is not particularly limited, but is preferably 3 or less, more preferably 2 or less, and particularly preferably 1. Preferable specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, and the like.
Rc2And Rc3In the case of an alicyclic cyclic hydrocarbon group, the alicyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 to 20, and more preferably 3 to 10. Examples of the monocyclic cyclic hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, tetracyclododecyl, and adamantyl.
Rc2And Rc3In the case of a heterocyclic group, the heterocyclic group is a five-or six-membered monocyclic ring containing at least 1 ring N, S, O, or a heterocyclic group in which the monocyclic rings are condensed with each other or the monocyclic ring is condensed with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings in a single ring constituting the condensed ring is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran, and the like.
Rc2And Rc3May be bonded to each other to form a ring. Comprising Rc2And Rc3The group of the ring formed is preferably a cycloalkylidene group. Rc2And Rc3When the cyclic alkylidene group is formed by bonding, the ring constituting the cycloalkylidene group is preferably a five-membered ring or a six-membered ring, and more preferably a five-membered ring.
Rc2And Rc3When the group formed by bonding is a cycloalkylidene group, cycloalkaneThe fork group may be fused to more than 1 other ring. Examples of the ring which may be condensed with a cycloalkylidene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring and the like.
R is as defined abovec2And Rc3Among them, as a preferable example of the group, formula-A1-A2The group shown. In the formula, A1Is a linear alkylene radical, A2Is an alkoxy group, a cyano group, a halogen atom, a haloalkyl group, a cyclic organic group, or an alkoxycarbonyl group.
A1The number of carbon atoms of the linear alkylene group (b) is preferably 1 to 10, more preferably 1 to 6. A. the2In the case of an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. A. the2In the case of a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable, and a fluorine atom, a chlorine atom, and a bromine atom are more preferable. A. the2In the case of a haloalkyl group, the halogen atom contained in the haloalkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom, a chlorine atom, or a bromine atom. The haloalkyl group may be linear or branched, and is preferably linear. A. the2Examples of cyclic organic radicals and Rc2And Rc3The same applies to the cyclic organic group which is a substituent. A. the2Examples of alkoxycarbonyl radicals and R when alkoxycarbonyl radicals are presentc2And Rc3The same applies to alkoxycarbonyl groups that may be present as substituents.
As Rc2And Rc3Preferable specific examples of the (C) include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl, 3-methoxy-n-propyl, 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-methoxy-n-hexyl, 7-methoxy-n-heptyl, 8-methoxy-n-octyl, 2-ethoxyethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl, 5-ethoxy-n-butylAlkoxyalkyl groups such as an n-pentyl group, a 6-ethoxy-n-hexyl group, a 7-ethoxy-n-heptyl group, and an 8-ethoxy-n-octyl group; cyanoalkyl groups such as 2-cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl, 5-cyano-n-pentyl, 6-cyano-n-hexyl, 7-cyano-n-heptyl, and 8-cyano-n-octyl; phenylalkyl groups such as 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and 8-phenyl-n-octyl; cycloalkylalkyl groups such as 2-cyclohexylethyl, 3-cyclohexyl-n-propyl, 4-cyclohexyl-n-butyl, 5-cyclohexyl-n-pentyl, 6-cyclohexyl-n-hexyl, 7-cyclohexyl-n-heptyl, 8-cyclohexyl-n-octyl, 2-cyclopentylethyl, 3-cyclopentyl-n-propyl, 4-cyclopentyl-n-butyl, 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-n-octyl; an alkoxycarbonylalkyl group such as a 2-methoxycarbonylethyl group, a 3-methoxycarbonyl-n-propyl group, a 4-methoxycarbonyl-n-butyl group, a 5-methoxycarbonyl-n-pentyl group, a 6-methoxycarbonyl-n-hexyl group, a 7-methoxycarbonyl-n-heptyl group, an 8-methoxycarbonyl-n-octyl group, a 2-ethoxycarbonylethyl group, a 3-ethoxycarbonyl-n-propyl group, a 4-ethoxycarbonyl-n-butyl group, a 5-ethoxycarbonyl-n-pentyl group, a 6-ethoxycarbonyl-n-hexyl group, a 7-ethoxycarbonyl-n-heptyl group, and an 8-ethoxycarbonyl-n-octyl group; haloalkyl groups such as 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro-n-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl, 8-chloro-n-octyl, 2-bromoethyl, 3-bromo-n-propyl, 4-bromo-n-butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl, 7-bromo-n-heptyl, 8-bromo-n-octyl, 3,3, 3-trifluoropropyl, and 3,3,4,4,5,5, 5-heptafluoro-n-pentyl.
As Rc2And Rc3Among the above groups, preferred are ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl, 2-cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3, 3-trifluoropropyl and 3,3,4,4,5,5, 5-heptafluoro-n-pentyl.
As Rc4Examples of preferred organic radicals of (1) with Rc1Similarly, there may be mentioned alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl, alkoxycarbonyl, saturated aliphatic acylAn aryloxy group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group and the like. Specific examples of these groups and for Rc1The same applies to the description. In addition, as Rc4Also preferred are cycloalkylalkyl groups, phenoxyalkyl groups which may have a substituent on the aromatic ring, and phenylthioalkyl groups which may have a substituent on the aromatic ring. Phenoxyalkyl group, and phenylthioalkyl group-optionally-substituted group and Rc1The same applies to the substituents which the phenyl group may have.
In the organic radical, as Rc4Preferred are alkyl, cycloalkyl, phenyl or cycloalkylalkyl groups which may have a substituent, and phenylthioalkyl groups which may have a substituent on the aromatic ring. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among cycloalkylalkyl groups, cyclopentylethyl is preferred. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the phenylsulfanylalkyl groups which may have a substituent on the aromatic ring, 2- (4-chlorophenylthio) ethyl is preferred.
In addition, as Rc4Further preferred is-A3-CO-O-A4The group shown. A. the3Is a divalent organic group, preferably a divalent hydrocarbon group, preferably an alkylene group. A. the4Is a monovalent organic group, preferably a monovalent hydrocarbon group.
A3In the case of an alkylene group, the alkylene group may be linear or branched, and is preferably linear. A. the3In the case of an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less.
As A4Preferable examples thereof include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. As A4Preferable specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, phenyl, naphthyl, benzyl, phenethyl, α -naphthylmethyl, and β -naphthylmethyl groups.
As a3-CO-O-A4Preferred specific examples of the group include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propyloxycarbonylethyl, 2-n-butyloxycarbonylethyl, 2-n-pentyloxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 3-ethoxycarbonyl-n-propyl, 3-n-propyloxycarbonyl-n-propyl, 3-n-butyloxycarbonyl-n-propyl, 3-n-pentyloxycarbonyl-n-propyl, 3-n-hexyloxycarbonyl-n-propyl, 3-benzyloxycarbonyl-n-propyl, and 3-phenoxycarbonyl-n-propyl.
Above, to Rc4Has been described as Rc4The group represented by the following formula (1a) or the following formula (1b) is preferable.
Figure BDA0003016372270000411
(in the formulae (1a) and (1b), Rc7And Rc8Each is an organic group, n3 is an integer of 0 to 4 inclusive, Rc7And Rc8When present in adjacent positions on the phenyl ring, Rc7And Rc8Can be bonded to each other to form a ring, n4 is an integer of 1 to 8 inclusive, n5 is an integer of 1 to 5 inclusive, n6 is an integer of 0 to (n5+3) inclusive, Rc9Is an organic group. )
R in the formula (1a)c7And Rc8Examples of organic radicals mentioned are Rc1The same is true. As Rc7Preferably alkyl or phenyl. Rc7In the case of an alkyl group, the number of carbon atoms is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less, and most preferably 1. Namely, Rc7Most preferred is methyl. Rc7And Rc8When a ring is bonded to form a bond, the ring may be an aromatic ring or an aliphatic ring. As Rc7And Rc8Preferred examples of the group represented by the formula (1a) having a ring formed thereon include naphthalen-1-yl, 1,2,3, 4-tetrahydronaphthalen-5-yl and the like. In formula (1a), n3 is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.
In the above formula (1b), Rc9Is an organic group. Examples of the organic group include those related to Rc1And the organic groups illustrated are the same. Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. As Rc9Preferable examples thereof include methyl, ethyl, propyl, isopropyl, butyl and the like, and among these, methyl is more preferable.
In formula (1b), n5 is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2. In formula (1b), n6 is an integer of 0 to (n5+3), preferably 0 to 3, more preferably 0 to 2, and particularly preferably 0. In formula (1b), n4 is an integer of 1 or more and 8 or less, preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and particularly preferably 1 or 2.
In the formula (1), Rc5Is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. As Rc5Examples of the substituent which may be contained in the alkyl group include a phenyl group and a naphthyl group. In addition, as Rc1Examples of the substituent which may be contained in the aryl group include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.
In the formula (1), as Rc5Preferable examples thereof include a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group and the like, and among these, methyl group or phenyl group is more preferable.
Preferable specific examples of the compound represented by the formula (1) include the following PI-1 to PI-41.
Figure BDA0003016372270000431
Figure BDA0003016372270000441
As the photopolymerization initiator (C), other photopolymerization initiators than the compound represented by the above formula (1) may be used. Other photopolymerization initiators may be used alone or in combination with the compound represented by the above formula (1). The other photopolymerization initiator is not particularly limited as long as it is a photopolymerization initiator that does not belong to the compound represented by the formula (1).
As preferable examples of other photopolymerization initiators, there can be exemplified: oxime ester compounds having structures other than those represented by the above formula (C1), such as 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl ] -1-octanone (commercially available as OXE-01(BASF corporation)), and O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl ] ethanone oxime (commercially available as OXE-02(BASF corporation)), and the like; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-dimethylaminophenyl) butan-1-one, 2- (4-methylbenzyl) -2-diethylamino-1- (4-morpholinophenyl) butan-1-one, 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1- [4- (hexyl) phenyl ] -2-morpholinopropan-1-one, and mixtures thereof, α -aminoketone compounds such as 2-ethyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one; α -hydroxyketone photopolymerization initiators such as 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) one, and 1-hydroxycyclohexyl phenyl ketone; benzoin-based photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzyl methyl ketal; benzophenone-based photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl, 4 '-methyldiphenyl sulfide, and 4, 4' -bisdiethylaminobenzophenone; thioxanthone-based photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone and 2, 4-diisopropylthioxanthone; 2,4, 6-trichloro-s-triazine, 2-phenyl-4, 6-bis (trichloromethyl) s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (p-tolyl) -4, 6-bis (trichloromethyl) s-triazine, 2-piperonyl (piperonyl) -4, 6-bis (trichloromethyl) s-triazine, 2, 4-bis (trichloromethyl) -6-styryl s-triazine, 2- (naphthalen-1-yl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-methoxy-naphthalen-1-yl) -4, 6-bis (trichloromethyl) s-triazine, 2, 4-trichloromethyl- (piperonyl) -6-triazine, triazine-based photopolymerization initiators such as 2, 4-trichloromethyl- (4' -methoxystyryl) -6-triazine and 2- [4- (4-methoxystyryl) phenyl ] -4, 6-bis (trichloromethyl) -1,3, 5-triazine; a carbazole-based photopolymerization initiator; 2,2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetrakis (4-ethoxycarbonylphenyl) -1,2 ' -biimidazole, 2 ' -bis (2-bromophenyl) -4,4 ', 5,5 ' -tetrakis (4-ethoxycarbonylphenyl) -1,2 ' -biimidazole, 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole, 2 ' -bis (2, 4-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole, 2 ' -bis (2,4, 6-trichlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, biimidazole photopolymerization initiators such as 2 '-biimidazole, 2' -bis (2-bromophenyl) -4,4,5,5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2, 4-dibromophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -biimidazole, and 2,2 '-bis (2,4, 6-tribromophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -biimidazole; a benzimidazoline photopolymerization initiator represented by the following formula; and so on.
Figure BDA0003016372270000461
Preferred specific examples of the other photopolymerization initiator include the following compounds.
Figure BDA0003016372270000471
Figure BDA0003016372270000481
Figure BDA0003016372270000491
Figure BDA0003016372270000501
Figure BDA0003016372270000511
Figure BDA0003016372270000521
Figure BDA0003016372270000531
Figure BDA0003016372270000541
Figure BDA0003016372270000551
Figure BDA0003016372270000561
When the compound represented by the above formula (1) is used as the photopolymerization initiator (C), the ratio of the mass of the compound represented by the above formula (1) to the mass of the photopolymerization initiator (C) is not particularly limited within a range that does not impair the object of the present invention. The ratio of the compound represented by the formula (1) is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 100% by mass, relative to the mass of the photopolymerization initiator (C).
The content of the photopolymerization initiator (C) is preferably 0.1 mass% or more and 30 mass% or less, and more preferably 0.5 mass% or more and 20 mass% or less, based on the mass of the entire solid content of the photosensitive composition. When the content of the photopolymerization initiator (C) is in the above range, a photosensitive composition having good curability and less likely to cause pattern shape defects can be obtained.
< organic solvent (S) >)
Typically, the photosensitive composition may contain an organic solvent (S) for the purpose of adjusting coatability, or the like. Examples of the organic solvent (S) include (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; (poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; alkyl lactate esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl acetoacetate, ethyl acetate, methyl propionate, ethyl butyrate, n-butyl butyrate, ethyl propionate, ethyl acetoacetate, ethyl propionate, and ethyl propionate, other esters such as ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide. These solvents may be used alone, or two or more of them may be used in combination.
The amount of the organic solvent (S) used may be determined as appropriate depending on the use of the photosensitive composition. As an example of the amount of the organic solvent (S), the amount in which the solid content concentration of the photosensitive composition is in the range of 1 mass% to 50 mass% is given.
< other ingredients >
The photosensitive composition may contain various additives other than those described above as necessary. Specifically, dispersing aids, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomeration agents, thermal polymerization inhibitors, defoaming agents, surfactants, and the like can be exemplified.
Examples of the thermal polymerization inhibitor used in the photosensitive composition include hydroquinone and hydroquinone monoethyl ether. In addition, as the defoaming agent, silicone-based, fluorine-based, and other compounds may be exemplified, and as the surfactant, anionic-based, cationic-based, and nonionic compounds may be exemplified.
< method for producing photosensitive composition >
The photosensitive composition can be prepared by uniformly mixing the above-mentioned respective components in desired amounts. When the photosensitive composition to be produced does not contain an insoluble component such as a pigment, the photosensitive composition can be made uniform by filtration using a filter.
Method for producing cured product
Typically, the photosensitive composition described above is prepared into a cured product by a method including the following steps:
a step of molding the photosensitive composition in accordance with the shape of the cured product; and
and exposing the molded photosensitive composition.
The cured product produced by the above method has a relative dielectric constant of preferably 2.86 or less, more preferably 2.84 or less, still more preferably 2.80 or less, and particularly preferably 2.77 or less. The cured product thus produced has high transparency, and therefore is useful for applications in display devices such as OLEDs, organic ELs, and liquid crystals, and is suitably used for a planarization film, an interlayer insulating film, a protective film for color filters, a spacer for keeping the thickness of a liquid crystal layer in a liquid crystal display device constant, a microlens in a solid-state imaging element, and the like.
The method for molding the photosensitive composition is not particularly limited, and may be appropriately selected depending on the shape of the cured product. Examples of the shape of the cured product include, but are not limited to, a film shape, a lens shape, a line shape, and a prism shape. Of these shapes, a film shape is preferable.
The method for molding the photosensitive composition is not particularly limited. When the shape of the cured product is a lens shape, a prism shape, or the like, the photosensitive composition may be filled in a mold conforming to the shape of the cured product by using a squeegee or the like.
When the shape of the cured product is a linear shape or the like, the photosensitive composition can be applied to the substrate in accordance with the shape of the cured product. Examples of the coating method include a printing method such as an inkjet method.
Examples of a method for applying the photosensitive composition in a film shape include a method using a contact transfer type coating apparatus such as a roll coater, a reverse coater, or a bar coater, and a non-contact type coating apparatus such as a spinner (rotary coating apparatus) or a curtain coater. Alternatively, the photosensitive composition may be applied in a film form by a printing method such as an ink jet method.
When the photosensitive composition is used, even if the surface of the substrate to be coated has a level difference, a coating film having a uniform film thickness can be formed following the level difference.
The thickness of the coating film is not particularly limited. The thickness of the coating film is preferably 0.05 μm or more, and more preferably 1 μm or more. The thickness of the coating film may be, for example, 7 μm or more, or 10 μm or more. The upper limit of the thickness of the coating film is not particularly limited, and may be, for example, 50 μm or less, and may be 20 μm or less. The thickness of the coating film is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 2 μm or less.
The thickness of the coating film is preferably in the range of 0.05 μm to 10 μm, more preferably 1 μm to 5 μm, and still more preferably 1 μm to 2 μm.
Subsequently, the coating film is dried as necessary. The drying method is not particularly limited. Examples of the drying method include: (1) a method of drying at a temperature of 80 ℃ to 120 ℃, preferably 90 ℃ to 100 ℃, for 60 seconds to 120 seconds, using a hot plate; (2) a method of standing at room temperature for several hours to several days; (3) a method of removing the solvent by placing the substrate in a warm air heater or an infrared heater for several tens of minutes to several hours; and so on.
By exposing the coating film to light, a cured film can be formed.
The light source in the exposure is not particularly limited, and examples thereof include a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and an LED. The coating film can be irradiated with ArF excimer laser, KrF excimer laser, F using such a light source2The coating film is exposed to radiation such as excimer laser light, Extreme Ultraviolet (EUV), Vacuum Ultraviolet (VUV), electron beam, X-ray, soft X-ray, g-line, i-line, h-line, j-line, k-line, or electromagnetic wave.
The exposure amount varies depending on the composition of the photosensitive composition, and is preferably 10mJ/cm, for example2Above 2000mJ/cm2Hereinafter, more preferably 100mJ/cm2Above and 1500mJ/cm2Hereinafter, more preferably 200mJ/cm2Above 1200mJ/cm2The following. The exposure illuminance also varies depending on the composition of the photosensitive composition, and is preferably 1mW/cm2Above 50mW/cm2Within the following ranges.
The cured film cured by exposure to light may be heated. The temperature at the time of heating is not particularly limited, but is preferably 180 ℃ or higher and 280 ℃ or lower, more preferably 200 ℃ or higher and 260 ℃ or lower, and particularly preferably 220 ℃ or higher and 250 ℃ or lower. The heating time is typically preferably 1 minute or more and 60 minutes or less, more preferably 10 minutes or more and 50 minutes or less, and particularly preferably 20 minutes or more and 40 minutes or less.
On the other hand, the coating film can be exposed position-selectively. In this case, the coating film is subjected to position-selective exposure through a negative mask having a light-transmitting portion with a shape corresponding to the pattern shape of the cured film.
The exposure method is the same as the above-described exposure method except that a negative mask is used.
Next, the exposed coating film is developed with a developing solution, thereby forming a patterned cured film. The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. Examples of the developer include organic developers such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.
The patterned cured film obtained after development may be heated in the same manner as in the method of applying the exposure method to the patterned coating film described above.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
[ examples 1 to 6 and comparative examples 1 to 4 ]
In examples and comparative examples, acrylic resins P1 to P3 having the following structures and acrylic resin P4 having the following structures were used as the alkali-soluble resin (a). The weight average molecular weight of the resin P1 in terms of polystyrene was 12000. The weight average molecular weight of the resin P2 in terms of polystyrene was 10000. The weight average molecular weight of the resin P3 in terms of polystyrene was 8000. The weight average molecular weight of the resin P4 in terms of polystyrene was 10000.
Figure BDA0003016372270000611
In examples and comparative examples, the following B-1 to B-3 were used as the photopolymerizable compound (B).
B-1: dipentaerythritol hexaacrylate
B-2: trimethylolpropane triacrylate
B-3: ditrimethylolpropane tetraacrylate
In examples and comparative examples, the following C-1 was used as the photopolymerization initiator (C).
Figure BDA0003016372270000621
13.73 parts by mass of an alkali-soluble resin (A) ((A) component) of the type shown in Table 1, 6.8 parts by mass of a photopolymerizable compound (B) ((B) component) of the type shown in Table 1, 1.22 parts by mass of a photopolymerizable compound (C) ((C) component) of the type shown in Table 1, 31.2 parts by mass of diethylene glycol methyl ethyl ether, 46.7 parts by mass of propylene glycol monomethyl ether acetate, 0.2 part by mass of 3-glycidoxypropyltrimethoxysilane, 0.05 part by mass of a surfactant (BYK-310, BYK-Chemie Co., Ltd.), and 0.1 part by mass of an antioxidant (IR1010, BASF Japan Co., Ltd.) were mixed to obtain photosensitive compositions of examples and comparative examples.
Using the obtained photosensitive composition, the relative dielectric constant and the pattern formability were evaluated in the following manner. The evaluation results are shown in Table 1.
< determination of relative dielectric constant >
As a method for measuring the relative dielectric constant, a mercury probe method was used. SSM-495 (manufactured by Semilab, Japan) was used as a device capable of measuring the relative permittivity by the mercury probe method. By the following steps 1) to 4), a film-shaped cured product having a film thickness of 1 μm was formed using the curable compositions of the examples and comparative examples. Then, the relative dielectric constant of the resulting cured product was measured.
1) A coating film is formed by coating a silicon wafer with the curable composition.
2) The formed coating film was heated at 100 ℃ for 120 seconds.
3) At 1J/cm2The exposure amount of (2) exposes the coating film.
4) The exposed coating film was heated at 230 ℃ for 20 minutes.
< evaluation of shape-Retention >
The photosensitive compositions of examples and comparative examples were applied to a glass substrate (680X 880mm) on which a structure having a thickness of 5 μm (W in FIG. 1) was partially formed, using a slit coater (TR-45000; manufactured by Tokyo Kaisha industries, Ltd.) using the prepared non-spin coating composition at a coating speed of 120 mm/sec, and then dried at 100 ℃ for 100 seconds to obtain a coating film. Next, a mirror projection alignment exposure apparatus (product name: MPA-6000, manufactured by Canon corporation) was used at 100mJ/cm2The exposure amount of (2) is used for whole surface exposure. Subsequently, a 0.04 mass% KOH aqueous solution at 23 ℃ was sprayed for 70 seconds to perform development. Then, at 230 ℃ underAfter 20 minutes of baking treatment (post-baking), as shown in the cross-sectional view of FIG. 1, a film having a thickness of about 2.4 μm was obtained as indicated by the difference (X-W) between the maximum film thickness (X; including the thickness (W) of the structure on the substrate) and the thickness (W) of the structure on the substrate.
As shown in the cross-sectional view of fig. 1, the difference (X-Y ═ Z) between the maximum film thickness (X; including the thickness (W) of the structure on the substrate) on the substrate and the minimum film thickness (Y) on the substrate was measured for the cross-section of the obtained post-baked film.
When the coating speed was 120 mm/sec, the coating speed was evaluated as Z less than 2, poor in shape retention (x), 2 or more and 2.4 or less, good in shape retention (good), and more than 2.4, particularly excellent in shape retention (excellent).
[ Table 1]
Figure BDA0003016372270000631
As is apparent from table 1, the photosensitive compositions of examples containing an acrylic resin containing 20 mass% or more of a structural unit (a-1) derived from a polycycloalkyl (meth) acrylate based on the total amount of structural units and having a weight average molecular weight of 9,000 or more as an alkali-soluble resin (a) can form cured products having a low relative dielectric constant and can form a coating film having good shape retention on a substrate having a level difference.
On the other hand, in the case of using the photosensitive composition of the comparative example containing an acrylic resin having a weight average molecular weight of less than 9,000 or containing only less than 20 mass% (relative to the amount of all structural units) of the structural unit (a-1) derived from a polycycloalkyl (meth) acrylate as the alkali-soluble resin (a), it is difficult to simultaneously form a cured product having a low relative dielectric constant and a coating film having a good shape retention on a substrate having a level difference.

Claims (8)

1. A photosensitive composition comprising an alkali-soluble resin (A), a photopolymerizable compound (B), and a photopolymerization initiator (C),
the alkali-soluble resin (A) contains an acrylic resin containing a structural unit (A-1) derived from a polycycloalkyl (meth) acrylate in an amount of 20 mass% or more relative to the amount of the total structural units,
the weight average molecular weight of the acrylic resin is 9,000 or more.
2. The photosensitive composition according to claim 1, wherein the acrylic resin contains the structural unit (A-1) in an amount of 20 to 40 mass% based on the total structural units.
3. The photosensitive composition according to claim 1 or 2, wherein the acrylic resin contains a structural unit (a-2) derived from an alicyclic epoxy group-containing (meth) acrylate in an amount of 30% by mass or more and 70% by mass or less with respect to the amount of the whole structural units.
4. The photosensitive composition according to claim 1 or 2, wherein the photopolymerizable compound (B) comprises a polyfunctional compound having 3 or more (meth) acryloyl groups.
5. The photosensitive composition according to claim 4, wherein the photopolymerizable compound (B) comprises a polyfunctional compound having 3 or 4 (meth) acryloyl groups.
6. The photosensitive composition according to claim 1 or 2, wherein the photopolymerization initiator (C) comprises a compound represented by the following formula (1),
Figure FDA0003016372260000011
in the formula (1), Rc1Is a hydrogen atom, a nitro group or a monovalent organic group, Rc2And Rc3Each can haveA chain alkyl group as a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, Rc2And Rc3May be bonded to each other to form a ring, Rc4Is a monovalent organic radical, Rc5Is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, n1 is an integer of 0 to 4, and n2 is 0 or 1.
7. A cured product of the photosensitive composition according to any one of claims 1 to 6.
8. A method for producing a cured product, comprising the steps of:
a step of molding the photosensitive composition according to any one of claims 1 to 6 in accordance with the shape of a cured product to be formed; and
and exposing the molded photosensitive composition.
CN202110390190.2A 2020-04-10 2021-04-12 Photosensitive composition, method for producing patterned cured film, and patterned cured film Pending CN113515011A (en)

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