CN108375878B - Polymerizable composition, method for producing cured film, and cured film - Google Patents

Polymerizable composition, method for producing cured film, and cured film Download PDF

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CN108375878B
CN108375878B CN201810085762.4A CN201810085762A CN108375878B CN 108375878 B CN108375878 B CN 108375878B CN 201810085762 A CN201810085762 A CN 201810085762A CN 108375878 B CN108375878 B CN 108375878B
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resin
substituent
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CN108375878A (en
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染谷和也
野田国宏
引田二郎
盐田大
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Tokyo Ohka Kogyo Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • G03F7/075—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor

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  • General Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Health & Medical Sciences (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Materials For Photolithography (AREA)
  • Silicon Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The subject of the invention is to provide: even if 1 or more kinds of filler (D) selected from the group consisting of inorganic filler (D1) containing a specific element and alkaline filler (D2) and a component containing a polymerizable group are contained, a photosensitive polymerizable composition capable of suppressing development residues from being generated in a non-pattern portion when a patterned functional film is formed by photolithography, a method for producing a cured film using the polymerizable composition, a cured film formed by curing the polymerizable composition, a transparent insulating film formed by curing a polymerizable composition containing the inorganic filler (D1), and a display device having the transparent insulating film. A photosensitive polymerizable composition comprising 1 or more fillers (D) selected from the group consisting of inorganic fillers (D1) containing a specific element and basic fillers (D2), and a polymerizable group-containing component, wherein the composition contains a specific silicon-containing resin (A).

Description

Polymerizable composition, method for producing cured film, and cured film
Technical Field
The present invention relates to a polymerizable composition, a method for producing a cured film using the polymerizable composition, a cured film obtained by curing the polymerizable composition, a transparent insulating film, and a display device having the transparent insulating film.
Background
Conventionally, various additives have been used for forming functional films. As additives for imparting a function to a film, for example, flame retardants such as magnesium hydroxide and aluminum hydroxide, and conductive polymers such as polypyrrole, polyaniline, and polyaniline-ethylene (japanese) are known (see patent documents 1 and 2).
In order to form a transparent insulating film having a high dielectric constant and excellent transparency, it is also known to blend an inorganic filler containing an element such as La, ce, nd, gd, ho, lu, hf or Ta into a film forming material (negative photosensitive composition).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2006-43974
Patent document 2: japanese patent application laid-open No. 2010-257981
Patent document 3: japanese patent laid-open publication 2016-75803
Disclosure of Invention
Problems to be solved by the invention
However, when an alkali filler, an alkali polymer, or an inorganic filler containing a specific kind of element, as described in patent documents 1 and 2, or as described in patent document 3, is blended into a photosensitive polymerizable composition containing a polymerization initiator and a polymerizable group-containing component, there is a problem that development residues are easily generated in non-pattern portions (unexposed portions) after development when a patterned functional film is formed by photolithography using the polymerizable composition.
The present application has been made in view of the above problems, and an object of the present application is to provide: a polymerizable composition which can inhibit the development residue from being generated in a non-pattern part (unexposed part) when a patterned functional film is formed by a photolithography method even if the composition contains 1 or more fillers (D) selected from the group consisting of an inorganic filler (D1) containing a specific element and an alkaline filler (D2), and a component containing a polymerizable group; a method for producing a cured film using the polymerizable composition; a cured film formed by curing the polymerizable composition; a transparent insulating film formed by curing a polymerizable composition containing the inorganic filler (D1); a display device having the transparent insulating film.
Means for solving the problems
The inventors of the present application have found that the above problems can be solved by containing a specific silicone-containing resin (a) in a photosensitive polymerizable composition containing 1 or more fillers (D) selected from the group consisting of an inorganic filler (D1) containing a specific element and an alkaline filler (D2), and a component containing a polymerizable group, and have completed the present application. Specifically, the present application provides the following means.
In embodiment 1 of the present application, there is provided a polymerizable composition,
Which is a polymerizable composition comprising a component containing a polymerizable group,
the polymerizable composition comprises:
a silicone-containing resin (A),
a polymerization initiator (C), and
a filler (D),
the aforementioned silicon-containing resin (A) contains at least 1 selected from the group consisting of silsesquioxane resin (A1), polysilane-polysiloxane resin (A-I), resin mixture (A-II) and polysilane structure-containing resin (A-III),
the silsesquioxane resin (A1) is a silsesquioxane resin having a structural unit represented by the following formula (A1 a),
[ chemical formula 1]
(in the formula (a 1 a), R a1 Is as followsA group represented by the formula (a 1 a-I),
-X a -B a -Y a -COOH……(a1a-I)
X a is a single bond, an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, or-R a6 -NH-R a7 -a group represented by formula (i),
R a6 and R is a7 Each independently represents an alkylene group having 1 to 3 carbon atoms,
Y a a cyclic organic group having 2 valences or a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms,
B a is-NH-CO-, -CO-NH-, -NH-CO-O-, and-O-CO-NH-, or-NH-CO-NH-,
X a and Y a Each independently may be substituted with 1 or more groups selected from the group consisting of (meth) acryloyloxy, vinyl, and epoxy-containing organic groups. )
The polysilane-polysiloxane resin (A-I) is a polysilane-polysiloxane resin having a polysilane structure (I-1) and a polysiloxane structure (I-2),
The resin mixture (A-II) is a mixture of a resin having a polysilane structure (II-1) and a resin having a polysiloxane structure (II-2),
the polysilane structure-containing resin (A-III) is a resin having a polysilane structure (II-1),
the polymerizable group-containing component contains at least 1 of the following (1) to (5),
(1) X in the above formula (a 1 a-I) having a structural unit represented by the above formula (a 1 a) a And Y a A silsesquioxane resin (A1-1) in which at least one of the silsesquioxane resins is substituted with 1 or more groups selected from the group consisting of (meth) acryloyloxy groups, vinyl groups and epoxy-containing organic groups,
(2) A silsesquioxane resin (A1-2) having a structural unit represented by the above formula (A1 a) and a structural unit represented by the following formula (a 2 a),
[ chemical formula 2]
(in the formula (a 2 a), R a2 Is a group represented by the following formula (a 1 a-II),
-Z a -A a ……(a1a-II)
Z a is a single bond, an alkylene group having 1 to 6 carbon atoms, or an arylene group having 6 to 12 carbon atoms,
A a is (meth) acryloyloxy, vinyl, or epoxy-containing organic groups. )
(3) A silsesquioxane resin (A2) which has a structural unit represented by the above formula (A2 a) and which does not belong to the silsesquioxane resin (A1),
(4) A polyfunctional polymerizable monomer (B1),
(5) A polymerizable group-containing resin (B2) which has 1 or more groups selected from the group consisting of (meth) acryloyloxy groups, vinyl groups, and epoxy group-containing organic groups, and which does not belong to any of the silsesquioxane resin (A1), the silsesquioxane resin (A2), and the polyfunctional polymerizable monomer (B1);
the filler (D) contains 1 or more selected from the group consisting of an inorganic filler (D1) and an alkaline filler (D2),
the inorganic filler (D1) is 1 or more selected from the group consisting of: at least 1 element selected from the group consisting of La, ce, nd, gd, ho, lu, hf and Ta, an oxide of the foregoing element, a chelate of the foregoing element, a salt of the foregoing element, and an alloy of the foregoing element,
the basic filler (D2) is at least one selected from the group consisting of basic fillers and basic polymers.
In accordance with embodiment 2 of the present invention, there is provided a method for producing a cured film, comprising the steps of:
a step of forming a coating film on a substrate using the polymerizable composition according to the embodiment 1,
a step of positionally selectively exposing the coating film, and
and developing the exposed coating film.
In accordance with claim 3 of the present invention, the cured film is formed by curing the polymerizable composition according to claim 1.
In accordance with claim 4 of the present invention, there is provided a transparent insulating film formed by curing the polymerizable composition according to claim 1, which contains the inorganic filler (D1) as the filler (D).
A 5 th aspect of the present invention is a display device having the transparent insulating film according to the 4 th aspect.
ADVANTAGEOUS EFFECTS OF INVENTION
The polymerizable composition of the present invention can suppress development residues in non-pattern portions (unexposed portions) when a patterned functional film is formed by photolithography, even when the composition contains 1 or more fillers (D) selected from the group consisting of inorganic fillers (D1) containing specific elements and basic fillers (D2), and a polymerizable group-containing component.
The present invention also provides a method for producing a cured film using the polymerizable composition, a cured film obtained by curing the polymerizable composition, a transparent insulating film obtained by curing a polymerizable composition containing the inorganic filler (D1), and a display device having the transparent insulating film.
Detailed Description
Polymerizable composition
The polymerizable composition comprises a component containing a polymerizable group. The polymerizable composition further comprises a silicone-containing resin (A), a polymerization initiator (C), and a filler (D).
The polymerizable composition contains a polymerizable group-containing component and a polymerization initiator (C). Therefore, the polymerizable composition has curability to be cured by exposure to light.
In addition, as described later, the polymerizable composition contains a silicon-containing resin (a) exhibiting alkali solubility. Therefore, if a coating film formed of the polymerizable composition is exposed positionally selectively, the uncured unexposed portion is soluble in an alkaline developer.
In addition, when a photosensitive composition containing a specific filler (D) described later is used, in general, when a patterned functional film is formed by photolithography and development is performed, residues are likely to be generated in an unexposed portion.
However, when a polymerizable composition containing a silicone resin (a) having a predetermined structure and a specific filler (D) in combination is used, the occurrence of residues in the unexposed portions during development can be suppressed.
Hereinafter, the essential or optional components in the polymerizable composition will be described.
Silicon-containing resin (A) >, and process for producing the same
The polymerizable composition must contain a silicone-containing resin (a). The silicon-containing resin (A) contains at least 1 selected from the group consisting of a silsesquioxane resin (A1), a polysilane-polysiloxane resin (A-I), a resin mixture (A-II), and a polysilane structure-containing resin (A-III) described later.
Silsesquioxane resin (A1)
The silsesquioxane resin (A1) is a silsesquioxane resin having a carboxyl group represented by the formula (A1 a-I). The silsesquioxane resin (A1) functions as an alkali-soluble resin in the polymerizable composition.
Therefore, the polymerizable composition is insoluble in an alkaline developer by polymerization of the polymerizable group-containing component when exposed to light, and is soluble in an alkaline developer in an unexposed state.
When the silicone-containing resin (a) contains the silsesquioxane resin (A1), the content of the silsesquioxane resin (A1) in the silicone-containing resin (a) is not particularly limited in a range that does not hinder the object of the present invention, and is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 100% by mass in view of the developability of the polymerizable composition.
As a general structure of the silsesquioxane compound, a cage type, an incomplete cage type, a ladder type, a random type, and the like are widely known. The structure of the silsesquioxane resin (A1) is not particularly limited, and may be any conventionally known structure such as a cage type, an incomplete cage type, a ladder type, a random type, and the like.
The silsesquioxane resin (A1) has a structural unit represented by the following formula (A1 a).
[ chemical formula 3]
(in the formula (a 1 a), R a1 Is a group represented by the following formula (a 1 a-I),
-X a -B a -Y a -COOH……(a1a-I)
X a is a single bond, an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, or-R a6 -NH-R a7 -a group represented by formula (i),
R a6 and R is a7 Each independently represents an alkylene group having 1 to 3 carbon atoms,
Y a a cyclic organic group having 2 valences or a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms,
B a is-NH-CO-, -CO-NH-, -NH-CO-O-, and-O-CO-NH-, or-NH-CO-NH-,
X a and Y a Each independently may be substituted with 1 or more groups selected from the group consisting of (meth) acryloyloxy, vinyl, and epoxy-containing organic groups. )
For example, the silsesquioxane resin (A1) may contain structural units represented by the following formula (A1 a-1), or (A1 a-2), in addition to structural units represented by the formula (A1 a).
R in the structural unit represented by the following formula (a 1 a-1) or (a 1 a-2) a0 When the organic group is an organic group, the organic group may contain 1 or more selected from an aromatic group, an amide bond, and a urethane bond.
[ chemical formula 4]
(in the formulae (a 1 a-1) and (a 1 a-2), R a0 Each independently is a hydrogen atom or a 1-valent organic group. )
R in the formula (a 1 a-1) and (a 1 a-2) a0 Is an organic groupIn the case of using a compound having a carbon number of not particularly limited, for example, 1 to 50, more preferably 1 to 30, particularly preferably 1 to 20. The organic group may have a linear structure, a branched structure, a cyclic structure, or a combination of these structures. The organic group may have 1 or more unsaturated bonds. The organic group may comprise a heteroatom. Examples of the hetero atom include a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom.
Preferable examples of the organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl 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 naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an amino group which is substituted with 1 or 2 organic groups, and the like.
Examples of the substituent that these groups may have include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, a phenyl group, a phenoxy group, a phenylthio group, a benzoyl group, a phenoxycarbonyl group, a benzoyloxy group, a phenylalkyl group having 7 to 20 carbon atoms, a naphthyl group, a naphthoxy group, a naphthoyl group, a naphthyloxycarbonyl group, a naphthoyloxy group, a naphthylalkyl group having 11 to 20 carbon atoms, a heterocyclic group, a heterocyclylcarbonyl group, an amino group substituted with 1 to 20 carbon atoms or 2 organic groups, a nitro group, a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, and the like.
In the formula (a 1 a), R a1 Is a group represented by the following formula (a 1 a-I).
-X a -B a -Y a -COOH……(a1a-I)
In the formula (a 1 a-I), X a Is a single bond, an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, or-R a6 -NH-R a7 -a group represented.
R a6 And R is a7 Each independently represents an alkylene group having 1 to 3 carbon atoms.
Y a A cyclic organic group having 2 valences or a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms.
B a is-NH-CO-, -CO-NH-, -NH-CO-O-, and-O-CO-NH-, or-NH-CO-NH-.
X a And Y a Each independently may be substituted with 1 or more groups selected from the group consisting of (meth) acryloyloxy, vinyl, and epoxy-containing organic groups.
As X a Specific examples of the alkylene group having 1 to 6 carbon atoms include methylene, ethane-1, 2-diyl, ethane-1, 1-diyl, propane-1, 3-diyl, propane-1, 2-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl and the like.
X a The number of carbon atoms of the arylene group is 6 to 12, preferably 6 to 10.
Preferred specific examples of the arylene group include an o-phenylene group, a m-phenylene group, a p-phenylene group, a naphthalene-1, 4-diyl group, a naphthalene-1, 5-diyl group, a naphthalene-2, 6-diyl group, and a biphenyl-4, 4' -diyl group.
as-R a6 -NH-R a7 Specifically, for example, -CH 2 -NH-CH 2 -、-(CH 2 ) 2 -NH-(CH 2 ) 2 -、-(CH 2 ) 3 -NH-(CH 2 ) 3 -、-CH 2 -NH-(CH 2 ) 2 -、-(CH 2 ) 2 -NH-CH 2 -、-(CH 2 ) 2 -NH-(CH 2 ) 3 -、-(CH 2 ) 3 -NH-(CH 2 ) 2 -、-CH 2 -NH-(CH 2 ) 3 -、-(CH 2 ) 3 -NH-CH 2 -and the like.
Y a The 2-valent cyclic organic group in (a) may be a group obtained by removing 2 hydrogen atoms from an aromatic ring or a group obtained by removing 2 hydrogen atoms from an aliphatic ring.
Y a When the aromatic ring is a 2-valent group, the 2-valent cyclic organic group is preferably a group obtained by removing 2 hydrogen atoms from an aromatic ring having 6 to 10 carbon atoms, which may have a substituent having 1 or 2 carbon atoms. Preferable examples of the aromatic ring having 6 to 10 carbon atoms include benzene ring, naphthalene ring, methyl benzene ring, and dimethyl benzene ring.
Y a When the aliphatic ring contains a 2-valent group, the 2-valent cyclic organic group is preferably a group obtained by removing 2 hydrogen atoms from an aliphatic ring having 5 to 16 carbon atoms. Preferable examples of the aliphatic ring having 5 to 16 carbon atoms include cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, dicyclopentadiene ring, norbornane ring, norbornene ring, cubane ring, and basket ring.
Y a In the case of a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms, the chain aliphatic hydrocarbon group may be a straight chain or branched chain, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
Preferred examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include alkylene groups such as methylene, ethane-1, 2-diyl, ethane-1, 1-diyl, propane-1, 3-diyl, propane-1, 2-diyl, ethylene, (2-octenyl) ethylene, and (2, 4, 6-trimethyl-2-nonenyl), alkylene groups having a double bond, and branched alkylene groups having 1 to 9 carbon atoms.
In the formula (a 1 a-I), X a And Y a Each independently may be substituted with 1 or more groups selected from the group consisting of (meth) acryloyloxy, vinyl, and epoxy-containing organic groups.
In addition, the silsesquioxane resin (A1) is preferably X a And Y a At least one of them is selected from (meth) acryloyloxy groupsA silsesquioxane resin (A1-1) substituted with 1 or more groups selected from the group consisting of vinyl groups and epoxy-containing organic groups. In this case, the silsesquioxane resin (A1-1) functions as both the silsesquioxane resin (A1) and the polymerizable group-containing component, and can impart desired properties to the polymerizable composition without excessively increasing the types of the constituent components of the polymerizable composition.
The silsesquioxane resin (A1-1) may contain other structural units than the structural unit represented by the formula (A1 a).
The other structural unit is not particularly limited, and the structural unit represented by the following formula (a 2 b) is preferable as the other structural unit.
[ chemical formula 5]
(in the formula (a 2 b), R a3 Represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. )
R a3 When the alkyl group is an alkyl group, for example, methyl, ethyl and n-propyl groups are preferable. R is R a3 In the case of aryl or aralkyl, for example, phenyl, benzyl, tolyl, xylyl, and naphthyl are preferable.
X in silsesquioxane resin (A1-1) a And Y a At least one of them is substituted with 1 or more selected from the group consisting of (meth) acryloyloxy, vinyl and epoxy-containing organic groups, and the proportion of the structural unit represented by the formula (a 1 a) is not particularly limited, and is 10 to 100 mol%, preferably 30 to 70 mol%.
The silsesquioxane resin (A1) is also preferably a silsesquioxane resin (A1-2) having a structural unit represented by the formula (A1 a) and a structural unit represented by the following formula (a 2 a).
[ chemical formula 6]
(in the formula (a 2 a), R a2 Is a group represented by the following formula (a 1 a-II),
-Z a -A a ……(a1a-II)
Z a is a single bond, an alkylene group having 1 to 6 carbon atoms or an arylene group having 6 to 12 carbon atoms,
A a is (meth) acryloyloxy, vinyl, or epoxy-containing organic groups. )
The silsesquioxane resin (A1-2) also functions as an alkali-soluble resin, and on the other hand, can be preferably used as a polymerizable group-containing component.
In the formula (a 1 a-II), Z is a Preferred examples of the alkylene group having 1 to 6 carbon atoms include methylene, ethane-1, 2-diyl, ethane-1, 1-diyl, propane-1, 3-diyl, propane-1, 2-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl and the like.
Z a The number of carbon atoms of the arylene group is 6 to 12, preferably 6 to 10.
Preferred specific examples of the arylene group include an o-phenylene group, a m-phenylene group, a p-phenylene group, a naphthalene-1, 4-diyl group, a naphthalene-1, 5-diyl group, a naphthalene-2, 6-diyl group, and a biphenyl-4, 4' -diyl group.
In the formula (a 1 a-II), A a Is (meth) acryloyloxy, vinyl, or epoxy-containing organic groups. The epoxy group-containing organic group is not particularly limited, and examples thereof include an oxirane group, a glycidyl group, a glycidoxy group, and the like.
The silsesquioxane resin (A1-2) comprises a structural unit represented by formula (a 2 a) having a polymerizable group. Accordingly, X in the structural unit represented by the formula (A1 a) in the silsesquioxane resin (A1-2) a And Y a It is not necessary to be substituted with 1 or more groups selected from the group consisting of (meth) acryloyloxy, vinyl and epoxy-containing organic groups. X in the formula (a 1 a) is preferable from the viewpoint of easy synthesis or easy availability of the compound providing the structural unit represented by the formula (a 1 a) a And Y a Is not substituted with the polymerizable group.
Specific examples of the group represented by the formula (A1 a-I) in the structural unit represented by the formula (A1 a) contained in the silsesquioxane resin (A1-2) include X a 、B a 、Y a Are the groups of the combinations shown in Table 1 below. Y in Table 1 a Having two chemical bonds, 1 of which is bonded to the carboxyl group and the other is bonded to B a And (5) bonding. With respect to B in Table 1 a Also, as with X a 、Y a And (5) bonding.
TABLE 1
Specific examples of the group represented by the formula (a 2 a-II) in the structural unit represented by the formula (a 2 a) contained in the silsesquioxane resin (A1-2) include, for example, Z a And A a Are the groups of the combinations shown in Table 2 below.
TABLE 2
The silsesquioxane resin (A1-2) may contain structural units other than the structural unit represented by the formula (A1 a) and the structural unit represented by the formula (a 2 a).
The other structural unit is not particularly limited, and the structural unit represented by the above formula (a 2 b) is preferable.
The proportion of the structural unit represented by the formula (a 2 a) in the silsesquioxane resin (A1-2) is not particularly limited, but is 5 to 90 mol%, preferably 10 to 70 mol%, and preferably 20 to 60 mol%.
The proportion of the structural unit represented by the formula (A1 a) in the silsesquioxane resin (A1-2) is not particularly limited, but is 5 to 90 mol%, preferably 10 to 70 mol%, and more preferably 20 to 60 mol%.
The silicon-containing resin (a) may contain a silsesquioxane resin (A2) having a structural unit represented by the above formula (A2 a) and not belonging to the silsesquioxane resin (A1). The silsesquioxane resin (A2) has a structural unit represented by the formula (A2 a) and thus contains a polymerizable group. Therefore, the silsesquioxane resin (A2) can be suitably used as the polymerizable group-containing component.
The silsesquioxane resin (A2) may be formed of only the structural unit represented by the formula (A2 a), or may be formed of the structural unit represented by the formula (A2 a) and other structural units. The other structural unit is not particularly limited, and the structural unit represented by the aforementioned formula (a 2 b) is preferable.
The proportion of the structural unit represented by the formula (A2 a) in the silsesquioxane resin (A2) is not particularly limited, but is 5 to 100 mol%, preferably 10 to 70 mol%, and more preferably 20 to 60 mol%. Preferably 30 mol% or more, more preferably 40 mol% or more, and particularly preferably 50 mol% or more.
When the silicone-containing resin (a) is the silsesquioxane resin (A1) or the silsesquioxane resin (A2), the weight average molecular weight Mw is in a generally available range of 1000 to 100000, preferably 1000 to 50000, more preferably 1500 to 20000.
Next, the polysilane-polysiloxane resin (A-I), the resin mixture (A-II) and the polysilane structure-containing resin (A-III) will be described.
The polysilane-polysiloxane resin (A-I) is a polysilane-polysiloxane resin having a polysilane structure (I-1) and a polysiloxane structure (I-2).
The resin mixture (A-II) is a mixture of a resin having a polysilane structure (II-1) and a resin having a polysiloxane structure (II-2).
The polysilane structure-containing resin (A-III) is a resin having a polysilane structure (II-1).
The polysiloxane structures (I-2) and (II-2) each independently preferably include a hydrolytic condensation structure of at least 1 silicon compound selected from the group consisting of silicon compounds represented by the following formulas (A-1-1) to (A-1-4).
R 1 R 2 R 3 SiX 1 (A-1-1)
R 4 R 5 SiX 2 2 (A-1-2)
R 6 SiX 3 3 (A-1-3)
SiX 4 4 (A-1-4)
(in the above formula, X 1 ～X 4 Each independently is a hydrolyzable group, R 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Each independently is a hydrogen atom or an organic group in which a hydrogen atom may be substituted with a halogen atom. )
As X 1 ～X 4 Examples of the hydrolyzable group include an alkoxy group, a halogen atom, an isocyanate group (NCO), and the like, and an alkoxy group is preferable.
Examples of the alkoxy group include an alkoxy group having 1 to 6 carbon atoms, specifically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t-butoxy, pentyloxy and the like.
The halogen atom may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a chlorine atom.
As R 1 ～R 6 The organic group represented by the formula (I) may be an organic group having 1 to 30 carbon atoms, and examples thereof include alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl and t-butyl (preferably alkyl groups having 1 to 6 carbon atoms, particularly alkyl groups having 1 to 4 carbon atoms and the like)]Cycloalkyl group (cycloalkyl group having 5 to 8 carbon atoms, particularly cycloalkyl group having 5 to 6 carbon atoms such as cyclohexyl group), alkenyl group having 2 to 10 carbon atoms such as alkenyl group, propenyl group, butenyl group (alkenyl group having 2 to 6 carbon atoms, particularly alkenyl group having 2 to 4 carbon atoms, etc. are preferable)]Cycloalkenyl group having 5 to 10 carbon atoms such as cycloalkenyl group [ 1-cyclopentenyl group, 1-cyclohexenyl group and the like (preferably cycloalkenyl group having 5 to 8 carbon atoms, particularly cycloalkenyl group having 5 to 7 carbon atoms and the like)]C such as aryl (aryl having 6 to 10 carbon atoms such as phenyl and naphthyl), aralkyl [ benzyl, phenethyl, etc.) 6-10 aryl-C 1-6 Alkyl (C) 6-10 aryl-C 1-4 Alkyl, etc.)]Amino, N-substituted amino (N-mono-or di-substituted amino substituted with the above alkyl, cycloalkyl, aryl, aralkyl, acyl, etc.), etc. The above alkyl group, cycloalkyl group, aryl group constituting aralkyl group, or the like may have 1 or more substituents. Examples of such a substituent include an alkyl group (particularly an alkyl group having 1 to 6 carbon atoms) as described above, an alkoxy group as described above, and the like. Examples of the organic group having such a substituent include C such as tolyl, xylyl, ethylphenyl, and methylnaphthyl 1-6 alkyl-C 6-10 Aryl (preferably mono-, di-or tri-C 1-4 alkyl-C 6-10 Aryl, especially mono-or di-C 1-4 Alkylphenyl, etc.); c such as methoxyphenyl, ethoxyphenyl, methoxynaphthyl and the like 1-10 Alkoxy C 6-10 Aryl (preferably C 1-6 Alkoxy C 6-10 Aryl, especially C 1-4 Alkoxyphenyl groups, etc.), and the like.
Examples of the silicon compounds represented by the above formulas (A-1-1) to (A-1-4) include trihalosilanes such as trichlorosilane, tribromosilane and trifluorosilane; tetrahalosilanes such as tetrachlorosilane, tetrabromosilane, and tetrafluorosilane; alkyl trihalosilanes such as methyltrichlorosilane, methyltribromosilane, methyltrifluorosilane, ethyltrichlorosilane, ethyltribromosilane, ethyltrifluorosilane, n-propyltrichlorosilane, n-propyltribromosilane, n-propyltrichlorosilane, isopropyltrichlorosilane, isopropyltribromosilane, isopropyltrifluorosilane, n-butyltrichlorosilane, n-butyltribromosilane, n-butyltrifluorosilane, isobutyltrichlorosilane, isobutyltribromosilane, isobutyltrifluorosilane, sec-butyltrichlorosilane, sec-butyltribromosilane, sec-butyltrifluorosilane, tert-butyltrichlorosilane, tert-butyltribromosilane, and tert-butyltrifluorosilane; phenyl trihalosilanes such as phenyl trichlorosilane, phenyl tribromosilane, and phenyl trifluorosilane; a dialkyldihalosilane such as dichlorodimethylsilane, dibromodimethylsilane, difluorodimethylsilane, dichlorodiethylsilane, dibromodiethylsilane, difluorodiethylsilane, dichlorodi-n-propylsilane, dibromodi-n-propylsilane, difluorodi-n-propylsilane, dichlorodiisopropylsilane, dibromodiisopropylsilane, difluorodi-n-butylsilane, dibromodi-n-butylsilane, difluorodi-n-butylsilane, dichlorodi-n-butylsilane, dibromodi-n-butylsilane, difluorodi-n-butylsilane, dichlorodiisobutylsilane, dibromodiisobutylsilane, difluorodiisobutylsilane, dichlorodi-sec-butylsilane, dibromodi-sec-butylsilane, difluorodi-tert-butylsilane, and dichlorodi-tert-butylsilane; diphenyldihalosilanes such as dichlorodiphenylsilane, dibromodiphenylsilane and difluorodiphenylsilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane phenyl trimethoxysilane, phenyl triethoxysilane, benzyl trimethoxysilane, benzyl triethoxysilane, tolyl trimethoxysilane, tolyl triethoxysilane, anisoyltrimethoxysilane, anisoyltriethoxysilane, phenethyl trimethoxysilane, phenethyl triethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, methylphenyl dimethoxysilane, methylphenyl diethoxysilane, trimethylmethoxysilane, dimethylethylmethoxysilane, dimethylphenylmethoxysilane, dimethylbenzylmethoxysilane, dimethylethylmethoxysilane, tetraisocyanatosilane, methyltrisolylsilane, ethyltriisocyanato silane, propyltriisocyanato silane, butyltriisocyanato silane, dimethyldiisocyanato silane, diethyldiisocyanato silane, dipropyldiisocyanato silane, dibutyldiisocyanato silane, trimethylisocyanatosilane, triethylisocyanatosilane, tripropyiisocyanatosilane, tributylisocyanatosilane, etc.
The silicon compound represented by the above formula (A-1-3) may be a silicon compound from which the structural unit represented by the above formula (A1 a) or (A2 a) is derived, and in this case, the resin having the polysiloxane structure (II-2) in the resin mixture (A-II) is the same as the above silsesquioxane resin (A1) or silsesquioxane resin (A2).
The conditions for the hydrolytic condensation reaction of at least 1 silicon compound selected from the group consisting of the silicon compounds represented by the above formulas (a-1-1) to (a-1-4) are not particularly limited as long as the hydrolytic condensation reaction proceeds, and known conditions can be used, and in this case, a catalyst may be used, and examples of the catalyst include tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, hydrochloric acid, sulfuric acid, formic acid, and oxalic acid. The reaction conditions may be, for example, 1 to 10 hours and 25 to 100 ℃.
The polysilane structures (I-1) and (II-1) each independently preferably contain at least 1 structure selected from the group consisting of polysilane compounds represented by the following formulas (A-2-1) and (A-2-2).
(R 7 R 8 R 9 Si) a1 (R 10 R 11 Si) a2 (R 12 Si) a3 (Si) a4 ……(A-2-1)
(in the above formula, R 7 、R 8 、R 9 、R 10 、R 11 And R is 12 Each independently is a hydrogen atom, a hydroxyl group, or an organic group. a1, a2, a3 and a4 are each independently a molar fraction a1+a2+a3+a4=1, 0.ltoreq.a1.ltoreq.1, 0.ltoreq.a2.ltoreq.1, 0.ltoreq.a3.ltoreq.1, and 0.ltoreq.a2.ltoreq.a4 a4≤1。)
[ chemical formula 7]
(in the above formula (A-2-2), R a1 And R is a2 Each independently represents a hydrogen atom, a hydroxyl group, or an organic group. n represents an integer of 3 to 20. )
As R 7 ～R 6 、R a1 And R is a2 Examples of the organic group represented by R include 1 ～R 6 The organic groups represented are the same as those described in the above specific examples and preferred examples.
As R 7 ～R 12 、R a1 And R is a2 The organic group represented can be introduced by the method described in JP 2003-261681A 0031, for example.
(polysilane-polysiloxane resin (A-I))
The polysilane-polysiloxane resin (A-I) has a polysilane structure (I-1) and a polysiloxane structure (I-2).
As the polysilane-polysiloxane resin (A-I), a polysilane-polysiloxane resin in which the polysilane structure (I-1) and the polysiloxane structure (I-2) are linked via an oxygen atom (ether bond (-O-)) is preferable.
In the polysilane-polysiloxane resin (a-I), the chemical bond between the polysilane structure and the linking part (for example, ether bond) of the polysiloxane structure is relatively unstable with respect to the si—si bond in the polysilane structure and the si—o bond in the polysiloxane structure, and is easily decomposed by the action of an alkali developer. Thus, when the polymerizable composition contains the polysilane-polysiloxane resin (A-I), the alkali developability is excellent.
As the polysilane-polysiloxane resin (A-I), at least 1 selected from the group consisting of structures represented by the following formulas (H1) and (H2) is preferably contained.
[ chemical formula 8]
A 1 -A 2 O-Psi-OA 2 -A 1 ... ( HI)
A 1 -A 2 O-Psi-OH...(H2)
(in the above formulae (H1) and (H2), A 1 Each independently represents a polysiloxane structure including at least 1 of structures represented by the following formula (HA 1) and including at least 1 leftmost structure.
-A 2 O-each independently represents any one of the linking groups represented by the following formula (HA 2). In the above formula (H1), -OA 2 -represents an-OSi-structure opposite to the bonding order of the backbone-SiO-in the following formula (HA 1). Psi represents polysilane structure (I-1). )
[ chemical formula 9]
[ chemical formula 10]
(in the above formulae (HA 1) and (HA 2), R 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Each independently is a hydrogen atom or an organic group in which a hydrogen atom may be substituted with a halogen atom. )
As R 1 ～R 6 Specific examples and preferred examples of the organic group are described above.
The polysilane structure (I-1) represented by Psi is a polysilane structure having 3 to 40 Si atoms, preferably a polysilane structure having 5 to 30 Si atoms.
The polysilane structure (I-1) represented by Psi preferably contains 1 or more kinds of polysilane structures represented by the following formula (HB 1).
[ chemical formula 11]
(in the above formula (HB 1), R 10 、R 11 And R is 12 Each independently represents a hydrogen atom, a hydroxyl group, or an organic group. * Representing a chemical bond. )
The polysilane structure (I-1) represented by Psi is more preferably one represented by the following formula (HB 1-1) in view of easy removal of the polymerizable composition film in the case of removing the polymerizable composition film at the time of processing in the production process or in the case of imparting lithographic performance to the polymerizable composition.
[ chemical formula 12]
(in the above formula (HB 1-1), R 10 And R is 11 The meaning is the same as that of the formula (HB 1). )
As R 10 ～R 12 Specific examples and preferred examples of the organic group represented are as R 1 ～R 6 Specific examples and preferred examples of the organic group shown are the same as those described above.
As 1 specific example of the structure represented by the above formula (H1), a structure represented by the following formula (H3) is given.
[ chemical formula 13]
A 1 -A 2 O-Psi-OA 2 -A 1 -A 2 O-Psi-OA 2 -A 1 (H3)
(in the above formula (H3), A 1 、-A 2 O-、-OA 2 -and Psi have the same meaning as in formula (H1). )
The mass average molecular weight (Mw) of the polysilane-polysiloxane resin (A-I) is not particularly limited as long as it does not interfere with the object of the present invention, and is preferably 500 to 20000, more preferably 1000 to 10000, and even more preferably 2000 to 8000.
In the present specification, the mass average molecular weight (Mw) is a measured value obtained by Gel Permeation Chromatography (GPC) in terms of polystyrene.
(Process for producing polysilane-polysiloxane resin (A-I))
The polysilane-polysiloxane resin (A-I) can be produced by subjecting at least 1 selected from the group consisting of silicon compounds represented by the above formulas (A-1-1) to (A-1-4), and hydrolysates, condensates and hydrolytic condensates of the above silicon compounds, to hydrolytic condensation reaction with a resin having a polysilane structure.
The resin having a polysilane structure used in the production is preferably at least 1 selected from the group consisting of polysilane compounds represented by the formulas (A-2-1) and (A-2-2).
The hydrolysis-condensation reaction conditions are not particularly limited, and the hydrolysis-condensation reaction may be carried out using, for example, 1 or more compounds selected from the group consisting of an inorganic acid, an aliphatic sulfonic acid, and an aromatic sulfonic acid as an acid catalyst. Examples of the acid catalyst that can be used in this case include hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, and the like. The amount of the catalyst to be used is preferably 10 based on 1 mol of the silicon compound represented by the above-mentioned formulas (A-1-1) to (A-1-4) -6 About 10 moles, more preferably 10 -5 About 5 moles, more preferably 10 -4 1 mole.
The amount of water used in the hydrolysis and condensation of the silicon compounds represented by the above-mentioned formulae (A-1-1) to (A-1-4) is preferably 0.01 to 100 mol, more preferably 0.05 to 50 mol, and even more preferably 0.1 to 30 mol, based on 1 mol of the hydrolyzable group of the silicon compound represented by the above-mentioned formulae (A-1-1) to (A-1-4).
The reaction temperature is preferably 0 to 100℃and more preferably 5 to 80 ℃.
As the organic solvent which can be added to the aqueous catalyst solution, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, acetone, acetonitrile, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, butanediol monomethyl ether, propanediol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propanediol monoethyl ether, ethylene glycol monoethyl ether, propanediol dimethyl ether, diethylene glycol dimethyl ether, propanediol monomethyl ether acetate, propanediol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propanediol mono-t-butyl ether acetate, gamma-butyrolactone, a mixture thereof, and the like are preferable.
Of these solvents, more preferable solvents are water-soluble solvents. Examples thereof include alcohols such as methanol, ethanol, 1-propanol and 2-propanol, polyhydric alcohols such as ethylene glycol and propylene glycol, polyhydric alcohol condensate derivatives such as butanediol monomethyl ether, propanediol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propanediol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propanediol monopropyl ether and ethylene glycol monopropyl ether, acetone, acetonitrile and tetrahydrofuran. Among them, a solvent having a boiling point of 100℃or lower is particularly preferable.
Further, as the above organic solvent, at least 1 solvent selected from terpene compounds having at least 1 group selected from the group consisting of hydroxyl groups and acetoxy groups, and acetate compounds containing a cyclic skeleton (excluding the above terpene compounds), which will be described later, may be preferably used.
The amount of the organic solvent used is preferably 0 to 1,000mL, particularly preferably 0 to 500mL, per 1 mol of the silicon compound represented by the above-mentioned formulas (A-1-1) to (A-1-4).
Then, if necessary, the catalyst may be neutralized, and the alcohol formed in the hydrolytic condensation reaction may be removed under reduced pressure to obtain an aqueous reaction mixture solution.
The polysilane compound represented by the above formula (A-2-1) or (A-2-2) can be produced by applying or using various production methods of polysilanes.
For example, the following methods are mentioned: (a) A method of dehalogenating and polycondensing halogenated silanes using magnesium as a reducing agent (e.g., a method described in "magnesium reduction method", WO98/29476, and Japanese patent application laid-open No. 2003-277507); (b) A method of coupling a dialkyldihalosilane or a dihalotetralkyldisilane in a toluene solvent by strongly stirring the mixture with an alkali metal such as metallic sodium at a temperature of 100℃or higher [ J.Am.chem.Soc.,103 (1981) 7352]; (c) A method of anionic polymerization of disilicide masked with biphenyl or the like (Japanese patent application laid-open No. 1-23063); (d) A method of ring-opening polymerizing cyclic silanes (Japanese patent application laid-open No. 5-170913); (e) A method in which a hydrosilane is subjected to dehydropolycondensation using a transition metal complex catalyst (Japanese patent publication No. 7-17753); (f) A method for producing polysilanes by electrode-reducing dihalosilanes at a temperature of room temperature or lower (Japanese patent application laid-open No. 7-309953); and the like, and a magnesium reduction method is preferable.
As the polysilane compound represented by the above formula (A-2-1) or (A-2-2), commercially available products such as OGSOL SI-10-10 (polymethylphenylsilane), SI-10-20 (polymethylphenylsilane), SI-20-10 (polyphenylsilane), SI-30-10 (cyclic polydiphenylsilane) manufactured by Osaka Gas Chemicals can be used. In addition, a product obtained by reacting them under the following alkaline conditions to obtain a low molecular weight can also be used.
(resin mixture (A-II))
As described above, the resin mixture (A-II) is a mixture of a resin having a polysilane structure (II-1) and a resin having a polysiloxane structure (II-2). The resin having the polysilane structure (II-1) and the resin having the polysiloxane structure (II-2) will be described below.
((resin having polysilane Structure (II-1))
The resin having the polysilane structure (II-1) may be a polysilane structure having 3 to 40 Si atoms, and preferably a polysilane structure having 5 to 30 Si atoms.
The resin having the polysilane structure (II-1) preferably contains at least 1 of the polysilane structures represented by the above formula (HB 1), more preferably contains the polysilane structure represented by the above formula (HB 1-1).
The resin having the polysilane structure (II-1) is preferably at least 1 selected from the group consisting of polysilane compounds represented by the above formulas (A-2-1) and (A-2-2).
When the resin having the polysilane structure (II-1) has a substituent represented by the above formula (a 1 a-II), the resin having the polysilane structure (II-1) can be suitably used as a component containing a polymerizable group (in the case of a resin containing a polymerizable group which is (5) described later).
The mass average molecular weight (Mw) of the resin having the polysilane structure (II-1) is not particularly limited as long as the object of the present invention is not impaired, and is preferably 500 to 20000, more preferably 1000 to 10000, and further preferably 2000 to 5000.
((resin having polysiloxane Structure (II-2))
The resin having the polysiloxane structure (II-2) preferably HAs a hydrolytic condensation structure of a mixture containing at least 1 kind selected from the group consisting of silicon compounds represented by the above formulas (A-1-1) to (A-1-4), more preferably contains at least 1 kind of polysiloxane structure represented by the above formula (HA 1).
The resin having the polysiloxane structure (II-2) can be produced by a hydrolytic condensation reaction of a mixture containing at least 1 selected from the group consisting of the silicon compounds represented by the above formulas (A-1-1) to (A-1-4).
The mass average molecular weight (Mw) of the resin having the polysiloxane structure (II-2) is not particularly limited as long as it does not interfere with the object of the present invention, and is preferably 500 to 20000, more preferably 1000 to 10000.
When the silicone-containing resin (A) is the resin mixture (A-II), the mixing ratio of the resin having the polysilane structure (II-1) to the resin having the polysiloxane structure (II-2) is not particularly limited, as long as the effect of the present invention is not impaired, and it is preferably 0.01 to 5 times by mass, more preferably 0.05 to 1 time by mass.
(polysilane Structure-containing resin (A-III))
The polysilane structure-containing resin (A-III) is a resin having a polysilane structure (II-1) and is the same as the resin having a polysilane structure (II-1) in the resin mixture (A-II).
When the silicon-containing resin (A) is a polysilane structure-containing resin (A-III), the resin having the polysilane structure (II-1) is preferably a resin having the polysilane structure or a substituent represented by the above formula (a 1 a-I) which has been treated (e.g., purified) under alkaline conditions.
As the alkali to be used in the treatment under alkaline conditions, various alkali compounds may be used as long as they are alkali compounds, and examples thereof include inorganic bases such as sodium hydroxide, potassium hydroxide, barium hydroxide, ammonia, tetramethylammonium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, lithium hydride, sodium hydride, potassium hydride, calcium hydride, etc., alkyl metals such as methyllithium, N-butyllithium, methylmagnesium chloride, ethylmagnesium bromide, etc., metal halides such as Cr, ga, fe (II), fe (III)), cd, co, ni, sn, pb, cu (Cu (II), cu (I)), ag, pd, pt, au, etc., metal (or metal ions), alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc., and organic bases such as triethylamine, diisopropylethylamine, N-dimethylaniline, pyridine, 4-dimethylaminopyridine, diazabicycloundecene (DBU), etc. The reaction temperature is preferably about-50℃to the boiling point of the solvent, and more preferably room temperature to 100 ℃.
When the silicone resin (a) contains a polysilane structure-containing resin (a-III), the silicone resin (a) is preferably further combined with a silsesquioxane resin (A1) and/or a polysilane-polysiloxane resin (a-I).
When the silicone-containing resin (a) contains a resin (a-III) having a polysilane structure, it is preferable to use the resin (a) in combination with (4) a polyfunctional polymerizable monomer (B) as a polymerization component.
The content of the silicone-containing resin (a) in the polymerizable composition is preferably 20 to 97% by mass, more preferably 30 to 90% by mass, and even more preferably 40 to 80% by mass, based on the entire solid content in the polymerizable composition.
By using the silicone resin (a) in the amount within the above range, the generation of residues in the unexposed portions can be easily suppressed, and good developability can be easily ensured.
< polyfunctional polymerizable monomer (B1) >)
The polymerizable composition may contain a polyfunctional polymerizable monomer (B1) as a polymerizable group-containing component. The polyfunctional polymerizable monomer is a compound having a (meth) acryloyloxy group, a vinyl group, or an epoxy group-containing organic group as a polymerizable group.
Preferable examples of the polyfunctional polymerizable monomer (B1) include an unsaturated compound (B1-1) having a (meth) acryloyloxy group or a vinyl group, and an epoxy compound (B1-2) having an epoxy group-containing organic group.
Among these polyfunctional polymerizable monomers (B1), from the viewpoint of improving the adhesion of the polymerizable composition to the substrate and the strength of the polymerizable composition after curing, the polyfunctional polymerizable monomer having 3 or more functions is preferable, the polyfunctional polymerizable monomer having 4 or more functions is more preferable, and the polyfunctional polymerizable monomer having 5 or more functions is still more preferable.
Examples of the unsaturated compound (B1-1) include 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, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloxypropyl ester, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, and diglycidyl ether di (meth) acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., a reactant with 2-hydroxyethyl (meth) acrylate such as toluene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, or 1, 6-hexamethylene diisocyanate), methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, a condensate of a polyhydric alcohol and N-methylol (meth) acrylamide, and the like, 1,3, 5-triacrylhexahydro-1, 3, 5-triazine (triacrylformal), and the like. These polyfunctional monomers may be used alone or in combination of 2 or more.
Among these ethylenically unsaturated compounds (B1-1), from the viewpoint of improving the adhesion of the polymerizable composition to the substrate and the strength of the polymerizable composition after curing, the unsaturated compound is preferably an unsaturated compound having 3 or more functions, more preferably an unsaturated compound having 4 or more functions, and still more preferably an unsaturated compound having 5 or more functions.
Specific examples of the epoxy compound (B1-2) include 2-functional epoxy resins such as bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, bisphenol AD-type epoxy resins, naphthalene-type epoxy resins, and biphenyl-type epoxy resins; glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; glycidyl amine type epoxy resins such as tetraglycidyl aminodiphenylmethane, triglycidyl para-aminophenol, tetraglycidyl meta-xylylenediamine, and tetraglycidyl bisaminomethyl cyclohexane; heterocyclic epoxy resins such as triglycidyl isocyanurate; 3-functional epoxy resins such as phloroglucinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenyl methane 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 tetraepoxypropoxy biphenyl.
The content of the polyfunctional polymerizable monomer (B1) in the case where the polymerizable composition contains the polyfunctional polymerizable monomer (B1) is preferably 1 to 80% by mass, more preferably 5 to 40% by mass, relative to the mass of the entire solid content of the polymerizable composition. The polyfunctional polymerizable monomer (B1) is preferably used in an amount of 10 to 200 parts by mass, more preferably 20 to 120 parts by mass, based on 100 parts by mass of the silicone resin (a). When the range is within the above range, there is a tendency that the sensitivity, developability, and uniformity of resolution performance are easily obtained.
< polymerizable group-containing resin (B2) >)
The polymerizable composition may contain, as a polymerizable group-containing component: a polymerizable group-containing resin (B2) which has 1 or more groups selected from the group consisting of (meth) acryloyloxy groups, vinyl groups, and epoxy group-containing organic groups and which does not belong to any of the silsesquioxane resins (A1), silsesquioxane resins (A2), and polyfunctional polymerizable monomers (B1).
The polymerizable group-containing resin (B2) may be used in combination with the polyfunctional polymerizable monomer (B1).
Preferable examples of the polymerizable group-containing resin (B2) include an unsaturated resin (B2-1) having a (meth) acryloyloxy group or a vinyl group, and an epoxy group-containing resin (B2-2) having an epoxy group-containing organic group.
The unsaturated resin (B2-1) and the epoxy group-containing resin (B2-2) will be described below.
[ unsaturated resin (B2-1) ]
The unsaturated resin (B2-1) is not particularly limited as long as it is a resin having a (meth) acryloyloxy group or a vinyl group. As a preferable example of the unsaturated resin (B2-1), there is a resin obtained by reacting at least a part of the epoxy groups contained in the epoxy group-containing resin (B2-2) described later with an unsaturated carboxylic acid.
Examples of the unsaturated carboxylic acid include (meth) acrylic acid; butenoic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, anhydrides of these dicarboxylic acids.
The unsaturated resin (B2-1) is preferably a resin having a Cardo structure represented by the following formula (B-1) (also referred to as a Cardo resin).
[ chemical formula 14]
In the formula (b-1), X b A group represented by the following formula (b-2). m1 represents an integer of 0 to 20.
[ chemical formula 15]
In the above formula (b-2), R b1 Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R b2 Each independently represents a hydrogen atom or a methyl group, R b3 Each independently represents a linear or branched alkylene group, m2 represents 0 or 1, W b The group represented by the following formula (b-3).
[ chemical formula 16]
In the formula (b-2), R is b3 The alkylene group having 1 to 20 carbon atoms is preferable, the alkylene group having 1 to 10 carbon atoms is more preferable, the alkylene group having 1 to 6 carbon atoms is particularly preferable, and ethane-1, 2-diyl, propane-1, 2-diyl, and propane-1, 3-diyl are most preferable.
Ring A in formula (b-3) b Can be condensed with an aromatic ring, and represents an aliphatic ring which may have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring.
Examples of the aliphatic ring include monocycloparaffins, bicycloparaffins, tricycloparaffins, tetracycloparaffins, and the like.
Specifically, monocycloparaffins such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane are mentioned.
The aromatic ring which may be condensed with the aliphatic ring may be an aromatic hydrocarbon ring, or may be an aromatic heterocyclic ring, and is preferably an aromatic hydrocarbon ring. Specifically, benzene rings and naphthalene rings are preferable.
Preferable examples of the 2-valent group represented by the formula (b-3) include the following groups.
[ chemical formula 17]
A 2-valent group X in the formula (b-1) b By providing residues Z b The tetracarboxylic dianhydride of (2 a) is reacted with a diol compound represented by the following formula (b-2 a) to be introduced into the Cardo resin.
[ chemical formula 18]
In the formula (b-2 a), R b1 、R b2 、R b3 And m2 are the same as those described for formula (b-2). With respect to ring A in formula (b-2 a) b The description is the same as that of the formula (b-3).
The diol compound represented by the formula (b-2 a) can be produced, for example, by the following method.
First, according to need, the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (b-2 b) is replaced with-R according to a conventional method b3 The group represented by-OH is then glycidylated using epichlorohydrin or the like to give an epoxy compound represented by the following formula (b-2 c).
Next, the epoxy compound represented by the formula (b-2 c) is reacted with acrylic acid or methacrylic acid to obtain the diol compound represented by the formula (b-2 a).
In the formula (b-2 b) and the formula (b-2 c), R b1 、R b3 And m2 are the same as those described for formula (b-2). With respect to the ring A in the formula (b-2 b) and the formula (b-2 c) b The description is the same as that of the formula (b-3).
The method for producing the diol compound represented by the formula (b-2 a) is not limited to the above method.
[ chemical formula 19]
As preferable examples of the diol compound represented by the formula (b-2 b), the following diol compounds are given.
[ chemical formula 20]
In the above formula (b-1), R b0 Is a hydrogen atom or-CO-Y b -COOH represents a group. Here, Y b Represents the residue resulting from the removal of the anhydride group (-CO-O-CO-) from the dicarboxylic anhydride. Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride, chlorendic anhydride (Chlorendic Anhydride), methyl tetrahydrophthalic anhydride, glutaric anhydride, and the like.
In the formula (b-1), Z b Represents a residue obtained by removing 2 acid anhydride groups from tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, and other tetracarboxylic dianhydrides having an alicyclic skeleton.
In the formula (b-1), m1 represents an integer of 0 to 20.
The weight average molecular weight of the Cardo resin is preferably 1000 to 40000, more preferably 1500 to 30000, and even more preferably 2000 to 10000. When the weight average molecular weight of the Cardo resin is in the above range, satisfactory developability can be obtained and sufficient heat resistance and film strength can be obtained.
[ epoxy group-containing resin (B2-2) ]
The epoxy group-containing resin (B2-2) may be a polymer obtained by polymerizing a monomer having an epoxy group or a monomer mixture containing a monomer having an epoxy group. The epoxy group-containing resin may be a resin obtained by introducing an epoxy group into a polymer having a reactive functional group such as a hydroxyl group, a carboxyl group, or an amino group, using a compound having an epoxy group such as epichlorohydrin. In view of easiness in obtaining, preparing, adjusting the amount of an epoxy group in the polymer, and the like, a polymer obtained by polymerizing a monomer having an epoxy group or a monomer mixture containing a monomer having an epoxy group is preferable as the polymer having an epoxy group.
Preferable examples of the epoxy group-containing resin (B2-2) include phenol-type epoxy resins, brominated phenol-type epoxy resins, o-cresol-type epoxy resins, bisphenol A-type epoxy resins, and bisphenol AD-type epoxy resins; cyclic aliphatic epoxy resins such as epoxide of dicyclopentadiene type phenolic resin; aromatic epoxy resins such as naphthalene type phenolic resins and epoxides.
Among the epoxy group-containing resins (B2-2), homopolymers of (meth) acrylates having epoxy groups or copolymers of (meth) acrylates having epoxy groups with other monomers are preferable in terms of easy preparation or easy adjustment of physical properties of the film to be formed.
The (meth) acrylate having an epoxy group may be a (meth) acrylate having a chain aliphatic epoxy group or may be a (meth) acrylate having an alicyclic epoxy group as described later. In addition, the (meth) acrylate having an epoxy group may contain an aromatic group. Among the (meth) acrylates having an epoxy group, aliphatic (meth) acrylates having a chain aliphatic epoxy group and aliphatic (meth) acrylates having an alicyclic epoxy group are preferable, and aliphatic (meth) acrylates having an alicyclic epoxy group are more preferable.
Examples of the (meth) acrylic acid ester having an epoxy group and containing an aromatic group include 4-glycidyloxyphenyl (meth) acrylate, 3-glycidyloxyphenyl (meth) acrylate, 2-glycidyloxyphenyl (meth) acrylate, 4-glycidyloxyphenyl methyl (meth) acrylate, 3-glycidyloxyphenyl methyl (meth) acrylate, and 2-glycidyloxyphenyl methyl (meth) acrylate.
Examples of the aliphatic (meth) acrylate having a chain aliphatic epoxy group include (meth) acrylate in which a chain aliphatic epoxy group is bonded to an oxygen group (-O-) in an ester group (-O-CO-) such as an epoxyalkyl (meth) acrylate and epoxyalkyloxyalkyl (meth) acrylate. The chain aliphatic epoxy group possessed by such a (meth) acrylate may contain 1 or more oxy groups (-O-) in the chain. The number of carbon atoms of the chain aliphatic epoxy group is not particularly limited, but is preferably 3 to 20, more preferably 3 to 15, and particularly preferably 3 to 10.
Specific examples of the aliphatic (meth) acrylate having a chain aliphatic epoxy group include alkylene (meth) acrylates such as glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, and 6, 7-epoxyheptyl (meth) acrylate; epoxy alkyl oxy (meth) acrylates such as 2-glycidyloxy ethyl (meth) acrylate, 3-glycidyloxy n-propyl (meth) acrylate, 4-glycidyloxy n-butyl (meth) acrylate, 5-glycidyloxy n-hexyl (meth) acrylate, and 6-glycidyloxy n-hexyl (meth) acrylate.
Specific examples of the aliphatic (meth) acrylate having an alicyclic epoxy group include compounds represented by the following formulas (b 1-1) to (b 1-15). Among these, compounds represented by the following formulas (b 1-1) to (b 1-5) are preferable, and compounds represented by the following formulas (a 1-1) to (a 1-3) are more preferable. In addition, the bonding site of the oxygen atom of the ester group to the alicyclic ring in each of these compounds is not limited to the site described herein, and may include a part of positional isomers.
[ chemical formula 21]
[ chemical formula 22]
[ chemical formula 23]
In the above formula, R b7 Represents a hydrogen atom or a methyl group, R b8 An aliphatic saturated hydrocarbon group having 2 valences and 1 to 6 carbon atoms, R b9 Represents a hydrocarbon group having 2 valence and 1 to 10 carbon atoms, t 0 An integer of 0 to 10. As R b8 Straight-chain or branched alkylene groups such as methylene, ethylene, propylene, 1, 4-butylene, ethylethylene, 1, 5-pentylene, 1, 6-hexylene are preferred. As R b9 For example, methylene, ethylene, propylene, 1, 4-butylene, ethylethylene, 1, 5-pentylene, 1, 6-hexylene, phenylene, cyclohexylene are preferred.
The polymer having an epoxy group may be a homopolymer of a (meth) acrylate having an epoxy group or a copolymer of a (meth) acrylate having an epoxy group and another monomer, and the content of the structural unit derived from a (meth) acrylate having an epoxy group in the polymer having an epoxy group is preferably 70% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 100% by mass.
When the polymer having an epoxy group is a copolymer of a (meth) acrylate having an epoxy group and another monomer, examples of the other monomer include unsaturated carboxylic acids, (meth) acrylates having no epoxy group, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These compounds may be used alone or in combination of 2 or more. From the viewpoints of storage stability of the polymerizable composition and chemical resistance of a film formed using the polymerizable composition to alkali and the like, it is preferable that the copolymer of the (meth) acrylate having an epoxy group and the other monomer does not contain a structural unit derived from an unsaturated carboxylic acid.
Examples of the unsaturated carboxylic acid include (meth) acrylic acid; (meth) acrylamide; butenoic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, anhydrides of these dicarboxylic acids.
Examples of the (meth) acrylic acid ester having no epoxy group include linear or branched alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, pentyl (meth) acrylate, and tert-octyl (meth) acrylate; chloroethyl (meth) acrylate, 2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (meth) acrylate; (meth) acrylic acid esters containing a group having an alicyclic skeleton. Among the (meth) acrylates having no epoxy group, preferred is a (meth) acrylate containing a group having an alicyclic skeleton.
In the (meth) acrylic acid ester containing a group having an alicyclic skeleton, the alicyclic group constituting the alicyclic skeleton may be a single ring or multiple rings. Examples of the monocyclic alicyclic group include cyclopentyl and cyclohexyl. Examples of the polycyclic alicyclic group include norbornyl, isobornyl, tricyclic nonyl, tricyclic decyl, and tetracyclododecyl.
Examples of the (meth) acrylate containing a group having an alicyclic skeleton include compounds represented by the following formulas (b 2-1) to (b 2-8). Among these, compounds represented by the following formulas (b 2-3) to (b 2-8) are preferable, and compounds represented by the following formulas (b 2-3) or (b 2-4) are more preferable.
[ chemical formula 24]
[ chemical formula 25]
In the above formula, R b10 Represents a hydrogen atom or a methyl group, R b11 Represents a single bond or a C1-6 aliphatic saturated hydrocarbon group having 2 valences, R b12 Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As R b11 Single bond, linear or branched alkylene groups such as methylene, ethylene, propylene, 1, 4-butylene, ethylethylene, 1, 5-pentylene, 1, 6-hexylene are preferred. As R b12 Methyl and ethyl are preferred.
Examples of the (meth) acrylamides 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, and N-hydroxyethyl-N-methyl (meth) acrylamide.
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; etc.
Examples of the vinyl ethers include aliphatic 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, tetrahydrofurfuryl vinyl ether, and the like; vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2, 4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthryl ether; etc.
Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, 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, and vinyl naphthoate.
Examples of the styrenes include styrene; alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc.; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.; halogenated styrenes such as chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, and the like; etc.
The molecular weight of the epoxy group-containing resin (B2-2) is not particularly limited within a range that does not hinder the object of the present invention, but the weight average molecular weight in terms of polystyrene is preferably 3,000 to 30,000, more preferably 5,000 to 15,000.
The content of the polymerizable group-containing resin (B2) in the case where the polymerizable composition contains the polymerizable group-containing resin (B2) is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, relative to the mass of the entire solid content of the polymerizable composition. When the content is within the above range, there is a tendency that the sensitivity, developability, and uniformity of resolution performance are easily obtained.
In the case of using the polyfunctional polymerizable monomer (B1) and the polymerizable group-containing resin (B2) together, the total content of both is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, based on the mass of the entire solid content of the polymerizable composition.
Polymerization initiator (C) >, and process for producing the same
The polymerization initiator (C) is not particularly limited as long as it can cause the polymerization reaction of the polymerizable group-containing component in the polymerizable composition. Typically, compounds used as photopolymerization initiators in various photosensitive compositions can be used without particular limitation.
Specific examples of the polymerization initiator (C) include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-dimethoxy-1, 2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino (morpholino) propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl ] ethanone oxime, (9-Ethyl-6-nitro-9H-carbazol-3-yl) [4- (2-methoxy-1-methylethoxy) -2-methylphenyl ] methanone O-acetoxime, 2- (benzoyloxy-imino) -1- [4- (phenylthio) phenyl ] -1-octanone, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, 4-benzoyl-4' -methyl dimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexyl benzoic acid, 4-dimethylamino-2-isopentylbenzoic acid benzil-beta-methoxyethyl acetal, benzil dimethyl ketal, 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl O-benzoylbenzoate, 2, 4-diethylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2, 4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1, 2-benzanthraquinone, 2, 3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4, 5-bis (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, 4' -bis-dimethylaminobenzophenone 4,4' -Didiethylaminobenzophenone, 4' -dichlorobenzophenone, 3-dimethyl-4-methoxybenzophenone, benzyl, benzoin methyl ether, benzoin ethyl ether benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2-diethoxy acetophenone, p-dimethyl acetophenone, p-dimethylamino propiophenone, dichloro acetophenone, trichloroacetophenone, p-t-butyl acetophenone, p-dimethylamino acetophenone, p-t-butyl trichloroacetophenone, p-t-butyl dichloro acetophenone, alpha, alpha-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, dibenzocycloheptanone (dibenzzosuberone), 4-dimethylaminobenzoate, 9-phenylacridine, 1, 7-bis- (9-acridinyl) heptane, 1, 5-bis- (9-acridinyl) pentane, 1, 3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4, 6-tris (trichloromethyl) s-triazine, 2-methyl-4, 6-bis (trichloromethyl) s-triazine, 2- [2- (5-methylfuran-2-yl) vinyl ] -4, 6-bis (trichloromethyl) s-triazine, 2- [2- (furan-2-yl) vinyl ] -4, 6-bis (trichloromethyl) s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) vinyl ] -4, 6-bis (trichloromethyl) s-triazine, 2- [2- (3, 4-dimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) s-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-ethoxystyryl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-n-butoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2, 4-bis trichloromethyl-6- (3-bromo-4-methoxy) phenyl s-triazine, 2, 4-bis trichloromethyl-6- (2-bromo-4-methoxy) phenyl s-triazine, 2, 4-bis (trichloromethyl-6- (3-bromo-4-phenyls-triazine), 2, 4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl s-triazine, and the like. These polymerization initiators may be used singly or in combination of 2 or more.
Among these, an oxime-based polymerization initiator is particularly preferably used in terms of sensitivity. Among these oxime-based polymerization initiators, particularly preferred are O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl ] ethanone oxime, 1- [ 9-ethyl-6- (pyrrol-2-ylcarbonyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetyl oxime), and 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl ] -1-octanone.
In the case where the polymerizable group is an epoxy group-containing organic group, a photosensitive cationic polymerization initiator such as an iodonium salt or sulfonium salt may be used as the polymerization initiator (C).
As the polymerization initiator (C), an oxime compound represented by the following formula (C1) is also preferably used.
[ chemical formula 26]
(R c1 Is a group selected from the group consisting of a 1-valent organic group, an amino group, a halogen group, a nitro group, and a cyano group,
n1 is an integer of 0 to 4,
n2 is 0 or 1 and is preferably selected from the group consisting of,
R c2 is phenyl which may have a substituent, or carbazolyl which may have a substituent,
R c3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )
In the formula (c 1), R c1 The organic group is not particularly limited insofar as it does not interfere with the object of the present invention, and may be appropriately selected from various organic groups. As R c1 Examples of the preferable organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl 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, and a naphthylalkyl group which may have a substituentHeterocyclic groups, amino groups substituted with 1 or 2 organic groups, morpholin-1-yl, and piperazin-1-yl, halogen, nitro, cyano, and the like. When n1 is an integer of 2 to 4, R c1 May be the same or different. The number of carbon atoms of the substituent does not include the number of carbon atoms of the substituent further included in the substituent.
R c1 In the case of an alkyl group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 6. In addition, R c1 When alkyl is used, the alkyl may be straight-chain or branched. As R c1 Specific examples of the 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. In addition, R c1 When alkyl, the alkyl group may contain an ether linkage (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.
R c1 In the case of an alkoxy group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 6. In addition, R c1 When the alkoxy group is a straight chain or branched chain. As R c1 Specific 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, isononyl, n-decyloxy, isodecyloxy and the like. In addition, R c1 In the case of alkoxy groups, the alkoxy groups may contain ether linkages (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, and propyloxyethoxyethoxyAnd methoxypropyloxy.
R c1 In the case of cycloalkyl or cycloalkoxy, the number of carbon atoms is preferably 3 to 10, more preferably 3 to 6. As R c1 Specific examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. As R c1 Specific examples of the cycloalkoxy group include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy.
R c1 In the case of a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms is preferably 2 to 20, more preferably 2 to 7. As R c1 Specific examples of the saturated aliphatic acyl group include acetyl, propionyl, n-butyryl, 2-methylpropanoyl, n-pentanoyl, 2-dimethylpropionyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecanoyl, and n-hexadecanoyl. As R c1 Specific examples of saturated aliphatic acyloxy groups include acetyloxy, propionyloxy, n-butyryloxy, 2-methylpropanoyloxy, n-pentanoyloxy, 2-dimethylpropionyloxy, n-hexanoyloxy, n-heptanoyloxy, n-octanoyloxy, n-nonanoyloxy, n-decanoyloxy, n-undecanoyloxy, n-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanoyloxy, and n-hexadecanoyloxy.
R c1 In the case of an alkoxycarbonyl group, the number of carbon atoms is preferably 2 to 20, more preferably 2 to 7. As R c1 Specific examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, and,N-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, isodecyloxycarbonyl and the like.
R c1 In the case of phenylalkyl groups, the number of carbon atoms is preferably 7 to 20, more preferably 7 to 10. In addition, R c1 In the case of a naphthylalkyl group, the number of carbon atoms is preferably 11 to 20, more preferably 11 to 14. As R c1 Specific examples of the phenylalkyl group include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. As R c1 Specific examples of the naphthylalkyl group include an α -naphthylmethyl group, a β -naphthylmethyl group, a 2- (α -naphthyl) ethyl group, and a 2- (β -naphthyl) ethyl group. R is R c1 R is phenylalkyl or naphthylalkyl c1 Further, a substituent may be present on the phenyl group or the naphthyl group.
R c1 When the heterocyclic group is a heterocyclic group, the heterocyclic group is a five-membered or six-membered monocyclic ring containing 1 or more N, S, O, or is a heterocyclic group in which the monocyclic rings are condensed with each other or the monocyclic rings are condensed with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is 3 or less. Examples of the heterocycle 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, and the like. R is R c1 When the heterocyclic group is a heterocyclic group, the heterocyclic group may further have a substituent.
R c1 When the amino group is substituted with 1 or 2 organic groups, preferable examples of the organic groups 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 20 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, and a naphthoyl group which may have a substituentNaphthyl alkyl having 11 to 20 carbon atoms, heterocyclic group, and the like. Specific examples of these preferred organic groups and R c1 Likewise, the same is true. 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-pentanoylamino, n-hexanoylamino, n-heptanoylamino, n-octanoylamino, n-decanoylamino, benzoylamino, α -naphthoylamino, β -naphthoylamino and the like.
As R c1 Examples of the substituent when the phenyl group, the naphthyl group and the heterocyclic group 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, morpholin-1-yl, piperazin-1-yl, halogen, nitro and cyano groups. R is R c1 When the phenyl group, the naphthyl group, and the heterocyclic group included in the compound further have a substituent, the number of the substituents is not limited within a range that does not hinder the object of the present invention, and is preferably 1 to 4.R is R c1 When the phenyl group, the naphthyl group, and the heterocyclic group included in (a) have a plurality of substituents, the plurality of substituents may be the same or different.
R c1 In the above, from the viewpoints of chemical stability, low steric hindrance, easiness in synthesizing oxime ester compounds, and the like, a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a saturated aliphatic acyl group having 2 to 7 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and a methyl group is particularly preferable.
For R c1 At the position bonded to the phenyl group, the position of the chemical bond between the phenyl group and the main skeleton of the oxime ester compound is defined as 1 position, and the position of the methyl group is defined as 1 positionWhen set as 2 bits, R c1 The bonding position on the phenyl group is preferably 4-position or 5-position, more preferably 5-position. N1 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.
R c2 Is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent. In addition, R c2 In the case of a carbazolyl group which may have a substituent, the nitrogen atom of the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.
R c2 The substituent of the phenyl group or the carbazolyl group is not particularly limited as long as it does not interfere with the object of the present invention. As examples of the preferable substituent which the phenyl group or the carbazolyl group may have on a carbon atom, examples thereof include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a phenylthio 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 having 7 to 20 carbon atoms which may have a substituent, naphthyl which may have a substituent, naphthoyl which may have a substituent, naphthoxycarbonyl which may have a substituent, naphthylalkyl having 11 to 20 carbon atoms which may have a substituent, heterocyclic group which may have a substituent, heterocyclylcarbonyl which may have a substituent, amino substituted with 1 or 2 organic groups, morpholin-1-yl, piperazin-1-yl, halogen, nitro, cyano and the like.
R c2 In the case of a carbazolyl group, as examples of a preferable substituent which can be contained in the carbazolyl group on a nitrogen atom, examples thereof 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 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent,Benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, naphthyl group which may have a substituent, naphthoyl group which may have a substituent, naphthyloxycarbonyl group which may have a substituent, naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, heterocyclic group which may have a substituent, heterocyclic carbonyl group which may have a substituent, and the like. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.
Specific examples of the substituent which may be contained in the phenyl group or the carbazolyl group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenylalkyl group which may be substituted, a naphthylalkyl group which may be substituted, a heterocyclic group which may be substituted, an amino group substituted with 1 or 2 organic groups, and R c1 Likewise, the same is true.
R c2 Examples of the substituent when the phenyl group, the naphthyl group, and the heterocyclic group included in the substituent of the phenyl group or the carbazolyl group further have a substituent include an alkyl group having 1 to 6 carbon atoms; alkoxy having 1 to 6 carbon atoms; saturated aliphatic acyl with 2-7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; saturated aliphatic acyloxy groups having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; benzoyl; a naphthoyl group; benzoyl substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, and phenyl; 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; morpholin-1-yl; piperazin-1-yl; halogen; a nitro group; cyano groups. When the phenyl group, the naphthyl group, and the heterocyclic group included in the substituents of the phenyl group or the carbazolyl group further have substituents, the number of the substituents is not limited within a range that does not hinder the object of the present invention, and is preferably 1 to 4. When the phenyl group, the naphthyl group, and the heterocyclic group have a plurality of substituents, the plurality of substituents may be the same or different.
R c2 Is easily obtained from In view of a polymerization initiator having excellent sensitivity, a group represented by the following formula (c 2) or (c 3) is preferable, a group represented by the following formula (c 2) is more preferable, and a group represented by the following formula (c 2) in which a is S is particularly preferable.
[ chemical formula 27]
(R c4 A is S or O, and n3 is an integer of 0 to 4. )
[ chemical formula 28]
(R c5 And R is c6 Organic groups each having a valence of 1. )
R in formula (c 2) c4 In the case of the organic group, the organic group may be selected from various organic groups within a range that does not hinder the object of the present invention. As R in formula (c 2) c4 Preferable examples of the organic group include an alkyl group having 1 to 6 carbon atoms; alkoxy having 1 to 6 carbon atoms; saturated aliphatic acyl with 2-7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; saturated aliphatic acyloxy groups having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; benzoyl; a naphthoyl group; benzoyl substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, and phenyl; 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; morpholin-1-yl; piperazin-1-yl; halogen; a nitro group; cyano groups.
R c4 Among them, benzoyl is preferable; a naphthoyl group; benzoyl substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, and phenyl; nitro, more preferably benzoyl; a naphthoyl group; 2-methylphenyl carbonyl; 4- (piperazin-1-yl) phenylcarbonyl; 4- (phenyl) benzeneAnd (3) a carbonyl group.
In the formula (c 2), n3 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. When n3 is 1, R c4 The position of the bond is preferably relative to R c4 The chemical bond of the bonded phenyl group to the oxygen atom or sulfur atom is para.
R in formula (c 3) c5 Can be selected from various organic groups within a range that does not hinder the object of the present invention. As R c5 Examples of the preferable group(s) 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 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl 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 naphthyloxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, and the like.
R c5 In these, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.
R in formula (c 3) c6 The organic group is not particularly limited insofar as it does not interfere with the object of the present invention, and may be selected from various organic groups. Regarding R as c6 Specific examples of the preferable group of (a) include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclic group which may have a substituent. In these radicals, R is the radical c6 More preferably a phenyl group which may have a substituent, and particularly preferably a 2-methylphenyl group.
As R c4 、R c5 Or R c6 The substituents when the phenyl group, naphthyl group and heterocyclic group contained in the above-mentioned compound 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 and a saturated lipid having 2 to 7 carbon atomsAliphatic acyloxy, monoalkylamino having an alkyl group having 1 to 6 carbon atoms, dialkylamino having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, halogen, nitro, cyano and the like. R is R c4 、R c5 Or R c6 When the phenyl group, the naphthyl group, and the heterocyclic group included in the compound further have a substituent, the number of the substituents is not limited within a range that does not hinder the object of the present invention, and is preferably 1 to 4.R is R c4 、R c5 Or R c6 When the phenyl group, the naphthyl group, and the heterocyclic group included in (a) have a plurality of substituents, the plurality of substituents may be the same or different.
R in formula (c 1) c3 Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. As R c3 Methyl or ethyl is preferred, and methyl is more preferred.
Among oxime ester compounds represented by the formula (c 1), the following PI-1 to PI-42 are particularly preferable.
[ chemical formula 29]
[ chemical formula 30]
[ chemical formula 31]
[ chemical formula 32]
[ chemical formula 33]
[ chemical formula 34]
Further, as the polymerization initiator (C), an oxime ester compound represented by the following formula (C4) is also preferable.
[ chemical formula 35]
(R c7 Is a hydrogen atom, a nitro group or a 1-valent organic group, R c8 And R is c9 Each is a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, R c8 And R is R c9 Can be bonded to each other to form a ring, R c10 An organic group of valence 1, R c11 Is 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, n4 is an integer of 0 to 4, and n5 is 0 or 1. )
Here, as the oxime compound used for producing the oxime ester compound of the formula (c 4), a compound represented by the following formula (c 5) is preferable.
[ chemical formula 36]
(R c7 、R c8 、R c9 、R c10 N4 and n5 are the same as in formula (c 4). )
In the formulae (c 4) and (c 5), R c7 Is a hydrogen atom, a nitro group or a 1-valent organic group. R is R c7 Bonded to the fluorene ring in formula (c 4) and- (CO) n5 -a six-membered aromatic ring different from the six-membered aromatic ring to which the represented group is bonded. In the formula (c 4), R c7 The bonding position with respect to the fluorene ring is not particularly limited. The compound represented by the formula (c 4) has 1 or more R c7 At the time, fromIn view of easy synthesis of the compound represented by the formula (c 4), 1 or more R are preferable c7 Is bonded to the 2-position in the fluorene ring. R is R c7 When there are a plurality of R c7 May be the same or different.
R c7 When the compound is an organic group, R c7 The organic group is not particularly limited insofar as it does not interfere with the object of the present invention, and may be appropriately selected from various organic groups. As R c7 Examples of the organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl 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 naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl 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, and a piperazin-1-yl group.
R c7 In the case of an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 6. In addition, R c7 When alkyl is used, the alkyl may be straight-chain or branched. As R c7 Specific examples of the 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. In addition, R c7 When alkyl, the alkyl group may contain an ether linkage (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.
R c7 In 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, R c7 When the alkoxy group is a straight chain or branched chain. As R c7 Specific 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, isononyl, n-decyloxy, isodecyloxy and the like. In addition, R c7 In the case of alkoxy groups, the alkoxy groups may contain ether linkages (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, and methoxypropyloxy groups.
R c7 In the case of cycloalkyl or cycloalkoxy, the number of carbon atoms of the cycloalkyl or cycloalkoxy is preferably 3 to 10, more preferably 3 to 6. As R c7 Specific examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. As R c7 Specific examples of the cycloalkoxy group include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy.
R c7 When the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is used, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, more preferably 2 to 7. As R c7 Specific examples of the saturated aliphatic acyl group include acetyl, propionyl, n-butyryl, 2-methylpropanoyl, n-pentanoyl, 2-dimethylpropionyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecanoyl, and n-hexadecanoyl. As R c7 Is saturated aliphatic acyloxySpecific examples of the above-mentioned groups include an acetoxy group, propionyloxy group, n-butyryloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2-dimethylpropionoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, and n-hexadecanoyloxy group.
R c7 In the case of an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 20, more preferably 2 to 7. As R c7 Specific examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyloxycarbonyl.
R c7 In the case of phenylalkyl groups, the number of carbon atoms of the phenylalkyl groups is preferably 7 to 20, more preferably 7 to 10. In addition, R c7 In the case of the naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 to 20, more preferably 11 to 14. As R c7 Specific examples of the phenylalkyl group include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. As R c7 Specific examples of the naphthylalkyl group include an α -naphthylmethyl group, a β -naphthylmethyl group, a 2- (α -naphthyl) ethyl group, and a 2- (β -naphthyl) ethyl group. R is R c7 R in the case of phenylalkyl or naphthylalkyl c7 Further, a substituent may be present on the phenyl group or the naphthyl group.
R c7 In the case of a heterocyclic group, the heterocyclic group is a five-membered or six-membered monocyclic ring containing 1 or more N, S, O, or a heterocyclic group in which the monocyclic rings are condensed with each other or the monocyclic rings are condensed with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings isIs 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle 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. R is R c7 When the heterocyclic group is a heterocyclic group, the heterocyclic group may further have a substituent.
R c7 In the case of a heterocyclylcarbonyl group, the heterocyclic group contained in the heterocyclylcarbonyl group is represented by R c7 The same applies to the case of heterocyclic groups.
R c7 When the amino group is substituted with 1 or 2 organic groups, preferable examples of the organic groups 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. Specific examples of these preferred organic groups and R c7 Likewise, the same is true. 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-pentanoylamino, n-hexanoylamino, n-heptanoylamino, n-octanoylamino, n-decanoylamino, benzoylamino, α -naphthoylamino, β -naphthoylamino and the like.
As R c7 ComprisesExamples of the substituent when the phenyl group, the naphthyl group and the heterocyclic group 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, morpholin-1-yl, piperazin-1-yl, halogen, nitro and cyano groups. R is R c7 When the phenyl group, the naphthyl group, and the heterocyclic group included in the compound further have a substituent, the number of the substituents is not limited within a range that does not hinder the object of the present invention, and is preferably 1 to 4.R is R c7 When the phenyl group, the naphthyl group, and the heterocyclic group included in (a) have a plurality of substituents, the plurality of substituents may be the same or different.
Of the groups described hereinabove, R is the group c7 Is nitro or R c12 The sensitivity tends to be improved when the group represented by-CO-is used, and this is preferable. R is R c12 The organic group is not particularly limited insofar as it does not interfere with the object of the present invention, and may be selected from various organic groups. Regarding R as c12 Examples of the preferable group of (a) include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclic group which may have a substituent. Of these groups, R is c12 Particularly preferred are 2-methylphenyl, thiophen-2-yl and α -naphthyl.
In addition, R c7 In the case of a hydrogen atom, transparency tends to be good, and is preferable. R is as follows c7 Is a hydrogen atom and R c10 When the group represented by the formula (c 4 a) or (c 4 b) is used as described below, transparency tends to be more excellent.
In the formula (c 4), R c8 And R is c9 Each is a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R is R c8 And R is R c9 Can be bonded to each other to form a ring. Of these groups, R is c8 And R is c9 A chain alkyl group which may have a substituent is preferable. R is R c8 And R is c9 To be provided with a takingIn the case of the chain alkyl group of the substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.
R c8 And R is c9 In the case of a chain alkyl group having no substituent, the number of carbon atoms of the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, particularly preferably 1 to 6. As R c8 And R is c9 Specific 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. In addition, R c8 And R is c9 When alkyl, the alkyl group may contain an ether linkage (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.
R c8 And R is c9 In the case of a substituted chain alkyl group, the number of carbon atoms of the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, 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 substituted chain alkyl group is preferably linear.
The substituent that the alkyl group may have is not particularly limited insofar as it does not interfere 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 cycloalkyl, aromatic hydrocarbon, and heterocyclic groups. As a specific example of cycloalkyl, R c7 The same applies to cycloalkyl groups. Specific examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, anthryl, phenanthryl, and the like. As a specific example of the heterocyclic group, R c7 The same applies to the heterocyclic group. R is R c7 In the case of an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may beThe linear or branched chain may be used, and is preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 to 10, more preferably 1 to 6.
When the chain alkyl group has a substituent, the number of substituents is not particularly limited. The number of preferred substituents varies depending on the number of carbon atoms of the chain alkyl group. The number of substituents is typically 1 to 20, preferably 1 to 10, more preferably 1 to 6.
R c8 And R is c9 When the cyclic organic group is an alicyclic group, the cyclic organic group may be an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group. R is R c8 And R is c9 In the case of a cyclic organic group, the cyclic organic group may have a substituent and R c8 And R is c9 The same applies to the case of a chain alkyl group.
R c8 And R is c9 When the aromatic hydrocarbon group is used, the aromatic hydrocarbon group is preferably: phenyl, a group formed by bonding a plurality of benzene rings through carbon-carbon bonds, or a group formed by fusing a plurality of benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or fusing a plurality of benzene rings, the number of rings of the benzene ring contained in the aromatic hydrocarbon group is not particularly limited, and is preferably 3 or less, more preferably 2 or less, and particularly preferably 1. Preferred examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, anthryl, phenanthryl and the like.
R c8 And R is c9 In the case of the aliphatic cyclic hydrocarbon group, the aliphatic cyclic hydrocarbon group may be a single ring or multiple rings. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 to 20, 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 groups.
R c8 And R is c9 In the case of a heterocyclic group, the heterocyclic group is a five-membered or six-membered monocyclic ring containing 1 or more N, S, O, or the monocyclic rings are condensed with each other, orAnd a heterocyclic group formed by fusing the monocyclic ring and the benzene ring. When the heterocyclic group is a condensed ring, the number of rings is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle 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.
R c8 And R is R c9 Can be bonded to each other to form a ring. From R c8 And R is R c9 The group formed by the ring is preferably a cycloalkylene (cyclylalkylidene). R is R c8 And R is R c9 When the cycloalkylene group is formed by bonding, the ring constituting the cycloalkylene group is preferably a five-membered ring to a six-membered ring, more preferably a five-membered ring.
R c8 And R is R c9 When the group formed by bonding is a cycloalkylene group, the cycloalkylene group may be condensed with 1 or more other rings. Examples of the ring which can be condensed with the cycloalkylene 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, and a pyrimidine ring.
R as described hereinabove c8 And R is c9 Examples of the preferable group include the formula-A 1 -A 2 A group represented by the formula (I). In the formula, there may be mentioned: a is that 1 Is a linear alkylene group, A 2 Is an alkoxy group, a cyano group, a halogen atom, a haloalkyl group, a cyclic organic group, or an alkoxycarbonyl group.
A 1 The number of carbon atoms of the linear alkylene group is preferably 1 to 10, more preferably 1 to 6.A is that 2 In 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 to 10, more preferably 1 to 6.A is that 2 When the halogen atom is a halogen atom, it is preferable thatThe fluorine atom, chlorine atom, bromine atom, or iodine atom is more preferably a fluorine atom, chlorine atom, or bromine atom. A is that 2 In 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, 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 is that 2 In the case of a cyclic organic group, examples of cyclic organic groups and R c8 And R is c9 The cyclic organic group which is provided as a substituent is the same. A is that 2 In the case of alkoxycarbonyl, examples of alkoxycarbonyl and R c8 And R is c9 The same applies to alkoxycarbonyl groups which are substituted.
As R c8 And R is c9 Specific examples of the preferable groups include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl; alkoxyalkyl groups such as 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-pentyl, 6-ethoxy-n-hexyl, 7-ethoxy-n-heptyl, and 8-ethoxy-n-octyl; cyanoalkyl groups such as 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n-pentyl group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group, and 8-cyano-n-octyl group; 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 group, 3-cyclohexyln-propyl group, 4-cyclohexyln-butyl group, 5-cyclohexyln-pentyl group, 6-cyclohexyln-hexyl group, 7-cyclohexyln-heptyl group, 8-cyclohexyln-octyl group, 2-cyclopentylethyl group, 3-cyclopentylethyl group, 4-cyclopentylen-butyl group, 5-cyclopentylen-pentyl group, 6-cyclopentylen-hexyl group, 7-cyclopentylen-heptyl group, and 8-cyclopentylen-octyl group; 2-methoxycarbonylethyl, 3-methoxycarbonyln-propyl, 4-methoxycarbonyln-butyl, 5-methoxycarbonyln-pentyl, 6-methoxycarbonyln-hexyl, 7-methoxycarbonyln-heptyl, 8-methoxycarbonyln-octyl, 2-ethoxycarbonylethyl, Alkoxycarbonylalkyl groups such as 3-ethoxycarbonyl n-propyl, 4-ethoxycarbonyl n-butyl, 5-ethoxycarbonyl n-pentyl, 6-ethoxycarbonyl n-hexyl, 7-ethoxycarbonyl n-heptyl, and 8-ethoxycarbonyl n-octyl; 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 haloalkyl such as 3, 3-trifluoropropyl, 3,4, 5-heptafluoro-n-pentyl, and the like.
As R c8 And R is c9 Preferred groups in the above are ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl 2-cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl 2-bromoethyl, 3-trifluoropropyl and 3,4, 5-heptafluoro-n-pentyl.
As R c10 Examples of preferred organic radicals of (2) are as follows c7 Similarly, examples thereof include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy 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 naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl 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 R c7 And the same is said. In addition, as R c10 Cycloalkyl alkyl, phenoxyalkyl which may have a substituent on the aromatic ring, and phenylthioalkyl which may have a substituent on the aromatic ring are also preferable. Phenoxyalkyl, phenylthioalkyl and R may have a substituent c7 ComprisesThe same substituents as those which the phenyl group of (a) may have.
In the organic radical, R is c10 Preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, a phenylthioalkyl group which may have a substituent on an 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 phenyl groups which may have a substituent, methylphenyl is preferable, and 2-methylphenyl is more preferable. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 to 8, more preferably 1 to 4, 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 to 8, more preferably 1 to 4, particularly preferably 2. Among phenylthioalkyl groups which may have a substituent on the aromatic ring, 2- (4-chlorophenylthio) ethyl is preferable.
In addition, as R c10 Also preferred is-A 3 -CO-O-A 4 A group represented by the formula (I). A is that 3 An organic group having a valence of 2, preferably a hydrocarbon group having a valence of 2, preferably an alkylene group. A is that 4 Is a 1-valent organic group, preferably a 1-valent hydrocarbon group.
A 3 In the case of an alkylene group, the alkylene group may be linear or branched, and is preferably linear. A is that 3 In the case of an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, particularly preferably 1 to 4.
As A 4 Preferable examples of (a) 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 A 4 Preferable examples of (a) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, phenyl, naphthyl, benzyl, phenethyl, a-naphthylmethyl, and β -naphthylmethyl.
as-A 3 -CO-O-A 4 Representation ofPreferable specific examples of the group of (a) include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonyl ethyl group, 2-n-butyloxycarbonyl ethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonyl ethyl group, 2-benzyloxycarbonyl ethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl n-propyl group, 3-ethoxycarbonyl n-propyl group, 3-n-propyloxycarbonyl n-propyl group, 3-n-butyloxycarbonyl n-propyl group, 3-n-pentyloxycarbonyln-propyl group, 3-n-hexyloxycarbonyl n-propyl group, 3-benzyloxycarbonyl n-propyl group, 3-phenoxycarbonyl n-propyl group and the like.
Above, for R c10 The description was given, but as R c10 The group represented by the following formula (c 4 a) or (c 4 b) is preferable.
[ chemical formula 37]
(in the formulae (c 4 a) and (c 4 b), R c13 And R is c14 Respectively organic groups, n6 is an integer of 0 to 4, R c13 And R is 8 When present at adjacent positions on the benzene ring, R c13 And R is R c14 Can be bonded to each other to form a ring, n7 is an integer of 1 to 8, n8 is an integer of 1 to 5, n9 is an integer of 0 to (n8+3), R c15 Is an organic group. )
R in formula (c 4 a) c13 And R is c14 Examples of organic radicals of (2) and R c7 Likewise, the same is true. As R c13 Alkyl or phenyl groups are preferred. R is R c13 In the case of an alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. I.e. most preferably R c13 Is methyl. R is R c13 And R is R c14 When bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. As R c13 And R is R c14 Preferred examples of the group represented by the formula (c 4 a) in the formation of the ring include naphthalen-1-yl and 1,2,3, 4-tetrahydronaphthalen-5-yl. In the above formula (c 4 a), n6 is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.
In the above formula (c 4 b), R c15 Is an organic group. Examples of the organic group include R c7 And the organic groups described are the same. Among the organic groups, alkyl groups are preferred. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3. As R c15 The methyl group, ethyl group, propyl group, isopropyl group, butyl group and the like are preferable, and among these, methyl group is more preferable.
In the above formula (c 4 b), n8 is an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2. In the above formula (c 4 b), n9 is 0 to (n8+3), preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0. In the above formula (c 4 b), n7 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.
In the formula (c 4), R c11 Is 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 R c11 Examples of the "substituent" which may be included in the alkyl group include preferably a phenyl group and a naphthyl group. In addition, as R c7 Examples of the "substituent" which may be included in the aryl group may include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.
In the formula (c 4), R is c11 The 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 are preferable, and among these, methyl group and phenyl group are more preferable.
The compound represented by the formula (c 4) can be produced by a method comprising the steps of: converting an oxime group (> c=n-OH) contained in the aforementioned compound represented by formula (C5) to > c=n-O-COR c11 Represented oxime ester group. R is R c11 And R in formula (c 4) c11 Likewise, the same is true.
Oximido (> c=n-OH) to > c=n-O-COR c11 The conversion of the oxime ester group represented by the formula (c 5) may be carried out by reacting the compound represented by the formula with an acylating agent.
As providing-COR c11 Examples of the acylating agent for the acyl group include (R c11 CO) 2 Anhydride represented by O, R c11 COHal (Hal is a halogen atom) is an acyl halide.
Preferable specific examples of the compound represented by the formula (c 4) include PI-43 to PI-83 described below.
[ chemical formula 38]
[ chemical formula 39]
The content of the polymerization initiator (C) is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, based on the total mass of the solid components of the polymerizable composition. When the content of the polymerization initiator (C) is within the above range, a polymerizable composition which is less likely to cause pattern defects can be obtained.
In addition, the polymerization initiator (C) may be combined with a photoinitiating auxiliary. Examples of the photoinitiating auxiliary include thiol compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N-dimethyl-p-toluidine, 4' -bis (dimethylamino) benzophenone, 9, 10-dimethoxyanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 2-ethyl-9, 10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, pentaerythritol tetramercaptoacetate and 3-mercaptopropionate. These photoinitiating aids may be used alone or in combination of 2 or more.
< Filler (D) >)
The polymerizable composition contains a filler (D). The filler (D) contains 1 or more selected from the group consisting of an inorganic filler (D1) and an alkaline filler (D2). The inorganic filler (D1) and the alkaline filler (D2) will be described in detail later.
Since the polymerizable composition contains the silsesquioxane resin (a) satisfying the above-described predetermined conditions, even when the inorganic filler (D1) and the alkaline filler (D2) are contained, generation of residues in the unexposed portions can be suppressed after development in patterning by photolithography.
[ inorganic filler (D1) ]
The inorganic filler (D1) is 1 or more selected from the group consisting of simple substances of at least 1 element selected from the group consisting of La, ce, nd, gd, ho, lu, hf and Ta, oxides of the foregoing elements, chelates of the foregoing elements, salts of the foregoing elements, and alloys of the foregoing elements.
The electron density of the above elements is high. Therefore, the dielectric constants of the simple substance of the element, the oxide of the element, the chelate of the element, the salt of the element, and the alloy of the element are high. In addition, the simple substance of the element, the oxide of the element, the chelate compound of the element, the salt of the element, and the alloy of the element are dispersed in a matrix constituting the film in the film formed by using the polymerizable composition, and thus the film is not likely to block the transmission of visible light.
Therefore, a film formed using the polymerizable composition containing the inorganic filler (D1) tends to have a high dielectric constant and excellent transparency, and can be suitably used as a transparent insulating film. The simple substance of the above elements, the oxide of the above elements, the chelate of the above elements, the salt of the above elements, and the alloy of the above elements may be used singly or in combination of 2 or more kinds.
The atomic valence of the above element contained in the oxide of the above element is not particularly limited.
Among the chelates of the above elements, as ligands forming a chelate with the above elements, pyridine, triphenylphosphine, carbon monoxide, ethylenediamine, bipyridine, catechol, ethylenediamine tetraacetic acid (EDTA), and the like can be mentioned.
The salt of the above element may be a salt of an inorganic acid or a salt of an organic acid. Preferred salts include halides, sulfates, nitrates, phosphates, acetates, formates, propionates, benzoates, and the like. The atomic valence of the above elements constituting the salt is not particularly limited.
The combination of metals (elements) contained in the alloy of the above elements is not particularly limited. In addition, the mixing ratio of the plurality of metals (elements) contained in the alloy is also not particularly limited.
Among the simple substance of the element, the oxide of the element, the chelate of the element, the salt of the element, and the alloy of the element, the oxide is preferable in that the composition is stable and a film excellent in transparency is easily formed using the polymerizable composition. As a preferable specific example of the oxide of the above element, la is given 2 O 3 、CeO 2 、Nd 2 O 3 、Gd 2 O 3 、Ho 2 O 3 、Lu 2 O 3 、HfO 2 Ta, ta 2 O 5 。
The shape of the inorganic filler (D1) is not particularly limited. The average particle diameter of the inorganic filler (D1) is preferably 200nm or less, more preferably 150nm or less, particularly preferably 100nm or less. When the average particle diameter of the inorganic filler (D1) is 200nm or less, the inorganic filler (D1) is less likely to precipitate in the dispersion, and a liquid polymerizable composition can be easily obtained. The lower limit of the average particle diameter of the inorganic filler (D1) is not particularly limited, but is preferably 40nm or more, more preferably 45nm or more. When the average particle diameter of the inorganic filler (D1) is 40nm or more, the surface of the inorganic filler (D1) is easily coated, and the film obtained by using the polymerizable composition is less likely to have a low dielectric constant and less likely to cause leakage current, and the inorganic filler (D1) is less likely to aggregate.
In the present specification, the average particle diameter refers to a volume average particle diameter measured by a dynamic light scattering measurement (DLS).
The content of the inorganic filler (D1) in the polymerizable composition is not particularly limited within a range that does not hinder the object of the present invention. The content of the inorganic filler (D1) in the polymerizable composition is typically 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, and particularly preferably 15 to 40 parts by mass, relative to 100 parts by mass of the silicone-containing resin (a).
[ alkaline Filler (D2) ]
The basic filler (D2) is at least one selected from the group consisting of basic fillers and basic polymers.
The basic filler and the basic polymer will be described in order.
(alkaline Filler)
The alkaline filler is a powdery, plate-like or short-fiber filler formed of a material whose surface is alkaline. The alkaline filler may be an organic filler or an inorganic filler. The shape of the alkaline filler is not particularly limited, and may be in the form of powder, plate, or staple fiber.
The size of the alkaline filler is not particularly limited within a range that does not hinder the object of the present invention, and may be appropriately selected according to the target pattern size or the like. In the case of spherical shape, the average diameter of the basic filler is preferably 1nm to 1500nm, more preferably 2 to 800nm, and even more preferably 10nm to 100nm. In the case of a plate-like or short fiber-like form, the average length is preferably 5nm to 1500nm, more preferably 10nm to 100nm. In the case of the fibrous form, the average length-diameter-to-short diameter ratio (L1/L2), which is the ratio of the average filler length (L1) to the average cross-sectional diameter (L2) of the filler, is not particularly limited, but is preferably 1.5 to 1000, more preferably 2 to 100.
Examples of the basic filler include basic metal carbonate, basic metal hydroxide, talc, mica, cement (segment) powder, basic activated alumina, hydrotalcite, and powder of a basic polymer described later. Examples of the basic metal carbonate include calcium carbonate and magnesium carbonate. Examples of the basic metal hydroxide include aluminum hydroxide and magnesium hydroxide.
The alkaline filler may be a filler whose surface is coated with an alkaline material or a filler whose surface is coated with an alkaline material. The surface of the filler treated with the alkaline material is not particularly limited in nature, and may be acidic, alkaline, or neutral.
Examples of the filler treated with the alkaline material include powders of metal oxides such as silica, alumina, zirconia, mullite, spinel, and zinc oxide; powder of metal hydroxide such as aluminum hydroxide and magnesium hydroxide; powders of metal carbonates such as calcium carbonate and magnesium carbonate; platy or short fibrous fillers such as mica, talc, glass short fibers, carbon short fibers, potassium titanate whiskers, barium titanate whiskers, aluminum borate whiskers, titanium oxide whiskers, calcium carbonate whiskers, and the like; a powder of an organic resin; and powders of metal particles such as iron, cobalt, nickel, copper, palladium, silver, tin, platinum, and gold.
Examples of the basic material that can be used for the surface treatment of the filler include ammonia, organic amines, silane coupling agents containing a nitrogen-containing basic group, basic nitrogen-containing cyclic compounds, and the like. Among these, the silane coupling agent containing a nitrogen-containing basic group is preferable because it is easily chemically bonded to the surface of the inorganic filler. Preferable examples of the silane coupling agent include N-phenyl- γ -aminopropyl trimethoxysilane and γ -aminopropyl triethoxysilane.
The treatment of the filler with the alkaline material may be a coating treatment with an alkaline polymer, a resin mixture containing an alkaline polymer, or the like, which will be described later. For example, a method of synthesizing metal particles stabilized with a lower ammonium ligand to some extent and then exchanging the ligand with a basic polymer, or a method of directly reducing metal ions of the metal in a solution of a basic polymer having an ammonium group to form a complex in which the basic polymer is attached to or coordinated to the metal particles, may be used. In addition, a powder obtained by granulating a homogeneous composition containing an alkaline polymer and a filler by a method such as pulverization may also be used as the alkaline filler.
(alkaline Polymer)
As the basic polymer, various conventionally known basic polymers can be used. Preferable examples of the basic polymer include polypyrrole, polyaniline, and polyaniline vinylene, and derivatives of these resins.
As the basic polymer, it is also preferable that: homopolymers or copolymers of monomers having an unsaturated bond, which contain a structural unit derived from a basic unsaturated monomer such as (meth) acrylate having a basic functional group such as dimethylaminoethyl group, diethylaminoethyl group, di-N-butylaminoethyl group, and N-ethyl-N-phenylaminoethyl group, vinylpyridine, vinylpyrrolidine, vinylpiperidine, N-vinylpyrrolidine, N-vinylcarbazole, N-vinylindole, and N-vinyllactam (N-vinylpyrrolidinone, etc.).
As such basic homo-or copolymer, acrylic resins, styrene acrylic resins, and the like are preferable.
The basic polymer may be a resin having a basic carboxylic acid base such as an alkali metal salt of a carboxylic acid. Examples of such resins include resins containing structural units derived from unsaturated carboxylic acids such as (meth) acrylic acid, and resins obtained by converting the carboxyl groups of the side chains of resins containing vinyl acetate units into basic carboxylic acid bases.
The basic polymer is not limited to a polymer having a linear main chain. As the basic polymer, a network polymer, a polymer having a so-called dendrimer (dendrimer) structure branched into a tree shape can also be used. When the basic polymer has a dendritic polymer structure, the basic functional group is preferably present in the outermost layer of the polymer.
Preferable examples of the polymer having a dendritic polymer structure include a polymer represented by the following formula (d 1).
[ chemical formula 40]
Wherein R is d1 Each independently represents a hydrogen atom or a methyl group. R is R d2 And R is d3 Each independently is a basic group or an organic group having a basic group at the end. t is an integer of 2 to 100000.
In the formula (d 1), A d1 Is a 2-valent group represented by the following formula (d 2).
[ chemical formula 41]
In the formula (d 2), A d2 Represents an alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond. In addition, Y d1 、Y d2 、Y d3 And Y d4 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxyl group, an amino group, a carboxyl group, or a cyano group.
In the formula (d 1), R is d2 And R is d3 Examples of the basic group included in (a) include basic heterocyclic groups such as ammonium salt groups and pyridyl groups, amino groups substituted with 1 or 2 organic groups, and the like.
As the ammonium salt group, preference is given to-N + R d4 R d5 R d6 ·Z - A group represented by the formula (I). R is R d4 、R d5 And R is d6 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or- (CH) 2 CH 2 O)u-R d7 A group represented by the formula (I). U is an integer of 2 to 100, R d7 Is a hydrogen atom or a methyl group. R is R d4 、R d5 And R d6 Any two of them may be bonded to each other to form a ring.
Z - Is an anion, preferably halogen atom, PF 6 - 、BF 4 - Or perfluoroalkanesulfonates.
As the amino group substituted with 1 or 2 organic groups, an alkylamino group or a dialkylamino group is preferable. The alkyl group contained in the alkylamino group or the dialkylamino group is preferably an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms.
As a solvent for the carbon atom or A d1 And R is R d2 Or R is d3 Examples of the group to which the basic group included in (a) is bonded include an alkylene group having 1 to 30 carbon atoms which may include an ether bond or an ester bond, -O-CO, -S-CS-, and the like. It should be noted thatIs, the chemical bond marked with is R d2 Or R is d3 A chemical bond to which a basic group contained in the polymer is bonded.
As A in the formula (d 1) d1 The following 2-valent group is preferable.
[ chemical formula 42]
That is, as the compound represented by the formula (d 1), a compound represented by the following formula (d 3) is preferable.
[ chemical formula 43]
In the above formula (d 3), R is d1 、R d2 、R d3 And t is the same as formula (d 1).
The basic polymer may be uniformly dissolved in the polymerizable composition or may be uniformly dispersed in the polymerizable composition.
The content of the basic filler (D2) in the polymerizable composition is not particularly limited within a range that does not hinder the object of the present invention. The content of the basic filler (D2) in the polymerizable composition is typically 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and particularly preferably 2 to 10 parts by mass, relative to 100 parts by mass of the silicone-containing resin (a). The content of the polymer is preferably 1 to 30% by mass, more preferably 1.5 to 25% by mass, based on the total solid content in the polymerizable composition.
< organic solvent (S) >)
For the purpose of adjusting the coatability, dispersing the filler (D), and the like, it is generally preferable for the polymerizable composition to contain (S) an organic solvent. The organic solvent (S) is not particularly limited, and organic solvents conventionally blended in various photosensitive compositions can be used.
Preferred examples of the organic solvent (S) include (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene 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, tripropylene glycol monoethyl ether, and the like; (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 (PGMEA), 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, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl 2-oxobutyrate and other esters; aromatic hydrocarbons such as toluene and xylene.
In addition, the organic solvent (S) may include a nitrogen-containing organic solvent. In particular, when the polymerizable composition contains the basic filler (D2), the organic solvent (S) preferably contains a nitrogen-containing organic solvent.
In this case, aggregation and dispersion failure of the basic filler and/or the basic polymer in the polymerizable composition can be suppressed, and thus a film having a smooth cross section and a smooth surface can be easily formed using the polymerizable composition.
The nitrogen-containing organic solvent may contain a nitrogen atom, and may be a polar solvent or a nonpolar solvent. As the nitrogen-containing organic solvent, a nitrogen-containing polar organic solvent is preferable.
Examples of the nitrogen-containing polar organic solvent include amides such as N, N-dimethylacetamide, N-dimethylformamide, N-diethylacetamide, and N, N-diethylformamide; heterocyclic polar organic solvents such as 1, 3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, N-ethylpyrrolidone, and gamma-butyrolactone. The nitrogen-containing organic solvent and the nitrogen-containing polar organic solvent are not limited to these examples. In addition, 2 or more nitrogen-containing organic solvents may be used in combination.
As the nitrogen-containing polar organic solvent, a compound represented by the following formula (S1) is preferable.
[ chemical formula 44]
(in the formula (S1), R s1 And R is s2 Each independently is an alkyl group having 1 to 3 carbon atoms, R s3 Is a group represented by the following formula (S1-1) or the following formula (S1-2).
[ chemical formula 45]
In the formula (S1-1), R s4 Is a hydrogen atom or a hydroxy group, R s5 And R is s6 Each independently represents an alkyl group having 1 to 3 carbon atoms. In the formula (S1-2), R s7 And R is s8 Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. )
R in the compound represented by the formula (S1) s3 Specific examples of the group represented by the formula (S1-1) include N, N, 2-trimethylpropionamide, N-ethyl-N, 2-dimethylpropionamide, N-diethyl-2-methylpropionamide, N,n, 2-trimethyl-2-hydroxy-propionamide, N-ethyl-N, 2-dimethyl-2-hydroxy-propionamide, N-diethyl-2-hydroxy-2-methylpropionamide, and the like.
R in the compound represented by the formula (S1) s3 Specific examples of the group represented by the formula (S1-2) include N, N, N ', N' -tetramethylurea, N, N, N ', N' -tetraethylurea, and the like.
Among the compounds represented by the formula (S1), N, 2-trimethylpropionamide and N, N' -tetramethylurea are particularly preferable from the viewpoint of not only favorably dissolving various materials but also easily inhibiting aggregation of the basic filler and/or the basic polymer in the polymerizable composition.
The content of the nitrogen-containing organic solvent in the organic solvent (S) is, for example, 5 to 100% by mass, and when the filler (D) contains the basic filler (D2), it is preferably 50 to 100% by mass, more preferably 60 to 90% by mass.
Further, as the solvent, at least 1 solvent selected from a terpene compound having at least 1 group selected from the group consisting of a hydroxyl group and an acetoxy group, and an acetate compound having a cyclic skeleton (wherein the above terpene compound is not included) may be used.
(terpene compound having at least 1 group selected from the group consisting of hydroxyl group and acetoxy group)
As the terpene compound having at least 1 group selected from the group consisting of a hydroxyl group and an acetoxy group, terpineol (terpineol), dihydroterpineol, 4- (acetoxy) - α, α, 4-trimethylcyclohexane methanol acetate, 2- [ 1-methyl-1- (4-methyl-3-cyclohexen-1-yl) ethoxy ] ethanol, and the like can be preferably given.
For terpineol, the following alpha-, beta-, gamma-isomers exist, and are commercially available from Japanese perfumery, inc., nippon Terpene Chemicals, inc.
[ chemical formula 46]
In addition, 2 compounds (1-hydroxy-p-terpineol and 8-hydroxy-p-terpineol) below exist for dihydroterpineol, which are commercially available from Nippon Terpene Chemicals, inc.
[ chemical formula 47]
4- (Acetyloxy) - α, α, 4-trimethylcyclohexane methanol acetate is a compound represented by the following formula C-3, and is commercially available as a mixture of a compound represented by the formula C-1 and a compound represented by the formula C-2, for example, from Nippon Terpene Chemicals, inc. as Terorb THA-90, terorb THA-70.
[ chemical formula 48]
2- [ 1-methyl-1- (4-methyl-3-cyclohexen-1-yl) ethoxy ] ethanol is a compound represented by the following formula, for example, commercially available as terorb TOE-100 from Nippon Terpene Chemicals, inc.
[ chemical formula 49]
Among these, terpineol, dihydroterpineol, tersporb THA-90, tersporb THA-70, tersporb TOE-100 are preferred, dihydroterpineol, tersporb THA-90, tersporb THA-70 are more preferred, and Tersporb THA-90, tersporb THA-70 are still more preferred.
The terpene compound may be used alone or in combination of 2 or more kinds.
(acetate Compound having a Cyclic skeleton)
The cyclic skeleton-containing acetate compound (excluding the terpene compound) is not particularly limited as long as it is an acetate solvent having a cyclic skeleton that does not impair the effect of the present invention, and is preferably a cycloalkyl acetate represented by the following formula (S1).
[ chemical formula 50]
(in the formula (S1), R s1 Each independently is an alkyl group, p is an integer of 1 to 6, and q is an integer of 0 to (p+1). )
As R s1 The alkyl group represented by the formula (I) may be an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl and isopropyl.
Specific examples of the cyclic alkyl acetate represented by the formula (S1) include cyclopropyl acetate, cyclobutyl acetate, cyclopentyl acetate, cyclohexyl acetate, cycloheptyl acetate and cyclooctyl acetate.
Among these, from the viewpoint of easiness of obtaining, the cyclooctyl acetate is preferable.
The above-mentioned acetate compound having a cyclic skeleton may be used alone or in combination of 2 or more.
The content of the organic solvent (S) is not particularly limited, and may be appropriately set according to the film thickness of the film formed from the polymerizable composition, and the like. Typically, the organic solvent (S) may be used in an amount such that the solid content concentration of the polymerizable composition is 1 to 50 mass%, preferably 5 to 30 mass%.
< other Components >)
The polymerizable composition may contain, in addition to the above-described components, additives such as a surfactant, a photobase generator, a photoacid generator, an adhesion improver, a colorant, a thermal polymerization inhibitor, a defoaming agent, and a curing accelerator, as required. All additives can be used as known in the art. Examples of the surfactant include anionic, cationic, nonionic, and other compounds. Examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether. Examples of the defoaming agent include silicone-based and fluorine-based compounds.
Process for producing polymerizable composition
The method for producing the polymerizable composition is not particularly limited as long as the predetermined components can be uniformly mixed. For example, the polymerizable composition can be prepared by mixing (dispersing and kneading) the above components by a mixer such as a three-roll mill, a ball mill, or a sand mill, and filtering the mixture, if necessary, with a filter such as a 5 μm membrane filter.
Method for producing cured film
The method for producing the cured film is not particularly limited as long as the film formed from the polymerizable composition can be cured. Typically, it is preferred to produce a patterned cured film.
Specific examples of the preferred method include the following steps:
a step of forming a coating film on a substrate using the aforementioned polymerizable composition,
a step of positionally selectively exposing the coating film, and
and developing the exposed coating film.
The base material is not particularly limited, and various substrates such as a glass substrate and a silicon substrate can be used without particular limitation.
For example, when the polymerizable composition contains the inorganic filler (D1), a transparent conductive film substrate such as an ITO film substrate can be preferably used as the base material.
Examples of the method of applying the polymerizable composition to the substrate include a method using a contact transfer type coating apparatus such as a roll coater, a reverse coater, a bar coater, or a slit coater, a spin coater (spin coater), or a curtain coater (curtain flow coater), or a non-contact type coating apparatus.
The applied polymerizable composition is dried as needed to form a coating film. The drying method is not particularly limited, and for example, the following methods are exemplified: (1) Drying at 80-120 deg.c, preferably 90-100 deg.c, with heating plate for 60-120 sec; (2) a method of standing at room temperature for several hours to several days; (3) A method of removing the solvent by placing the mixture in a hot air heater or an infrared heater for several tens of minutes to several hours; etc.
Next, the coating film is exposed to light. The exposure can be performed by irradiation with active energy rays such as ultraviolet rays and excimer laser light. The exposure may be performed by, for example, a method of performing exposure through a negative mask, or the like. The amount of the energy ray to be irradiated varies depending on the composition of the polymerizable composition, and is preferably 40 to 300mJ/cm 2 Left and right.
After exposing the coating film to light, the coating film is developed with a developer to form a pattern having a desired shape. The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. The developer may be appropriately selected according to the composition of the polymerizable composition. As the developer, an aqueous alkali solution can be preferably used. The aqueous alkali may be an aqueous solution of an inorganic base or an aqueous solution of an organic base. The developer is preferably an aqueous alkaline solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, or a quaternary ammonium salt, and particularly preferably an aqueous solution of tetramethylammonium hydroxide.
The patterned cured film after development is preferably heated (baked). The baking temperature is not particularly limited as long as the patterned cured film is not thermally decomposed or excessively deformed, and is preferably 180 to 280 ℃, more preferably 190 to 260 ℃.
By the above operation, a cured film of the polymerizable composition having a pattern formed in a desired shape can be obtained.
Since the above-described polymerizable composition is used for the cured film obtained by the above-described method, residues are less likely to be generated in the unexposed portions when the cured film is developed with an aqueous alkali solution.
Transparent insulating film and display device
In particular, when a polymerizable composition containing an inorganic filler (D1) is used, a transparent insulating film can be formed by the above method. In addition, since the transparent insulating film formed in the above manner is excellent in transparency and has a high dielectric constant, it can be suitably used in manufacturing various display devices. Because of these advantages, the transparent insulating film formed in the above manner is expected to be a substitute material for a transparent insulating film made of silicon nitride, which has been conventionally used in display devices such as liquid crystal displays.
Examples
Hereinafter, the present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
[ preparation example 1 ]
First, 235g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110mg of tetramethyl ammonium chloride, 100mg of 2, 6-di-t-butyl-4-methylphenol, and 72.0g of acrylic acid were placed in a four-necked flask having a capacity of 500mL, and air was blown thereinto at a rate of 25 mL/min, followed by dissolution by heating at 90℃to 100 ℃. Then, the temperature was gradually raised to 120℃in a state where the solution was cloudy, and the solution was completely dissolved. Here, the solution gradually became transparent and viscous, and stirring was continued while maintaining this state. During which the acid value was measured, and stirring was continued with heating until the acid value became lower than 1.0mgKOH/g. It took 12 hours for the acid value to reach the target. And then cooling to room temperature to obtain bisphenol fluorene type epoxy acrylate.
Then, 600g of 3-methoxybutyl acetate was added to 307.0g of the bisphenol fluorene type epoxy acrylate obtained in the above-described manner, and dissolved, followed by mixing 80.5g of benzophenone tetracarboxylic dianhydride and 1g of tetraethylammonium bromide, and then slowly heating the mixture to perform a reaction at 110℃to 115℃for 4 hours. After confirming the disappearance of the acid anhydride, 38.0g of 1,2,3, 6-tetrahydrophthalic anhydride was mixed and reacted at 90℃for 6 hours to give resin 4 (mass average molecular weight: 3400) having a Cardo structure. The disappearance of the anhydride was confirmed by IR spectroscopy.
[ examples 1 to 4 and comparative examples 1 to 5 ]
In examples 1 to 4, the following silsesquioxane resin 1 was used as the alkali-soluble resin.
Silsesquioxane resin 1: a silsesquioxane resin comprising 2- (3- (triethoxysilylpropyl) carbamoyl) cyclohexanecarboxylic acid (40 mol%), 3- (trimethoxysilyl) propyl methacrylate (40 mol%), and phenyltrimethoxysilane (20 mol%) as monomer components.
In comparative examples 1 to 4, as the alkali-soluble resin, resin 2, which is an acrylic resin formed of structural units I to IV represented by the following formulas and whose amount of each structural unit is a value (mass%) below right of brackets of each unit, was used.
In comparative example 5, resin 4, which is the resin having the Cardo structure obtained in preparation example 1, was used as the alkali-soluble resin.
[ chemical formula 51]
In examples 1 to 3 and comparative examples 1 to 3, ceO was used as the inorganic filler 2 (average particle diameter 50 nm).
In example 4, comparative example 4 and comparative example 5, basic alumina fine particles (average particle diameter: 700 nm) were used as the basic filler.
In examples and comparative examples, dipentaerythritol hexaacrylate (DPHA) was used as the polyfunctional polymerizable monomer.
In examples and comparative examples, the following compounds were used as polymerization initiators.
[ chemical formula 52]
In examples 1 to 3 and comparative examples 1 to 3, the materials in the amounts shown in table 3 were uniformly mixed with PGMEA so that the solid content concentration became 12 mass%, and in examples 4, comparative example 4, and comparative example 5, the materials in the amounts shown in table 3 were uniformly mixed with a mixed solvent of N, N' -tetramethylurea and PGMEA (mass ratio 80:20) so that the solid content concentration became 16 mass%, respectively, to obtain polymerizable compositions of examples 1 to 4 and comparative examples 1 to 5.
The following evaluation was performed using the obtained polymerizable composition. The evaluation results are shown in Table 3.
[ evaluation of unexposed portion residue and leakage Current ]
The polymerizable compositions of examples and comparative examples were applied to a glass substrate using a spin coater, and then baked at 90℃for 120 seconds to obtain a coating film having a film thickness of 1. Mu.m.
The resulting coating film was subjected to a mask capable of forming a line pattern having a line width of 3. Mu.m, and was subjected to a mask treatment at a rate of 30mJ/cm in examples 1 to 3 and comparative examples 1 to 3 2 Exposure was performed at 300mJ/cm in example 4, comparative example 4, and comparative example 5 2 Exposure is performed by the exposure amount of (2).
The exposed coating film was developed using an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.38 mass% at a temperature of 23 ℃.
The developed coating film was baked at 230℃for 20 minutes to obtain a cured film having a linear pattern.
The unexposed portions (non-pattern portions) were observed under a microscope, and residues of the unexposed portions were evaluated. The case where almost no residue was confirmed after development was judged as o, and the case where residue was confirmed after development was judged as x.
In addition, the leakage current was measured by a dielectric constant measuring device SSM495 (manufactured by japan SSM). The leakage current was judged to be equal to or less than 1.0XE-8, and the leakage current was judged to be equal to or less than 1.0XE-9. The leakage current value exceeding 1.0XE-8 was judged as X.
The residue from the inorganic filler or the alkaline filler is one of the causes of the increase in the leakage current value.
< evaluation of gas production >
The polymerizable composition was coated on a 10cm×10cm glass substrate, and then dried at 90 ℃ for 120 seconds to form a coating film.
Next, the exposure apparatus using a high-pressure mercury lamp was used at a rate of 50mJ/cm 2 The coating film is subjected to full-face exposure.
The exposed coating film was post-baked at 230℃for 30 minutes to obtain a cured film having a film thickness of 2. Mu.m.
The amount of generated gas was evaluated by gas chromatography mass spectrometry (P & T-GC/MS) equipped with a purge-trap sampler (thermal desorption apparatus) using the formed cured film as a sample. The measurement and the quantification of the gas were performed according to the following steps (i) to (iii).
(i) Gas generation and trapping to a secondary adsorption tube
A primary trapping tube was filled with 1mg of a cured film, and heated at 230℃for 10 minutes using a thermal desorption apparatus (Perkin Elmer: tarbo Matrix ATD) to adsorb the desorbed gas to a secondary trapping tube.
(ii) GC/MS analysis
The secondary trap was heated at 250℃for 1 minute, and the separated gas was analyzed by GC/MS (manufactured by Agilent Technologies Co., ltd.: 7890B (GC), 5977AMSD (MS)).
(iii) Quantitative analysis
The peak areas of the graphs obtained by PT-GC/MS analysis of the resin composition were quantified. Specifically, the total area% of the peaks of the detected outgas (outgas) is specified as an evaluation value.
Based on the obtained evaluation value (total area%), the amount of generated gas was evaluated according to the following criteria.
O: the evaluation value is less than 5.0E 9 。
X: the evaluation value was 5.0E 9 The above.
TABLE 3
As is clear from table 3, in the case of the polymerizable composition of the example containing the silicone resin (a) having a predetermined structure, even if the polymerizable composition contains the specific type of inorganic filler (D1) and the alkaline filler (D2), the generation of residues at the time of development with the aqueous alkali solution can be suppressed.
In particular, it is found that outgas generated from a cured film formed using a polymerizable composition containing a silicone resin (a) having a predetermined structure is small.
On the other hand, it is found that when an alkali-soluble resin having another structure is used instead of the polymerizable composition containing a silicon resin having a predetermined structure, residues are likely to be generated during development with an aqueous alkali solution, and outgas is likely to be generated from a cured film.

Claims (6)

1. A polymerizable composition comprising a component containing a polymerizable group,
The polymerizable composition comprises a silicon-containing resin A, a polymerization initiator C and a filler D,
the silicon-containing resin a comprises a silsesquioxane resin A1,
the silsesquioxane resin A1 is a silsesquioxane resin having a structural unit represented by the following formula (A1 a),
[ chemical formula 1]
In the formula (a 1 a), R a1 Is a group represented by the following formula (a 1 a-I),
-X a -B a -Y a -COOH……(a1a-I)
X a is a single bond, an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, or-R a6 -NH-R a7 -a group represented by formula (i),
R a6 and R is a7 Each independently represents an alkylene group having 1 to 3 carbon atoms,
Y a a cyclic organic group having 2 valences or a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms,
B a is-NH-CO-, -CO-NH-, -NH-CO-O-, and-O-CO-NH-, or-NH-CO-NH-,
X a and Y a Each independently may be 1 or more selected from the group consisting of (meth) acryloyloxy, vinyl and epoxy-containing organic groupsThe substitution of the groups is carried out,
the polymerizable group-containing component comprises at least 1 of the following (1) to (5),
(1) X in the above formula (a 1 a-I) having a structural unit represented by the above formula (a 1 a) a And Y a At least one of which is a silsesquioxane resin A1-1 substituted with 1 or more groups selected from the group consisting of (meth) acryloyloxy groups, vinyl groups and epoxy-containing organic groups,
(2) A silsesquioxane resin A1-2 having a structural unit represented by the above formula (A1 a) and a structural unit represented by the following formula (a 2 a),
[ chemical formula 2]
In the formula (a 2 a), R a2 Is a group represented by the following formula (a 1 a-II),
-Z a -A a ……(a1a-II)
Z a is a single bond, an alkylene group having 1 to 6 carbon atoms, or an arylene group having 6 to 12 carbon atoms, A a Is a (meth) acryloyloxy, vinyl, or epoxy-containing organic group,
(3) A silsesquioxane resin A2 having a structural unit represented by the above formula (A2 a) and not belonging to the silsesquioxane resin A1,
(4) A polyfunctional polymerizable monomer B, and
(5) A polymerizable group-containing resin having 1 or more groups selected from the group consisting of a (meth) acryloyloxy group, a vinyl group, and an epoxy group-containing organic group, and not belonging to any one of the silsesquioxane resin A1, the silsesquioxane resin A2, or the polyfunctional polymerizable monomer B;
the polyfunctional polymerizable monomer B is a polyfunctional monomer having 5 or more functions,
the filler D contains 1 or more selected from the group consisting of an inorganic filler D1 and an alkaline filler D2,
the inorganic filler D1 is 1 or more selected from the group consisting of: at least 1 element selected from the group consisting of La, ce, nd, gd, ho, lu, hf and Ta, an oxide of the element, a chelate of the element, a salt of the element, and an alloy of the element,
The alkaline filler D2 is at least one selected from alkaline fillers and alkaline polymers.
2. A method of producing a cured film, the method comprising the steps of:
a process for forming a coating film on a substrate using the polymerizable composition according to claim 1,
a step of exposing the coating film positionally selectively, and
and developing the exposed coating film.
3. The method for producing a cured film according to claim 2, wherein the exposed coating film is developed using an aqueous alkali solution as a developing solution.
4. A cured film formed by curing the polymerizable composition according to claim 1.
5. A transparent insulating film formed by curing the polymerizable composition according to claim 1 containing the inorganic filler D1 as the filler D.
6. A display device having the transparent insulating film according to claim 5.
CN201810085762.4A 2017-01-31 2018-01-29 Polymerizable composition, method for producing cured film, and cured film Active CN108375878B (en)

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