CN111417669A - Fluorine-containing active energy ray-curable resin, liquid repellent, resin composition containing same, and cured film - Google Patents

Fluorine-containing active energy ray-curable resin, liquid repellent, resin composition containing same, and cured film Download PDF

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CN111417669A
CN111417669A CN201880077226.8A CN201880077226A CN111417669A CN 111417669 A CN111417669 A CN 111417669A CN 201880077226 A CN201880077226 A CN 201880077226A CN 111417669 A CN111417669 A CN 111417669A
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active energy
energy ray
fluorine
acid
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CN111417669B (en
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笹本慎
植野纯平
高野启
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DIC Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/142—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

Abstract

The invention provides a fluorine-containing active energy ray-curable resin, a liquid repellent agent, a resin composition containing the same, and a cured film, wherein the resin structure is easy to adjust the fluorine atom content, the surface segregation is excellent, and the fluorine-containing active energy ray-curable resin can show sufficient leveling property, water repellency, oil repellency, liquid repellency and the like even when the amount of the fluorine-containing active energy ray-curable resin is small. Specifically, a fluorine-containing active energy ray-curable resin having the following structural unit in 1 molecule is used: having an alkylene chain (A) having hydroxyl groups at both ends and having at least 1 of the hydrogen atoms replaced by a fluorine atomA residue of a 2-valent phenolic hydroxyl group-containing compound (B) other than the above (A) and/or a residue of a 2-valent carboxylic acid (C) represented by the following formula (1) [ X is a hydrogen atom, an organic group having a polymerizable group (X1) or an organic group having an acid group (X2)]The linking groups shown are linked, and at least one of the linking groups shown in the structural formula (1) contained in 1 molecule is a 1-valent organic group (x1) having a polymerizable group.

Description

Fluorine-containing active energy ray-curable resin, liquid repellent, resin composition containing same, and cured film
Technical Field
The present invention relates to a fluorine-containing active energy ray-curable resin which can be suitably used as a surface modifier for surface smoothness, water/oil repellency, and the like of a cured film or as a liquid repellent, a resin composition containing the same, and a cured film thereof.
Background
Heretofore, a fluorine-based surfactant or a fluorine-based surface modifier has been widely used for various coating materials, surface modifiers, and the like because of its excellent leveling property, wettability, permeability, blocking resistance, sliding property, water-and oil-repellency, stain resistance, and the like.
A cured film obtained by applying and curing a coating material formed of an active energy ray-curable composition containing the fluorine-based surfactant or the fluorine-based surface modifier (hereinafter, these are collectively referred to as "fluorine-based surfactant") exhibits excellent surface characteristics, but on the other hand, some of the fluorine-based surfactant is easily detached or volatilized from the surface of the cured film due to heating, humidification, exposure to chemicals such as acids and alkalis, washing for removing stains, and the like, and as a result, there is a problem that the production line is contaminated or the stain-proofing property of the surface of the coating film is lowered.
As a means for solving such a problem, a method has been proposed in which a fluorine-based surfactant is made to have an active energy ray-curable functional group in its structure so as to be strongly bonded to the surface of a cured film (see, for example, patent document 1). By using the fluorine-containing polymerizable resin proposed in patent document 1 as one component of the active energy ray-curable resin composition, the problems such as detachment from the surface of the cured film are reduced, and the functions such as stain resistance of the surface can be maintained for a long period of time. However, in order to produce a fluorine-based surfactant having a balanced balance of various properties, the acrylic copolymer of patent document 1 has an upper limit on the content of fluorine atoms that can be contained in 1 molecule, and it is necessary to increase the amount of the fluorine-based surfactant added to the composition.
In recent years, a liquid repellent is known as one use of a fluorine-based surfactant, and is an additive contained in a photosensitive resin composition when partition walls are formed by a photolithography method using the photosensitive resin composition in order to prevent mixing of ink between adjacent dots and uniformly apply the ink for dot formation when an organic layer such as a light emitting layer is pattern-printed in the form of dots by an Inkjet (IJ) method in the production of an optical element such as an organic E L (Electro-L electroluminescence) element, a quantum dot display, a TFT (Thin Film Transistor) array, a Thin Film solar cell, or the like, and to form a partition wall by a photolithography method (see, for example, patent document 2).
The partition walls need to exhibit sufficient liquid repellency on the upper surface thereof, and therefore, a fluorine-based surfactant is blended in the photosensitive resin composition, while the openings for dot formation surrounded by the partition walls including the side surfaces of the partition walls need to have ink affinity. The film obtained from the resist composition containing the liquid repellent proposed in patent document 2 can form such partitions, but when a finer pattern is printed, the liquid repellent on the upper surface may be insufficient, or the components derived from the fluorine-based surfactant may migrate to the side surfaces of the partitions to cause insufficient ink affinity at the openings, and a liquid repellent having higher performance (exhibiting higher liquid repellency and exhibiting an effect by adding a smaller amount) is required.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2012 and 092308
Patent document 2: japanese patent laid-open publication No. 2010-140043
Disclosure of Invention
Problems to be solved by the invention
In view of the above circumstances, an object of the present invention is to provide a fluorine-containing active energy ray-curable resin, a liquid repellent, a resin composition containing the same, and a cured film, each of which has a resin structure in which the fluorine atom content can be easily adjusted, has excellent surface segregation when used as 1 component of an active energy ray-curable composition, and can exhibit sufficient leveling properties, water/oil repellency, liquid repellency, and the like even when used in a small amount.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by using a fluorine-containing active energy ray-curable resin having a structure in which a structural unit containing a fluorine-containing alkylene chain and a structural unit formed from another 2-valent hydrocarbon group are connected in a straight chain, and the connecting portion includes an active energy ray-curable functional group.
That is, the present invention provides a fluorine-containing active energy ray-curable resin characterized by having the following structural unit in 1 molecule, a liquid repellent, a resin composition containing the same, and a cured film thereof: which has at least one alkylene chain having hydroxyl groups at both ends and at least 1 of hydrogen atoms substituted by fluorine atoms (wherein the alkylene chain includes a chain having an etheric oxygen atom), (A) and
at least one of the residues of the 2-valent phenolic hydroxyl group-containing compound (B) other than the above (A) and/or the residue of the 2-valent carboxylic acid (C),
they are linked by a linking group represented by the following structural formula (1),
Figure BDA0002513854360000031
[ in the formula (1), X represents a hydrogen atom, a 1-valent organic group having a polymerizable group (X1), or a 1-valent organic group having an acid group (X2) ],
and at least one of the linking groups represented by the aforementioned structural formula (1) contained in the 1 molecule is a 1-valent organic group (x1) having a polymerizable group.
Further, the present invention provides a fluorine-containing active energy ray-curable resin, a method for producing the same, a liquid repellent, a resin composition containing the same, and a cured film thereof, wherein 1 molecule of the fluorine-containing active energy ray-curable resin has the following structural unit: having at least one alkylene chain having carboxyl groups at both ends and at least 1 of hydrogen atoms substituted with a fluorine atom (wherein the alkylene chain includes a chain having an etheric oxygen atom), (D) or
At least one alkylene chain having hydroxyl groups at both ends and at least 1 of hydrogen atoms substituted with a fluorine atom (wherein the alkylene chain includes a chain having an etheric oxygen atom), (A) a residue of a reactant with a dicarboxylic anhydride (E), and
at least one residue of a 2-valent hydroxyl group-containing compound (F) other than the aforementioned (A),
they are linked by a linking group represented by the following structural formula (1),
Figure BDA0002513854360000041
[ in the formula (1), X represents a hydrogen atom, a 1-valent organic group having a polymerizable group (X1), or a 1-valent organic group having an acid group (X2) ],
and at least one of the linking groups represented by the aforementioned structural formula (1) contained in the 1 molecule is a 1-valent organic group (x1) having a polymerizable group.
ADVANTAGEOUS EFFECTS OF INVENTION
The fluorine-containing active energy ray-curable resin of the present invention can be used as a liquid repellent agent, and is suitable as a material for an active energy ray-curable resin composition used for pattern formation in the production of optical elements such as organic E L elements, quantum dot displays, TFT arrays, and thin-film solar cells, which have recently been increasingly refined.
Drawings
FIG. 1 is a GPC chart of the fluorine-containing active energy ray-curable resin (1-i) obtained in example 1.
Detailed Description
The fluorine-containing active energy ray-curable resin of the present invention is characterized by having the following structural unit in 1 molecule: which has at least one residue of an alkylene chain having hydroxyl groups at both ends and at least 1 of hydrogen atoms substituted with a fluorine atom (wherein the alkylene chain includes a chain having an etheric oxygen atom), (A)
At least one of the residues of the 2-valent phenolic hydroxyl group-containing compound (B) other than the above (A) and/or the residue of the 2-valent carboxylic acid (C),
they are linked by a linking group represented by the following structural formula (1),
Figure BDA0002513854360000051
[ in the formula (1), X represents a hydrogen atom, a 1-valent organic group having a polymerizable group (X1), or a 1-valent organic group having an acid group (X2) ],
and at least one of the linking groups represented by the aforementioned structural formula (1) contained in the 1 molecule is a 1-valent organic group (x1) having a polymerizable group. Hereinafter, it may be referred to as a fluorine-containing active energy ray-curable resin (I-1).
Further, the fluorine-containing active energy ray-curable resin of the present invention is characterized by having the following structural unit in 1 molecule: having at least one alkylene chain having carboxyl groups at both ends and at least 1 of hydrogen atoms substituted with a fluorine atom (wherein the alkylene chain includes a chain having an etheric oxygen atom), (D) or
At least one alkylene chain having hydroxyl groups at both ends and at least 1 of hydrogen atoms substituted with a fluorine atom (wherein the alkylene chain includes a chain having an etheric oxygen atom), (A) a residue of a reactant with a dicarboxylic anhydride (E), and
at least one residue of a 2-valent hydroxyl group-containing compound (F) other than the aforementioned (A),
they are linked by a linking group represented by the following structural formula (1),
Figure BDA0002513854360000052
[ in the formula (1), X represents a hydrogen atom, a 1-valent organic group having a polymerizable group (X1), or a 1-valent organic group having an acid group (X2) ],
and at least one of the linking groups represented by the aforementioned structural formula (1) contained in the 1 molecule is a 1-valent organic group (x1) having a polymerizable group. Hereinafter, it may be referred to as a fluorine-containing active energy ray-curable resin (I-2).
Conventionally, as a fluorine-containing compound such as a fluorine-based surfactant, a large number of copolymers obtained by copolymerizing an acrylic monomer having a perfluoroalkyl chain (wherein the alkyl chain includes a chain having an etheric oxygen atom) or a perfluoroalkylene chain (wherein the alkylene chain includes a chain having an etheric oxygen atom) and a monomer copolymerizable therewith have been provided. Also disclosed is a copolymer of a bifunctional monomer having a (meth) acryloyl group at each end of a perfluoroalkylene chain (wherein the alkylene chain includes a chain having an etheric oxygen atom) and another polymerizable monomer. Also disclosed is a fluorine-containing active energy ray-curable resin which is obtained by introducing an active energy ray-curable functional group into a portion corresponding to a side chain in the molecular structure.
Since the fluorine-containing compound obtained by these acrylic copolymerization methods uses a bifunctional monomer having a (meth) acryloyl group at both ends of a perfluoroalkylene chain (wherein the alkylene chain includes a chain having an etheric oxygen atom), if the fluorine atom content in 1 molecule is to be increased, gelation occurs. Therefore, the amount of fluorine atoms that can be introduced into 1 molecule has an upper limit, and the degree of freedom in design is low. In addition, in order to exhibit predetermined effects such as water-and oil-repellency and leveling property which the fluorine atom originally has, it is necessary to increase the amount of the fluorine-containing compound (fluorine-based surfactant) to be blended in the composition. Further, since a copolymerization method using a bifunctional monomer and an acrylic monomer is employed, a production method for suppressing gelation is required, and as a result, there is a problem that a copolymer having a relatively low molecular weight is easily contained.
In order to solve these problems, the present invention has devised a fluorine-containing active energy ray-curable resin having a novel structure using a raw material which is easily commercially available. In the present invention, "(meth) acryloyl group" means either or both of a methacryloyl group and an acryloyl group, "(meth) acrylate" means either or both of a methacrylate and an acrylate, and "(meth) acrylic acid" means either or both of methacrylic acid and acrylic acid.
In the present invention, the residue, specifically, the residue of the (a) alkylene chain having hydroxyl groups at both ends and at least 1 of hydrogen atoms substituted by fluorine atoms (wherein the alkylene chain includes a chain having an etheric oxygen atom), the residue of the (B) phenolic hydroxyl group-containing compound having a valence of 2, and the residue of the (F) hydroxyl group-containing compound having a valence of 2 are each a structure in which a hydrogen atom of a hydroxyl group in the structure is removed, i.e., a chain-like structural unit having both ends "O", and the starting material is not limited to the use of an alkylene chain having hydroxyl groups at both ends and at least 1 of hydrogen atoms substituted by fluorine atoms (wherein the alkylene chain includes a chain having an etheric oxygen atom) (a), the (B) phenolic hydroxyl group-containing compound having a valence of 2, and the (F) hydroxyl group-containing compound having a valence of 2. Similarly, the residue of the reactant of (a) a carboxylic acid (C) having a valence of 2, the residue of an alkylene chain having carboxyl groups at both terminals and having at least 1 of hydrogen atoms substituted with a fluorine atom (wherein the alkylene chain includes a chain having an etheric oxygen atom), (D), the residue of an alkylene chain having hydroxyl groups at both terminals and having at least 1 of hydrogen atoms substituted with a fluorine atom (wherein the alkylene chain includes a chain having an etheric oxygen atom), (a), and a dicarboxylic anhydride (E) each refer to a structure in which a hydrogen atom in a carboxyl group in the structure is removed, i.e., a chain-like structural unit having "C (═ O) O" at both terminals.
The alkylene chain in (a) an alkylene chain in which both ends are hydroxyl groups and at least 1 of hydrogen atoms is substituted with a fluorine atom (wherein the alkylene chain includes a chain having an etheric oxygen atom), and (D) an alkylene chain in which both ends are carboxyl groups and at least 1 of hydrogen atoms is substituted with a fluorine atom (wherein the alkylene chain includes a chain having an etheric oxygen atom) (a) an alkylene chain having a partial structure having a fluorine atom, and at least one of hydrogen atoms in the alkylene chain is substituted with a fluorine atom, may be a fluoroalkylene chain, or a fluoroalkylene ether chain in which hydrogen atoms are connected via an oxygen atom, and the alkylene chain may have a linear, branched, or cyclic alkylene structure in which a part thereof forms a ring.
Among these, from the viewpoint of ease of handling, a C1-6 perfluoroalkylene chain or a C1-6 perfluoroalkylene chain in which a plurality of C1-6 perfluoroalkylene chains are connected to each other via oxygen atoms is preferable, and a perfluoroalkylene ether chain is preferable from the viewpoint of ease of adjustment of the fluorine atom content. Further, a structure in which hydroxyl groups are directly bonded to both ends of a perfluoroalkylene ether chain may be employed, or a structure in which hydroxyl groups are bonded via an alkylene chain having no fluorine atom.
The number of carbon atoms to which fluorine atoms contained in 1 molecule are directly bonded is preferably in the range of 1 to 100, and in the case of a perfluoroalkylene chain, the number of carbon atoms is preferably in the range of 1 to 6, and particularly preferably in the range of 4 to 6, as described above. In the case of a perfluoroalkylene ether chain, the number of carbon atoms to which fluorine atoms are directly bonded is preferably 1 to 6 and the number of repetitions is in the range of 1 to 50, and a perfluoroalkylene ether chain having an alkylene chain of 1 to 3 carbon atoms as a repeating unit and the number of repetitions is in the range of 1 to 50 is particularly preferred.
The residue of the alkylene chain (a) having hydroxyl groups at both ends and at least 1 of hydrogen atoms substituted with a fluorine atom (wherein the alkylene chain includes a chain having an etheric oxygen atom) is represented by the above-mentioned "O-", and when an alkylene chain having at least 1 of hydrogen atoms substituted with a fluorine atom is referred to as "Rf", for example, the residue is a structural unit represented by "-O-Rf-O-".
Similarly, the residue of the alkylene chain (D) having carboxyl groups at both ends and at least 1 of hydrogen atoms substituted by fluorine atoms (wherein the alkylene chain includes a chain having an etheric oxygen atom) has the same structure as described above, and has "C (═ O) O" at both ends, and if Rf is used as described above, it is a structural unit represented by "— O — C (═ O) -Rf-C (═ O) -O-".
The fluorine-containing active energy ray-curable resin (I-1) of the present invention has a structural unit represented by "-O-Rf-O-" and a residue of the 2-valent phenolic hydroxyl group-containing compound (B) and/or a residue of the 2-valent carboxylic acid (C) other than the above (A) as described above.
When the aromatic ring moiety is referred to as "φ", the residue of the 2-valent phenolic hydroxyl group-containing compound (B) is a structural unit represented by "-O- φ -O-".
The aromatic ring portion may be formed of a single benzene ring or condensed rings such as naphthalene, anthracene, phenanthrene, acenaphthene, fluorene, fluoranthene, pyrene, or the like, or may be a structure in which 2 or more benzene rings and condensed rings are directly bonded, or a structure in which 2-valent linking groups such as a branched or linear alkylene chain (in which a part or all of hydrogen atoms may be substituted by fluorine atoms), an oxygen atom, a sulfur atom, -NR- (wherein R is a hydrogen atom or an alkyl group), or the like are linked, and further, a 1-valent substituent other than a hydroxyl group may be present on the benzene ring or the condensed rings. Furthermore, the residues of the 2-valent phenolic hydroxyl group-containing compound (B) present in 1 molecule may all be the same or may have different residues.
The substituent may be a monovalent group, and examples thereof include: bromine atom, chlorine atom, iodine atom, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N-dialkylamino group, N-arylamino group, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N-dialkylcarbamoyloxy group, N-diarylamino groupA formyloxy group, an N-alkyl-N-arylcarbamoyloxy group, an alkylsulfinic (alkyl suxy group), an arylsulfoxy (aryl suxy group), a thioyl group, an acylamino group, an N-alkylacylamido group, an N-arylacylamino group, an ureido group, an N ' -alkylureido group, an N ', N ' -dialkylureido group, an N ' -arylureido group, an N ', N ' -diarylureido group, an N ' -alkyl-N ' -arylureido group, an N-alkylureido group, an N-arylureido group, an N ' -alkyl-N-alkylureido group, an N ' -alkyl-N-arylureido group, an N ', N ' -dialkyl-N-alkylureido group, an N ', N ' -dialkyl-N-arylureido group, an N ' -alkyl-N-arylureido group, an N ', N ' -dialkyl, N ' -aryl-N-alkylureido, N ' -aryl-N-arylureido, N ' -diaryl-N-alkylureido, N ' -diaryl-N-arylureido, N ' -alkyl-N ' -aryl-N-alkylureido, N ' -alkyl-N ' -aryl-N-arylureido, alkoxycarbonylamino, aryloxycarbonylamino, N-alkyl-N-alkoxycarbonylamino, N-alkyl-N-aryloxycarbonylamino, N-aryl-N-alkoxycarbonylamino, N-aryl-N-aryloxycarbonylamino, formyl, acyl, carboxyl, alkoxycarbonyl, N ' -arylcarbonylamino, N ' -aryloxycarbonylamino, N ' -arylcarbonylamino, formyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N-dialkylcarbamoyl, N-arylcarbamoyl, N-diarylcarbamoyl, N-alkyl-N-arylcarbamoyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfo (-SO)3H) And the conjugated base thereof (known as the sulfonic acid group), alkoxysulfonyl, aryloxysulfonyl, sulfamoyl, N-alkylsulfamoyl, N-dialkylsulfamoyl, N-arylsulfamoyl, N-diarylsulfamoyl, N-alkyl-N-arylsulfamoyl, phosphono (-PO) group3H2) And its conjugated base group (called phosphonic acid group), dialkyl phosphono group (-PO)3(alkyl)2) "alkyl ═ alkyl, same below", diarylphosphono (-PO)3(aryl)2) "aryl ═ aryl, the same below", alkylaryl phosphono (-PO)3(alkyl) (aryl)), monoalkyl phosphono (-PO)3(alkyl)) and its conjugated base (called alkylphosphine)Acid group), monoarylphosphono (-PO)3H (aryl) and its conjugated base (called aryl phosphonic acid group), phosphonoxy (-OPO)3H2) And conjugate bases thereof (called phosphonato), dialkylphosphonoxy (-OPO)3H(alkyl)2) Diaryl phosphonyloxy (-OPO)3(aryl)2) Alkyl aryl phosphonoxy (-OPO)3(alkyl) (aryl)), monoalkylphosphonoxy (-OPO)3H (alkyl) and its conjugated basic group (called alkylphosphonoxy), monoarylphosphonoxy (-OPO)3H (aryl)), a conjugated basic group thereof (referred to as arylphosphonooxy group), a cyano group, a nitro group, an aryl group, a heterocyclic group, a silyl group, an ethenyl group, an alkenyl group such as a 1-propenyl group, a 1-butenyl group, a cinnamyl group, a 2-chloro-1-ethenyl group, an alkynyl group such as an ethynyl group, a 1-propynyl group, a 1-butynyl group, or a trimethylsilylethynyl group.
Among these, structural units derived from biphenol, bisphenol, binaphthol, or naphthalene diol which may have a substituent on the ring are preferable, structural units derived from biphenol or bisphenol are particularly preferable, and structural units derived from bisphenol a or bisphenol F are most preferable, from the viewpoint of being industrially easily produced by the production method described later.
Further, in the fluorine-containing active energy ray-curable resin (I-1) of the present invention, the residue of the 2-valent carboxylic acid (C) is represented by, for example, R as a skeleton portion as described above1In the case of (a), is represented by "-O-C (═ O) -R1-C (═ O) -O- "represents a structural unit.
The R is1The moiety is not particularly limited, and may be derived from an aliphatic compound or may have an aromatic ring. Examples thereof include: structural units derived from aliphatic 2-valent carboxylic acids such as malic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, and compounds having the aforementioned 1-valent substituent on the aromatic ring thereof, and the like, and the residue of the 2-valent carboxylic acid (C) present in 1 molecule may be formed from the same compoundAnd may have a plurality of different residues. Among these, structural units [ residues ] derived from succinic acid and maleic acid are preferable from the viewpoint of being excellent in balance among easiness of availability of industrial raw materials in the production method described later and performances such as heat resistance and surface segregation of the obtained fluorine-containing active energy ray-curable resin]。
The fluorine-containing active energy ray-curable resin (I-2) of the present invention has, as described above: a structural unit represented by "— O — C (═ O) -Rf-C (═ O) -O-", or a residue of a reaction product of (a) an alkylene chain having hydroxyl groups at both ends and having at least 1 of hydrogen atoms substituted with a fluorine atom (wherein the alkylene chain includes a chain having an etheric oxygen atom) and a dicarboxylic anhydride (E), and a residue of a 2-valent hydroxyl group-containing compound (F) other than the above (a).
The residue of the reaction product of (A) an alkylene chain having hydroxyl groups at both ends and at least 1 of hydrogen atoms substituted with a fluorine atom (wherein the alkylene chain includes a chain having an etheric oxygen atom) and (E) a dicarboxylic anhydride (E) is represented by R as the skeleton of the dicarboxylic anhydride (E)2In the case of (a), is represented by "-O-C (═ O) -R2A structural unit represented by — (O) — O — Rf-O- ", or a structural unit represented by — (O — C) — (O) — (R)2-C(＝O)-O-Rf-O-C(＝O)-R2-C (═ O) -O- "represents a structural unit.
R mentioned above2The moiety is not particularly limited, and may be derived from an aliphatic compound or may have an aromatic ring. Examples of the structure include those derived from phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and the like, and R's having a plurality of groups in 1 molecule may have the same structure or may have a plurality of different structures. Among these, structural units derived from succinic anhydride and maleic anhydride are preferable from the viewpoint of ease of purchase of industrial raw materials in the production method described later, and excellent balance of properties such as heat resistance and surface segregation of the obtained fluorine-containing active energy ray-curable resin.
Containing a valence of 2 other than the above (A)Examples of the residue of the hydroxyl compound (F) include: the residue of the above-mentioned 2-valent phenolic hydroxyl group-containing compound (B) and the residue of an aliphatic diol have the skeleton portion denoted by "R3"in the case of a compound represented by the formula" -O-R3-O- "represents a structural unit.
R mentioned above3Some examples are: the same groups as φ exemplified as the residue of the above-mentioned 2-valent phenolic hydroxyl group-containing compound (B), or rings such as an alkylene chain, an oxyalkylene chain, cyclopentane, cyclohexane and the like, have a plurality of R's in 1 molecule3May be the same structure or may include a plurality of different structures. Among these, an alkylene chain having 1 to 6 carbon atoms is preferable from the viewpoint of ease of purchase of industrial raw materials in the production method described later, and excellent balance of properties such as heat resistance and surface segregation of the obtained fluorine-containing active energy ray-curable resin.
The fluorine-containing active energy ray-curable resin of the present invention is characterized by having a linear structure as described above, and having a structural unit in which structural units having oxygen atoms forming ether bonds at the terminals as described in detail above are linked via a linking group represented by the following structural formula (1):
Figure BDA0002513854360000111
[ in the formula (1), X represents a hydrogen atom, a 1-valent organic group having a polymerizable group (X1), or a 1-valent organic group having an acid group (X2) ],
and at least one of the linking groups represented by the aforementioned structural formula (1) contained in the 1 molecule is a 1-valent organic group (x1) having a polymerizable group.
Examples of the polymerizable group contained in the organic group (x1) include a vinyl group and a (meth) acryloyl group, and from the viewpoint of polymerizability in the case of preparing an active energy ray-curable resin composition described later, an organic group containing a (meth) acryloyl group is preferable.
In the structural formula (1), examples of the method using a 1-valent organic group (X1) having a polymerizable group as X include: a method of reacting a secondary hydroxyl group in which X is a hydrogen atom with a compound having an isocyanate group, a carboxyl group or a carboxylic acid halide group and a vinyl group or a (meth) acryloyl group.
Among these, from the viewpoint of easy reaction, a group obtained by reacting a secondary hydroxyl group with a (meth) acrylate having an isocyanate group is preferable, and a linking group having a structure represented by the following structural formula (2) is particularly preferable:
Figure BDA0002513854360000121
[ in the formula (2), Y is a linking group having a valence of 2, and R is a hydrogen atom or a methyl group ].
Examples of the (meth) acrylate having an isocyanate group include the following compounds: a monomer having 1 isocyanate group and 1 (meth) acryloyl group, a monomer having 1 isocyanate group and 2 (meth) acryloyl groups, a monomer having 1 isocyanate group and 3 (meth) acryloyl groups, a monomer having 1 isocyanate group and 4 (meth) acryloyl groups, a monomer having 1 isocyanate group and 5 (meth) acryloyl groups, and the like.
Figure BDA0002513854360000122
[ formula (3), R' is a C2-4 alkylene chain, R is a hydrogen atom or methyl, n is an integer of 1-5. ]
Specific examples of the (meth) acrylate having an isocyanate group include: 2-acryloyloxyethyl isocyanate (trade name: Karenz AOI manufactured by Showa Denko K.K.), 2-methacryloyloxyethyl isocyanate (trade name: Karenz MOI manufactured by Showa Denko K.K.), 1-bis (acryloyloxymethyl) ethyl isocyanate (trade name: Karenz BEI manufactured by Showa Denko K.K.), and the like.
Further, there may be mentioned: a compound obtained by adding a hydroxyl group-containing (meth) acrylate compound to one isocyanate group of a diisocyanate compound. The diisocyanate compound used in this reaction can be exemplified by: aliphatic diisocyanates such as butane-1, 4-diisocyanate, hexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene diisocyanate;
alicyclic diisocyanates such as cyclohexane-1, 4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, 1, 3-bis (isocyanotomethyl) cyclohexane, methylcyclohexane diisocyanate, and the like;
aromatic diisocyanates such as 1, 5-naphthylene diisocyanate, 4 ' -diphenylmethane diisocyanate, 4 ' -diphenyldimethylmethane diisocyanate, 4 ' -dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, and toluene diisocyanate. These may be used alone or in combination of two or more.
At least one of X in the general formula (1) is the 1-valent organic group (X1) having a polymerizable group as described above, and among a plurality of linking groups present in 1 molecule, when used as a curable composition, particularly a resist composition, described later, it is preferable to also have the 1-valent organic group (X2) having an acid group.
The acid group is not particularly limited, and examples thereof include: a carboxyl group, a sulfo group, a phosphate group, and the like, and particularly, a linking group having a carboxyl group is preferably used from the viewpoint of good alkali solubility and easiness of purchase of raw materials.
The method for introducing the acid group is not particularly limited, and examples thereof include: a method of reacting a secondary hydroxyl group in which X is a hydrogen atom with a compound having an acid anhydride group.
When the fluorine-containing active energy ray-curable resin of the present invention is used as a negative resist composition, introduction of an acid group makes the alkali developability more excellent, and is more useful for high-definition pattern formation. From such a viewpoint, the amount of the acid group to be introduced is suitably set in accordance with the use and performance level thereof, and the acid value is preferably in the range of 5 to 120mgKOH/g, more preferably in the range of 7 to 100mgKOH/g, and further more preferably in the range of 10 to 80 mgKOH/g.
The fluorine-containing active energy ray-curable resin of the present invention has chain-like structural units as described above, and the terminal thereof is not particularly limited as long as it is derived from a compound used as a raw material, and when synthesized by a production method described later, the terminal is a hydrogen atom, a glycidyl group, or a carboxyl group. These terminal structures are naturally determined by the addition ratio of raw materials, the reaction sequence, and a plurality of compounds contained in the resin, whether formed only of substances having the same terminal structure or a mixture of compounds having different terminal structures, may be preferably used.
Examples of the fluorine-containing active energy ray-curable resin of the present invention include those represented by the following formulae. In the following formula, m and n each represent a repetition number and are integers of 1 or more. Furthermore, PFPE represents a perfluoroalkylene ether chain.
Figure BDA0002513854360000141
Figure BDA0002513854360000151
Figure BDA0002513854360000161
The fluorine atom content in the fluorine-containing active energy ray-curable resin of the present invention can be easily set depending on the application, desired water-and oil-repellency, liquid-repellency, leveling property, and the like, and is preferably in the range of 1 to 45 mass%, and particularly preferably in the range of 3 to 40 mass%, from the viewpoint of compatibility with other resins, compounds, solvents, and the like when the resin composition is produced as an active energy ray-curable resin composition.
The fluorine atom content can be calculated from the type of raw material and the ratio thereof at the time of designing the resin, or can be actually measured by combustion ion chromatography. In the present invention, the latter measured value is preferably within the above range.
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the fluorine-containing active energy ray-curable resin of the present invention are preferably in the range of 500 to 100,000, more preferably in the range of 1,000 to 50,000, because they have good compatibility with other compounding ingredients when producing a curable resin composition and can easily achieve high leveling property, water/oil repellency, and liquid repellency. The weight average molecular weight (Mw) is preferably in the range of 5,000 to 200,000, more preferably 10,000 to 100,000. The number average molecular weight (Mn) and the weight average molecular weight (Mw) are values in terms of polystyrene measured by a permeation gel chromatography (hereinafter abbreviated as "GPC"). The measurement conditions of GPC are as follows.
[ GPC measurement conditions ]
Measuring apparatus H L C-8220GPC manufactured by Tosoh corporation,
Chromatographic column A guard column "HHR-H" (6.0mmI.D. × 4cm) manufactured by Tosoh corporation
+ Tosoh corporation of "TSK-GE L GMHHR-N" (7.8mmI.D. × 30cm)
+ Tosoh corporation of "TSK-GE L GMHHR-N" (7.8mmI.D. × 30cm)
+ Tosoh corporation of "TSK-GE L GMHHR-N" (7.8mmI.D. × 30cm)
+ Tosoh corporation of "TSK-GE L GMHHR-N" (7.8mmI.D. × 30cm)
Detector E L SD (manufactured by Alltech "E L SD 2000")
Data processing: "GPC-8020 Model II data analysis version 4.30" manufactured by Tosoh corporation "
The measurement conditions were as follows: column temperature 40 deg.C
Tetrahydrofuran (THF) as developing solvent
Flow rate 1.0 ml/min
Sample preparation: a sample (5. mu.l) obtained by filtering a tetrahydrofuran solution at 1.0 mass% in terms of solid content of the resin was filtered through a microfilter.
Standard sample: the following monodisperse polystyrene having a known molecular weight was used according to the manual of measurement of "GPC-8020 Model II data analysis version 4.30" described above.
(monodisperse polystyrene)
"A-500" manufactured by Tosoh corporation "
"A-1000" manufactured by Tosoh corporation "
"A-2500" manufactured by Tosoh corporation "
"A-5000" manufactured by Tosoh corporation "
"F-1" manufactured by Tosoh corporation "
"F-2" manufactured by Tosoh corporation "
"F-4" manufactured by Tosoh corporation "
"F-10" manufactured by Tosoh corporation "
"F-20" manufactured by Tosoh corporation "
"F-40" manufactured by Tosoh corporation "
"F-80" manufactured by Tosoh corporation "
"F-128" manufactured by Tosoh corporation "
"F-288" manufactured by Tosoh corporation "
"F-550" manufactured by Tosoh corporation "
In addition, the fluorine-containing active energy ray-curable resin of the present invention preferably has an active energy ray-curable functional group concentration in the range of 0.5 to 3.0mmol/g, from the viewpoint of excellent curability when prepared into a curable resin composition described later and excellent water/oil repellency, liquid repellency, and the like of the surface of a cured film for a long period of time.
The method for producing the fluorine-containing active energy ray-curable resin of the present invention is not particularly limited, and the production is preferably carried out by the following method from the viewpoint of excellent industrial availability of raw materials and production efficiency in production.
The manufacturing method 1: a method in which a compound (a1) having an epoxy group and an alkylene chain in which at least 1 of the hydrogen atoms is substituted with a fluorine atom (wherein the alkylene chain includes a chain having an etheric oxygen atom) and a 2-valent phenolic hydroxyl group-containing compound (a2) and/or a 2-valent carboxylic acid (a3) are reacted as essential raw materials, and a compound (a4) having an active energy ray-curable functional group and an isocyanate group is reacted with a secondary hydroxyl group in the obtained reaction product.
The manufacturing method 2: a method in which a compound (a5) having a carboxyl group or a hydroxyl group and a 2-valent epoxy compound (a6) are reacted with an alkylene chain having at least 1 of hydrogen atoms substituted with a fluorine atom (wherein the alkylene chain includes a chain having an etheric oxygen atom), and a compound (a 3526) having a carboxyl group or a hydroxyl group as essential raw materials, and a compound (a4) having an active energy ray-curable functional group and an isocyanate group is reacted with a secondary hydroxyl group in the obtained reaction product.
First, the production method 1 will be described in detail.
The alkylene chain in the compound (a1) having an alkylene chain in which at least 1 of the hydrogen atoms is substituted with a fluorine atom (wherein the alkylene chain includes a chain having an etheric oxygen atom) and an epoxy group is synonymous with the above, and is preferably a perfluoroalkylene chain having 1 to 6 carbon atoms or a perfluoroalkylene ether chain having a repeating structure in which perfluoroalkylene chains having 1 to 6 carbon atoms are linked by an oxygen atom.
Examples of the compound (a1) include those represented by the following structural formulae.
Figure BDA0002513854360000191
Since the terminal epoxy group in the compound (a1) has excellent reactivity, a linear compound can be obtained by a ring-opening reaction with an epoxy group of the 2-valent phenolic hydroxyl group-containing compound (a2) or the 2-valent carboxylic acid (a3), and a secondary hydroxyl group derived from an epoxy group can be formed in a linking group portion thereof.
The fluorine-containing active energy ray-curable resin can be easily obtained by reacting the secondary hydroxyl group with the compound (a4) having an active energy ray-curable functional group and an isocyanate group as described above.
In this reaction, in order to adjust the molecular weight to a desired value, or to adjust the heat resistance, fluorine atom content, or the like, a 2-valent epoxy compound (a6) other than the above-mentioned compound (a1) may be used in combination.
The terminal structure of the resin thus obtained, that is, the terminal of the fluorine-containing active energy ray-curable resin can be obtained by any of a hydrogen atom, a glycidyl group and a carboxyl group depending on the ratio of the raw materials used.
The ratio of the compound (a1) to the 2-valent phenolic hydroxyl group-containing compound (a2) or the 2-valent carboxylic acid (a3), or the ratio of the 2-valent epoxy compound (a6) to be used in combination is not particularly limited, and for example, the total number of moles of the phenolic hydroxyl groups or the carboxyl groups is preferably 0.9 to 1.1 relative to the total number of moles of the epoxy groups in the compound (a1) and the epoxy groups in the 2-valent epoxy compound (a6) to be used in combination as needed. Since this reaction is a general ring-opening reaction of an epoxy group, a reaction product can be easily obtained by stirring at 150 to 180 ℃ in a solvent-free or organic solvent using a catalyst such as a quaternary onium salt, an imidazole, or TPP.
The organic solvent that can be used herein is not particularly limited, and examples thereof include: ketones such as acetone, methyl ethyl ketone and cyclohexanone, alcohol compounds such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, sec-butanol and tert-butanol, glycol ethers such as methyl cellosolve, ethyl cellosolve and propylene glycol monomethyl ether acetate, ether compounds such as tetrahydrofuran, 1, 4-dioxane, 1, 3-dioxane and diethoxyethane, aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide, and the like. These organic solvents may be used alone, or 2 or more kinds thereof may be used in combination as appropriate for adjusting the polarity.
Examples of the 2-valent phenolic hydroxyl group-containing compound (a2) include: resorcinol, catechol, hydroquinone, biphenol, bisphenol a, bisphenol F, bisphenol S, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol Z, binaphthol, dihydroxynaphthalene, and compounds having the aforementioned substituent having a valence of 1 on the aromatic ring thereof.
Further, the compound may be a compound represented by the following structural formula.
Figure BDA0002513854360000211
(in the formula, R1Each independently represents any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group and an aralkyl group, p is an integer of 1 to 4, l is 0 or 1, and q is 1 or 2. )
These may be used alone, or 2 or more of them may be used in combination. Among these, from the viewpoint of ease of industrial availability of raw materials, and excellent balance of properties such as heat resistance and surface segregation of the obtained fluorine-containing active energy ray-curable resin, biphenol, bisphenol, binaphthol, or naphthalene diol is preferably used, and bisphenol a and bisphenol F are particularly preferably used.
The 2-valent carboxylic acid (a3) may be any of aliphatic and aromatic carboxylic acids, and examples thereof include: and aliphatic 2-valent carboxylic acids such as malic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, fumaric acid, and maleic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acids, and compounds having the aforementioned 1-valent substituent on the aromatic ring thereof. These may be used alone, or 2 or more of them may be used in combination. Among these, succinic acid and maleic acid are preferably used from the viewpoint of being excellent in balance among the easiness of obtaining industrial raw materials and the heat resistance, surface segregation and other properties of the obtained fluorine-containing active energy ray-curable resin.
As the compound (a4) having an active energy ray-curable functional group and an isocyanate group, a compound having an isocyanate group and a (meth) acryloyl group is used, and from the viewpoint of good reactivity, any of the above-mentioned compounds can be preferably used, and 2-ethylisocyanatoacrylate and 2-ethylisocyanatomethacrylate are preferably used. These may be used alone, or 2 or more of them may be used in combination. Since this reaction is a reaction between an isocyanate group and a hydroxyl group, it can be carried out, for example, by the following method: amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; phosphines such as triphenylphosphine and triethylphosphine; organotin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate, tin octylate and the like; and a urethane-forming catalyst such as an organic metal compound (e.g., zinc octoate) is added dropwise to the obtained product having a secondary hydroxyl group, and the mixture is heated to 50 to 120 ℃.
The ratio of the compound (a4) having an active energy ray-curable functional group and an isocyanate group can be appropriately set according to the target functional group concentration, and for example, the number of moles of the isocyanate group is preferably in the range of 0.3 to 1.0 relative to the secondary hydroxyl group.
The 2-valent epoxy compound (a6) that can be used in combination for the purpose of, for example, adjusting the molecular weight is not particularly limited, and examples thereof include: bisphenol a type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, dihydroxynaphthalene type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, and the like. Further, the compound may be a compound obtained by epoxidizing an alkylene oxide adduct of a bisphenol.
Further, when a curable composition for a resist to be described later is prepared, it is preferable that an acid group is further introduced. The acid group can be easily obtained by, for example, reacting a secondary hydroxyl group that is not reacted with an isocyanate group with the acid anhydride group-containing compound (a 7).
The acid anhydride group-containing compound (a7) is not particularly limited, and examples thereof include: phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and the like, and may be used alone or in combination of 2 or more. From the viewpoint of ease of reaction, succinic anhydride and maleic anhydride are preferably used.
Next, the production method 2 will be described in detail.
In the production method 2, a compound (a5) having an alkylene chain in which at least 1 of hydrogen atoms is substituted with a fluorine atom (wherein the alkylene chain includes a chain having an etheric oxygen atom), a carboxyl group or a hydroxyl group, and a 2-valent epoxy compound (a6) are reacted as essential raw materials, and a secondary hydroxyl group in the obtained reaction product is reacted with a compound (a4) having an active energy ray-curable functional group and an isocyanate group to introduce an active energy ray-curable functional group, and the 2-valent epoxy compound, the active energy ray-curable functional group, and the isocyanate group-containing compound (a4) used in this case may be the same compounds as those used in the production method 1, and preferred compounds are also the same.
The alkylene chain in the compound (a5) having an alkylene chain in which at least 1 of the hydrogen atoms is substituted with a fluorine atom (wherein the alkylene chain includes a chain having an etheric oxygen atom) and a carboxyl group or a hydroxyl group is synonymous with the above, and is preferably a perfluoroalkylene chain having 1 to 6 carbon atoms or a perfluoroalkylene ether chain having a repeating structure in which perfluoroalkylene chains having 1 to 6 carbon atoms are linked by an oxygen atom.
Examples of the compound (a5) include those represented by the following structural formulae. In the following formula, PFPE is the same as described above. The method of introducing a carboxyl group into a terminal can be easily obtained by reacting a compound having a hydroxyl group at the terminal with a dicarboxylic anhydride.
Figure BDA0002513854360000231
The reaction between the carboxyl group or hydroxyl group in the compound (a5) and the 2-valent epoxy compound (a6) is a general ring-opening reaction of an epoxy group, and by this reaction, a reactant having a structure in which the compound (a5) and the compound (a6) are linked by a linking group having a secondary hydroxyl group can be obtained. The secondary hydroxyl group can be introduced with an active energy ray-curable functional group or an acid group by the same raw material and reaction as in production method 1.
In addition, the aforementioned 2-valent carboxylic acid (a3) and the aforementioned 2-valent phenolic hydroxyl group-containing compound (a2) other than the aforementioned compound (a5) may be used in combination for the purpose of adjusting the molecular weight to a desired value, the heat resistance, the fluorine atom content, and the like.
The terminal structure of the resin thus obtained, that is, the terminal of the fluorine-containing active energy ray-curable resin can be obtained by any of a hydrogen atom, a glycidyl group and a carboxyl group depending on the ratio of the raw materials used.
Since this reaction is a general ring-opening reaction of an epoxy group, a reaction product can be easily obtained by stirring at 150 to 180 ℃ in a solvent-free or organic solvent using a catalyst such as a quaternary onium salt, an imidazole, or TPP.
The organic solvent that can be used herein is not particularly limited, and examples thereof include: ketones such as acetone, methyl ethyl ketone and cyclohexanone, alcohol compounds such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, sec-butanol and tert-butanol, glycol ethers such as methyl cellosolve, ethyl cellosolve and propylene glycol monomethyl ether acetate, ether compounds such as tetrahydrofuran, 1, 4-dioxane, 1, 3-dioxane and diethoxyethane, aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide, and the like. These organic solvents may be used alone, or 2 or more kinds thereof may be used in combination as appropriate for adjusting the polarity.
The subsequent reaction is the same as in production method 1. Since the above-mentioned reactions proceed in a stoichiometric ratio, the compounds used as raw materials hardly remain in an unreacted state in the system, and thus the resulting resin is characterized in that it is not likely to contain low-molecular-weight compounds. Therefore, when the obtained resin is used in the same manner as in the conventional fluorine-based surfactant, volatilization during curing, detachment from the surface of the cured film, and the like can be effectively suppressed.
The fluorine-containing active energy ray-curable resin of the present invention can be used as a main agent of an active energy ray-curable composition by itself and has extremely excellent surface modification performance, and therefore, by using the fluorine-containing active energy ray-curable resin as a fluorine-containing surfactant (fluorine-containing surface modifier) added to the active energy ray-curable composition, excellent stain resistance such as water repellency, oil repellency, and liquid repellency (ink repellency) and excellent leveling property can be imparted to a cured film.
The active energy ray-curable composition of the present invention contains the fluorine-containing active energy ray-curable resin of the present invention, and contains, as a main component thereof, an active energy ray-curable resin (II) or an active energy ray-curable monomer (III) other than the fluorine-containing active energy ray-curable resin. In the active energy ray-curable composition of the present invention, the active energy ray-curable resin (II) and the active energy ray-curable monomer (III) may be used alone or in combination. The fluorine-containing active energy ray-curable resin of the present invention [ hereinafter, this may be referred to as a fluorine-containing active energy ray-curable resin (I) ] functions as a surface modifier in the active energy ray-curable composition.
Examples of the active energy ray-curable resin (II) include: urethane (meth) acrylate resins, unsaturated polyester resins, epoxy (meth) acrylate resins, acrylic acrylate resins, maleimide group-containing resins, Cardo resins, and the like.
Examples of the urethane (meth) acrylate resin include: and resins having a urethane bond and a (meth) acryloyl group obtained by reacting an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound with a hydroxyl group-containing (meth) acrylate compound.
Examples of the aliphatic polyisocyanate compound include: tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1, 5-pentane diisocyanate, 3-methyl-1, 5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, cyclohexyl diisocyanate, etc., and further, examples of the aromatic polyisocyanate compound include: toluene diisocyanate, 4' -diphenylmethane diisocyanate, xylylene diisocyanate, 1, 5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, and the like.
Examples of the aromatic polyisocyanate compound include: 4,4 '-diphenylmethane diisocyanate, 2, 4' -diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, toluene diisocyanate, naphthalene diisocyanate, and the like.
Examples of the hydroxyl group-containing (meth) acrylate compound include: mono (meth) acrylates of 2-membered alcohols such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1, 5-pentanediol mono (meth) acrylate, 1, 6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, hydroxypivalic acid neopentyl glycol mono (meth) acrylate, and the like; 3-membered alcohol mono-or di- (meth) acrylates such as trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerol di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, and hydroxyl group-containing mono-and di (meth) acrylates obtained by modifying a part of alcoholic hydroxyl groups thereof with caprolactone; a compound having a 1-functional hydroxyl group and a (meth) acryloyl group having 3 or more functional groups, such as pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate, or a hydroxyl group-containing polyfunctional (meth) acrylate obtained by further modifying the compound with caprolactone; (meth) acrylate compounds having an oxyalkylene chain such as dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polyethylene glycol mono (meth) acrylate; (meth) acrylate compounds having an oxyalkylene chain with a block structure, such as polyethylene glycol-polypropylene glycol mono (meth) acrylate and polyoxybutylene-polyoxypropylene mono (meth) acrylate; and (meth) acrylate compounds having an oxyalkylene chain of a random structure, such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate.
The reaction of the above-mentioned aliphatic polyisocyanate compound or aromatic polyisocyanate compound with the hydroxyl group-containing (meth) acrylate compound can be carried out by a conventional method, for example, in the presence of a urethanization catalyst. Specific examples of the urethanization catalyst that can be used herein include: amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; phosphines such as triphenylphosphine and triethylphosphine; organotin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate, tin octylate and the like; organic metal compounds such as zinc octoate.
Among these urethane (meth) acrylate resins, those obtained by reacting an aliphatic polyisocyanate compound with a hydroxyl group-containing (meth) acrylate compound are particularly preferable from the viewpoint of excellent transparency of the cured film, good sensitivity to active energy rays, and excellent curability.
Examples of the unsaturated polyester resin include α -unsaturated dibasic acid or an anhydride thereof, dibasic acids other than the dibasic acid or the anhydride thereof, and curable resins obtained by polycondensation of glycols, and examples of α -unsaturated dibasic acid or an anhydride thereof include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof.
Examples of the dibasic acid and the acid anhydride thereof other than the α -unsaturated dibasic acid and the acid anhydride thereof include aromatic saturated dibasic acid, aliphatic dibasic acid, alicyclic saturated dibasic acid, and acid anhydrides thereof, examples of the aromatic saturated dibasic acid and the acid anhydride thereof include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halophthalic anhydride, and esters thereof, examples of the aliphatic dibasic acid, alicyclic saturated dibasic acid, and acid anhydride thereof include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof, and examples of the diol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1, 3-butanediol, 1, 4-butanediol, 2-methylpropane-1, 3-diol, triethylene glycol, tetraethylene glycol, 1, 5-pentanediol, 1, 6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene carbonate, 2-dipropylene glycol, 2-hydroxypropylene oxide, and the like, and oxides thereof can be used in addition.
Examples of the epoxy (meth) acrylate resin include: and epoxy groups of epoxy resins such as bisphenol a type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, and cresol novolac type epoxy resins, and (meth) acrylic acid.
The acrylic acrylate resin is an acrylic resin containing an acryloyl group. Specific examples thereof include: examples of the acrylic resin include a compound obtained by adding acrylic acid to an acrylic resin obtained by copolymerizing glycidyl methacrylate, a compound obtained by adding 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, pentaerythritol triacrylate, or the like to an acrylic resin obtained by copolymerizing 2-acryloyloxyethyl isocyanate, and a resin obtained by adding 2-acryloyloxyethyl isocyanate to an acrylic resin obtained by copolymerizing a hydroxyl group-containing monomer.
Examples of the maleimide group-containing resin include: a 2-functional maleimide carbamate compound obtained by carbamating N-hydroxyethylmaleimide and isophorone diisocyanate, a 2-functional maleimide ester compound obtained by esterifying maleimidoacetic acid and polytetramethylene glycol, a 4-functional maleimide ester compound obtained by esterifying a tetracyclooxirane adduct of maleimidocaproic acid and pentaerythritol, a polyfunctional maleimide ester compound obtained by esterifying maleimidoacetic acid and a polyol compound, and the like. These active energy ray-curable resins may be used alone, or 2 or more kinds may be used in combination.
The Cardo resin is a general term for a resin having a structure in which a cyclic group is directly bonded to a polymer chain, and examples thereof include resins having the following structures.
Figure BDA0002513854360000281
(wherein R represents a hydrogen atom or an alkyl group, R' represents a hydrogen atom or a methyl group, and n is an integer of 0 to 20.)
Examples of the active energy ray-curable monomer (III) include compounds having one or more ethylenically unsaturated bonds.
Examples of the compound having one ethylenically unsaturated bond include: (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycerol mono (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate;
hydroxyl group-containing (meth) acrylates such as hydroxyalkyl (meth) acrylates including 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate, and glycerol mono (meth) acrylate;
aromatic vinyl compounds such as styrene and derivatives thereof; vinyl compounds such as N-vinylpyrrolidone; n-substituted maleimides such as N-cyclohexylmaleimide, N-phenylmaleimide and N-benzylmaleimide;
(meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, cinnamic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylsalic acid, 2- (meth) acryloyloxyethylsmaleic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2- (meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxypropylhydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxybutylsuccinic acid, 2- (meth) acryloyloxybutylhutylhelic acid, crotonic acid, fumaric acid, cinnamic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyl, Polymerizable monomers such as 2- (meth) acryloyloxybutylmethylellic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, and 2- (meth) acryloyloxybutylphthalic acid;
polymerizable monomers obtained by adding lactones such as caprolactone, β -propiolactone, gamma-butyrolactone and valerolactone to acrylic acid, polymerizable monomers obtained by adding succinic acid, maleic acid, phthalic acid or anhydrides thereof to hydroxyalkyl (meth) acrylates;
2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropylsulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, or salts thereof;
polymethyl (meth) acrylate macromonomers, polystyrene macromonomers, poly (meth) acrylic acid 2-hydroxyethyl ester macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, polycaprolactone macromonomers and the like.
Examples of the active energy ray-curable monomer having two ethylenically unsaturated bonds include: 1, 3-butanediol di (meth) acrylate, 1, 3-butanediol (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, bis (acryloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, and the like.
Examples of the active energy ray-curable monomer having three ethylenically unsaturated bonds include: trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, a reaction product of pentaerythritol tri (meth) acrylate and an acid anhydride, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, a reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate and an acid anhydride, a reaction product of caprolactone-modified dipentaerythritol penta (meth) acrylate and an acid anhydride, and the like.
Examples of the active energy ray-curable monomer having four ethylenically unsaturated bonds include: pentaerythritol tetra (meth) acrylate, tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, and the like.
Examples of the active energy ray-curable monomer having 5 or more ethylenically unsaturated bonds include: dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, a reaction product of dipentaerythritol penta (meth) acrylate and an acid anhydride, a reaction product of tripentaerythritol hepta (meth) acrylate and an acid anhydride, caprolactone-modified trimethylolpropane tri (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol hepta (meth) acrylate, pentaerythritol hexa (meth) acrylate, and a reaction product of caprolactone-modified tripentaerythritol octa (meth) acrylate, caprolactone-modified tripentaerythritol hepta (meth) acrylate, and an acid anhydride.
Of these, from the viewpoint of excellent hardness of the cured coating film, multifunctional (meth) acrylates having 3 or more functions such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like are particularly preferable. These active energy ray-curable monomers (III) may be used alone, or 2 or more of them may be used in combination.
In the active energy ray-curable composition of the present invention, when the fluorine-containing active energy ray-curable resin (I) of the present invention is used as the surface modifier, the amount thereof is preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.1 to 5 parts by mass, relative to 100 parts by mass of the total of the active energy ray-curable resin (II) and the active energy ray-curable monomer (III), from the viewpoint of easily achieving sufficient leveling property, water/oil repellency, and stain resistance of the obtained cured film and having an excellent balance with sufficient hardness and transparency after curing of the composition.
The fluorine-containing active energy ray-curable resin (I) of the present invention alone or the active energy ray-curable composition described above can form a cured film by applying to a substrate and then irradiating with an active energy ray, examples of the active energy ray include ionizing radiation such as ultraviolet ray, electron ray, α ray, β ray and γ ray, when the cured film is formed by irradiating with ultraviolet ray as an active energy ray, it is preferable to add a photopolymerization initiator to improve the curability, and if necessary, a photosensitizer may be further added to improve the curability.
Examples of the photopolymerization initiator include intramolecular cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators. Examples of the intramolecular cleavage type photopolymerization initiator include: acetophenone compounds such as diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzildimethylketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone; benzoins such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and the like; acylphosphine oxide compounds such as 2,4, 6-trimethylbenzoin diphenylphosphine oxide and bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide; benzil, methylphenylglyoxylate, and the like.
Examples of the hydrogen abstraction-type photopolymerization initiator include: benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4 ' -dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4 ' -methyl-diphenyl sulfide, acrylated benzophenone, 3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 3,3 ' -dimethyl-4-methoxybenzophenone; thioxanthone compounds such as 2-isopropylthioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone and 2, 4-dichlorothioxanthone; aminobenzophenone compounds such as michelsone and 4, 4' -diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9, 10-phenanthrenequinone, camphorquinone, and the like.
Among the above photopolymerization initiators, 1-hydroxycyclohexyl phenyl ketone and benzophenone are preferable, and 1-hydroxycyclohexyl phenyl ketone is particularly preferable, from the viewpoint of excellent compatibility with the active energy ray-curable resin (II) and the active energy ray-curable monomer (III) in the active energy ray-curable composition. These photopolymerization initiators may be used alone, or 2 or more of them may be used in combination.
Examples of the photosensitizer include: amines such as aliphatic amines and aromatic amines, ureas such as o-tolylthiourea, and sulfur compounds such as sodium diethyldithiophosphate and p-toluenesulfonic acid-s-benzylisothiouronium salt.
The amounts of the photopolymerization initiator and the photosensitizer used are preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and still more preferably 0.3 to 7 parts by mass, respectively, based on 100 parts by mass of nonvolatile components in the active energy ray-curable composition.
Furthermore, depending on the purpose of use, characteristics, and the like, the active energy ray-curable composition of the present invention may be used in combination with various compounding materials for the purpose of adjusting viscosity and refractive index, or adjusting color tone of a coating film, adjusting other coating properties, and coating film physical properties, within a range not impairing the effects of the present invention, for example: examples of the organic solvent include various organic solvents, acrylic resins, phenol resins, polyester resins, polystyrene resins, urethane resins, urea resins, melamine resins, alkyd resins, epoxy resins, polyamide resins, polycarbonate resins, petroleum resins, fluorine resins, and other various resins, PTFE (polytetrafluoroethylene), polyethylene, polypropylene, carbon, titanium oxide, alumina, copper, silica particles, and other various organic or inorganic particles, and further include polymerization initiators, polymerization inhibitors, antistatic agents, defoaming agents, viscosity modifiers, light stabilizers, weather stabilizers, heat stabilizers, antioxidants, rust inhibitors, slip agents, waxes, gloss modifiers, mold release agents, compatibilizers, conductivity modifiers, pigments, dyes, dispersants, dispersion stabilizers, silicones, hydrocarbon surfactants, and the like.
Among the above-mentioned components, the organic solvent is useful for appropriately adjusting the solution viscosity of the active energy ray-curable composition of the present invention, and particularly, when a thin film is to be applied, the film thickness can be easily adjusted. Examples of the organic solvent that can be used herein include: aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, and tert-butanol; esters such as ethyl acetate and propylene glycol monomethyl ether acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. These solvents may be used alone, or 2 or more of them may be used in combination.
The active energy ray for curing the active energy ray-curable composition of the present invention is an ionizing radiation ray such as an ultraviolet ray, an electron ray, α ray, β ray or γ ray as described above, and specific examples of the energy source or curing device include a germicidal lamp, a fluorescent lamp for ultraviolet ray, a carbon arc, a xenon lamp, a high-pressure mercury lamp for copying, a medium-or high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an electrodeless lamp, a metal halide lamp, an ultraviolet ray using natural light or the like as a light source, an electron ray obtained by a scanning type or curtain type electron beam accelerator, and the like.
Among these, ultraviolet rays are particularly preferable, and in order to avoid inhibition of curing by oxygen or the like, ultraviolet rays are preferably irradiated under an inert gas atmosphere such as nitrogen gas. Further, heat may be used in combination as an energy source, and heat treatment may be performed after curing with ultraviolet rays, if necessary.
The method of applying the active energy ray-curable composition of the present invention varies depending on the application, and examples thereof include: a coating method using a gravure coater, a roll coater, a comma coater, a knife coater, an air knife coater, a curtain coater, a kiss coater, a spray coater, a wheel coater (spinner coater), a spin coater, dipping, screen printing, spraying, an applicator, a bar coater, or the like, or a molding method using various dies, or the like.
The cured film of the present invention has excellent stain resistance, scratch resistance, and the like, and therefore, by applying and curing the film on the surface of an article, stain resistance, scratch resistance, and the like can be imparted to the surface of the article. In addition, the cured film of the present invention can maintain the stain-proofing property of the surface of the cured film even after wiping off stains adhering to the surface of the cured film. Further, the fluorine-containing active energy ray-curable resin (I) of the present invention can impart leveling properties to a coating material by being added to the coating material as a surface modifier, and therefore the active energy ray-curable composition of the present invention has high leveling properties.
Examples of articles to which the fluorine-containing active energy ray-curable resin (I) or the active energy ray-curable composition of the present invention can be used to impart antifouling properties include films for polarizing plates of liquid crystal displays (L CD) such as TAC films, various display screens such as Plasma Displays (PDP) and organic E L displays, touch panels, cases or screens of electronic terminals such as mobile phones, transparent protective films for color filters (hereinafter referred to as "CF") for liquid crystal displays, organic insulating films for liquid crystal TFT arrays, optical recording media such as CD, DVD and Blu-ray disks, transfer films for insert molding dies (IMD and IMF), rubber rolls for office equipment such as copiers and printers, glass surfaces of reading units of office equipment such as copiers and scanners, optical lenses and lenses such as cameras, video cameras and glasses, windshields and glass surfaces for watches, windshields and glass surfaces for automobiles and railway vehicles, cover glasses or films for solar cells, various building materials such as decorative sheets, window glasses for houses, woodworking materials such as furniture, artificial/or synthetic leather, cases for home appliances, various articles such as glass (FRP), and various energy ray-curable coatings, and various energy-curable compositions of these compositions can be applied to surfaces of articles, and then applied to ultraviolet rays, and cured, and applied to various articles, and then, the fluorine-containing the present invention can be applied to impart antifouling properties, and the ultraviolet rays, and the surface of these articles, and the present invention can be applied to the articles, and the.
Further, as coating materials which can be added with the fluorine-containing active energy ray-curable resin (I) of the present invention to improve leveling property and impart stain resistance and chemical resistance to a coating film, there are listed hard coating materials for films for polarizing plates of L CD such as TAC film, anti-glare (AG: anti-glare) coating materials or anti-reflection (L R) coating materials, hard coating materials for screens of various displays such as Plasma Display (PDP) and organic E L display, hard coating materials for touch panel, printing inks, ink jet inks or paints, paints or hard coating materials for housings of electronic terminals such as mobile phones, hard coating materials for screens of mobile phones, paints for transparent protective films for CF surfaces, paints for organic insulating films of liquid crystal TFT arrays, hard coating materials for optical recording media such as CD, DVD, Blu-ray disc, hard coating materials for insert molding molds (IMD, IMF), hard coating materials for transfer films for office equipment such as copying machines and printers, coating materials for office equipment such as reading units such as scanner, hard coating materials for optical recording media such as CD, optical recording media such as DVD, IMF, hard coating materials for glass cover plates for glass, coating materials for home glass, coating materials such as plastic coating materials, coating materials for home glass, coating materials for car lenses, coating materials for home glass, coating materials for car glasses, and coating materials for home glass, and synthetic glass, and materials for car lenses, and synthetic glass coating materials for car glasses, and synthetic glass, and the like, and the coating materials for car glass coating.
Further, examples of articles to which scratch resistance (scratch resistance) and stain resistance can be imparted by using the fluorine-containing active energy ray-curable resin (I) or the active energy ray-curable composition of the present invention include prism sheets and diffusion sheets which are backlight members of L CD, and furthermore, by adding the fluorine-containing active energy ray-curable resin (I) of the present invention to a coating material for prism sheets or diffusion sheets, it is possible to improve leveling property of the coating material and impart scratch resistance (scratch resistance) and stain resistance to a coating film of the coating material.
Further, the cured film of the fluorine-containing active energy ray-curable resin (I) of the present invention has a low refractive index, and therefore, can be used as a coating material for a low refractive index layer in an anti-reflection layer for preventing reflection from various display surfaces such as L CD, for example, a fluorescent lamp, and further, by adding the fluorine-containing active energy ray-curable resin (I) of the present invention to a coating material for an anti-reflection layer, particularly a coating material for a low refractive index layer in an anti-reflection layer, it is possible to impart stain resistance to the surface of a coating film while maintaining the low refractive index of the coating film.
Further, other applications in which the fluorine-containing active energy ray-curable resin (I) or the active energy ray-curable composition of the present invention can be used include: optical fiber cladding materials, waveguides, liquid crystal panel sealing materials, various optical sealing materials, optical adhesives, and the like.
In particular, when the active energy ray-curable composition of the present invention is used as an anti-glare coating material for a protective film of a polarizing plate for L CD, it is preferable to add inorganic or organic fine particles such as silica fine particles, acrylic resin fine particles, and polystyrene resin fine particles in the above-described respective compositions in a proportion of 0.1 to 0.5 times the total mass of all the curing components in the active energy ray-curable composition of the present invention, because the anti-glare property is excellent.
When the fluorine-containing active energy ray-curable resin (I) or the active energy ray-curable composition of the present invention is used for an antiglare coating material for a protective film of a polarizing plate for L CD, it can also be applied to a transfer method in which the coating material is brought into contact with a mold having an uneven surface shape before being cured, and then the active energy ray is irradiated from the side opposite to the mold for curing, and the surface of the coating layer is embossed to impart antiglare properties.
The curable composition containing the fluorine-containing active energy ray-curable resin (I) of the present invention can be suitably used as a resist composition. Examples of the resist composition include: photoresist compositions, color resist compositions, and the like. The photoresist composition is formed, for example, from the fluorine-containing active energy ray-curable resin (I) of the present invention and a photoresist containing, for example, an alkali-soluble resin, a radiation-sensitive substance (photosensitive substance), and a solvent.
Here, alkali solubility refers to the property of being dissolved in an aqueous solution (developer) of an alkali compound. Specifically, for example, the following properties can be illustrated: a resin film having a film thickness of 1 μm is formed on a substrate by using a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20 mass%, and when the substrate is immersed in a KOH aqueous solution having a concentration of 0.05 mass% for 1 minute, the resin film having a film thickness of 0.01 μm or more is dissolved.
The alkali-soluble resin is not particularly limited as long as it is soluble in an alkali developer, and a resin having at least 1 acid group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group and a sulfonic acid group, or a salt thereof is preferable.
Examples of the alkali-soluble resin include an alkali-soluble resin that does not have a photocurable property (an alkali-soluble resin that does not contain a photocurable group), an alkali-soluble resin that has a photocurable property (an alkali-soluble resin that contains a photocurable group), and the like.
Examples of the alkali-soluble resin not containing a photocurable group include the following resins.
The alkali-soluble resin (1) is obtained by polymerizing a (meth) acrylic polymerizable monomer having an acid group as an essential component.
An alkali-soluble resin (2) obtained by reacting a polymer having no acidic group, which is obtained by polymerizing a (meth) acrylic polymerizable monomer having a reactive group as an essential component, with a compound having a reactive group reactive with the reactive group and an acid group.
Examples of the photocurable group-containing alkali-soluble resin include the following resins.
The alkali-soluble resin (3) is obtained by adding an unsaturated monocarboxylic acid to at least a part of epoxy groups of a copolymer of an epoxy group-containing (meth) acrylate and another polymerizable monomer, and further performing an addition reaction between at least a part of hydroxyl groups generated by the addition reaction of the unsaturated monocarboxylic acid and an acid anhydride of a polybasic acid.
An epoxy (meth) acrylate resin (4) having a carboxyl group and a polymerizable unsaturated group.
Cardo-type resin (5) having a carboxyl group and a polymerizable unsaturated group.
The above (1) to (5) will be described in detail below.
Examples of the alkali-soluble resin (1) include: an alkali-soluble resin obtained by polymerizing a (meth) acrylic polymerizable monomer having a carboxyl group as an essential component, an alkali-soluble resin obtained by polymerizing a (meth) acrylic polymerizable monomer having a sulfonic acid group as an essential component, and the like. Among them, an alkali-soluble resin obtained by polymerizing a (meth) acrylic polymerizable monomer having a carboxyl group as an essential component is preferable.
Examples of the (meth) acrylic polymerizable monomer having a carboxyl group include: (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, cinnamic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylsalic acid, 2- (meth) acryloyloxyethylsmaleic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2- (meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxypropylhydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxybutylsuccinic acid, 2- (meth) acryloyloxybutylhutylhelic acid, crotonic acid, fumaric acid, cinnamic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyl, Polymerizable monomers such as 2- (meth) acryloyloxybutylmethylellic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, and 2- (meth) acryloyloxybutylphthalic acid;
and polymerizable monomers obtained by adding a lactone such as caprolactone, β -propiolactone, γ -butyrolactone, or valerolactone to acrylic acid, and polymerizable monomers obtained by adding succinic acid, maleic acid, phthalic acid, or an acid anhydride thereof to a hydroxyalkyl (meth) acrylate.
Examples of the (meth) acrylic polymerizable monomer having a sulfonic acid group include: 2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropylsulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, or salts thereof.
When the alkali-soluble resin (1) is prepared, other polymerizable monomers may be used in combination within a range not impairing the effects of the present invention. Examples of the other monomers include: (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycerol mono (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate;
hydroxyl group-containing (meth) acrylates such as hydroxyalkyl (meth) acrylates including 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate, and glycerol mono (meth) acrylate;
aromatic vinyl compounds such as styrene and derivatives thereof; vinyl compounds such as N-vinylpyrrolidone; n-substituted maleimides such as N-cyclohexylmaleimide, N-phenylmaleimide and N-benzylmaleimide;
polymethyl (meth) acrylate macromonomers, polystyrene macromonomers, poly (meth) acrylic acid 2-hydroxyethyl ester macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, polycaprolactone macromonomers and the like. The other polymerizable monomers may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Among the other polymerizable monomers, styrene, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, N-cyclohexylmaleimide, N-benzylmaleimide and N-phenylmaleimide are preferable from the viewpoint of good transparency and less deterioration of heat resistance.
The amount of the other polymerizable monomer is preferably 95% by mass or less, more preferably 85% by mass or less, of the total polymerizable monomer components.
Specific examples of the alkali-soluble resin (1) include: copolymers of (meth) acrylic acid with a hydroxyl-free polymerizable monomer such as methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, or cyclohexylmaleimide, and a hydroxyl-containing polymerizable monomer such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, or 4-hydroxybutyl (meth) acrylate;
copolymers of (meth) acrylic acid with (meth) acrylic esters such as methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-hydroxyethyl methacrylate;
and (2) a copolymer of (meth) acrylic acid and styrene, (a copolymer of (meth) acrylic acid and styrene and α -methylstyrene, (a copolymer of (meth) acrylic acid and cyclohexylmaleimide), among the alkali-soluble resins (1), an alkali-soluble resin in which benzyl (meth) acrylate is used is preferable.
The acid value of the alkali-soluble resin (1) is preferably in the range of 10 to 300, more preferably in the range of 20 to 350, and still more preferably in the range of 30 to 300. The weight average molecular weight (Mw) of the alkali-soluble resin (1) in terms of polystyrene as measured by GPC is preferably in the range of 2,000 to 100,000, more preferably in the range of 3,000 to 70,000, and still more preferably in the range of 4,000 to 50,000.
In the alkali-soluble resin (1), the alkali-soluble resin (1-1) obtained by adding an epoxy group-containing unsaturated compound to a carboxyl group of a carboxyl group-containing alkali-soluble resin obtained by polymerizing a (meth) acrylic polymerizable monomer having a carboxyl group as an essential component can also be used as the alkali-soluble resin having a photocurable group.
Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl acrylate- α -ethyl ester, crotonyl glycidyl ether, glycidyl (iso) crotonate, N- (3, 5-dimethyl-4-glycidyl) benzyl acrylamide, and 4-hydroxybutyl (meth) acrylate glycidyl ether.
Examples of the alicyclic epoxy group contained in the alicyclic epoxy group-containing unsaturated compound include: 2, 3-epoxycyclopentyl, 3, 4-epoxycyclohexyl, 7, 8-epoxy [ tricyclo [5.2.1.0] decan-2-yl ], and the like. Further, as the ethylenically unsaturated group, (meth) acryloyl group is preferable. The alicyclic epoxy group-containing unsaturated compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The addition of the epoxy group-containing unsaturated compound to the carboxyl group portion of the carboxyl group-containing alkali-soluble resin can be carried out by a known method. For example, by reacting a carboxyl group-containing alkali-soluble resin with an epoxy group-containing unsaturated compound in the presence of a tertiary amine such as triethylamine, benzylmethylamine, etc.; quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride, and the like; in the presence of a catalyst such as pyridine, triphenylphosphine or the like, the reaction is carried out in an organic solvent at a reaction temperature of 50-150 ℃ for several hours to several tens of hours, and an epoxy group-containing unsaturated compound can be added to the carboxyl group of the resin.
The acid value of the alkali-soluble resin (1-1) is preferably in the range of 10 to 300, more preferably in the range of 20 to 250, and still more preferably in the range of 30 to 200. The weight average molecular weight of the alkali-soluble resin (1-1) in terms of polystyrene as measured by GPC is preferably in the range of 2,000 to 100,000, more preferably in the range of 4,000 to 50,000, and still more preferably in the range of 5,000 to 30,000.
Among the alkali-soluble resins (1), alkali-soluble resins (1-2) obtained by using, as a polymerizable monomer, an ether dimer or a (meth) acrylate having an alicyclic structure such as an adamantyl group are preferable.
Examples of the ether dimer include: dimethyl 2,2 ' - [ oxybis (methylene) ] bis-2-acrylate, diethyl 2,2 ' - [ oxybis (methylene) ] bis-2-acrylate, di-n-propyl 2,2 ' - [ oxybis (methylene) ] bis-2-acrylate, diisopropyl 2,2 ' - [ oxybis (methylene) ] bis-2-acrylate, di-n-butyl 2,2 ' - [ oxybis (methylene) ] bis-2-acrylate, diisobutyl 2,2 ' - [ oxybis (methylene) ] bis-2-acrylate, di-tert-butyl 2,2 ' - [ oxybis (methylene) ] bis-2-acrylate, di-tert-pentyl 2,2 ' - [ oxybis (methylene) ] bis-2-acrylate, distearyl 2,2 ' - [ oxybis (methylene) ] bis-2-acrylate, Dilauryl 2,2 '- [ oxybis (methylene) ] bis-2-acrylate, di (2-ethylhexyl) 2, 2' - [ oxybis (methylene) ] bis-2-acrylate, di (1-methoxyethyl) 2,2 '- [ oxybis (methylene) ] bis-2-acrylate, di (1-ethoxyethyl) 2, 2' - [ oxybis (methylene) ] bis-2-acrylate, dibenzyl 2,2 '- [ oxybis (methylene) ] bis-2-acrylate, diphenyl 2, 2' - [ oxybis (methylene) ] bis-2-acrylate, dicyclohexyl 2,2 '- [ oxybis (methylene) ] bis-2-acrylate, di (tert-butylcyclohexyl) 2, 2' - [ oxybis (methylene) ] bis-2-acrylate, Bis (dicyclopentadienyl) 2,2 ' - [ oxybis (methylene) ] bis-2-acrylate, bis (tricyclodecanyl) 2,2 ' - [ oxybis (methylene) ] bis-2-acrylate, diisobornyl 2,2 ' - [ oxybis (methylene) ] bis-2-acrylate, diadamantyl 2,2 ' - [ oxybis (methylene) ] bis-2-acrylate, bis (2-methyl-2-adamantyl 2,2 ' - [ oxybis (methylene) ] bis-2-acrylate, and the like. Of these, dimethyl 2,2 '- [ oxybis (methylene) ] bis-2-acrylate, diethyl 2, 2' - [ oxybis (methylene) ] bis-2-acrylate, dicyclohexyl 2,2 '- [ oxybis (methylene) ] bis-2-acrylate, and dibenzyl 2, 2' - [ oxybis (methylene) ] bis-2-acrylate are preferable. These ether dimers may be used in a single amount of 1 kind, or may be used in combination of 2 or more kinds.
The solvent used in the solution polymerization method may be a solvent used in a general radical polymerization reaction. Specifically, examples thereof include: ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform; dimethyl sulfoxide, and the like. These solvents may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
When the polymerizable monomer is polymerized, a polymerization initiator may be used as needed. Examples of the polymerization initiator include: organic peroxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyisopropylcarbonate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, and the like; azo compounds such as 2,2 '-azobis (isobutyronitrile), 1' -azobis (cyclohexanecarbonitrile), 2 '-azobis (2, 4-dimethylvaleronitrile), and dimethyl 2, 2' -azobis (2-methylpropionate). These polymerization initiators may be used alone in 1 kind, or may be used in combination in 2 or more kinds. The amount of the polymerization initiator to be used may be appropriately set depending on the combination of monomers to be used, reaction conditions, the molecular weight of the target alkali-soluble resin, and the like, and is not particularly limited, and is preferably in the range of 0.1 to 15% by mass, and more preferably in the range of 0.2 to 10% by mass, based on the total polymerizable monomer components, since the alkali-soluble resin having a weight average molecular weight of several thousand to several tens of thousands can be obtained without gelation.
The chain transfer agent may be added for the purpose of adjusting the molecular weight, and examples of the chain transfer agent include a thiol chain transfer agent such as n-dodecylmercaptan, thioglycolic acid and methyl thioglycolate, α -methylstyrene dimer, n-dodecylmercaptan and thioglycolic acid which are preferable because of their high chain transfer effect, reduced amount of polymerizable monomers remaining in the reaction system and easy availability, and the amount of the chain transfer agent used may be appropriately set depending on the combination of monomers used, reaction conditions, molecular weight of the target monomer, and the like, and is not particularly limited, and an alkali-soluble resin having a weight average molecular weight of several thousand to several tens of thousands can be obtained without gelation, and is preferably in the range of 0.1 to 15 mass%, more preferably in the range of 0.5 to 10 mass%, based on the total monomers.
The alkali-soluble resin (2) used in the present invention is obtained by reacting a polymer having no acidic group, which is obtained by polymerizing a (meth) acrylic polymerizable monomer having a reactive group as an essential component, with a compound having a group reactive with the reactive group and an acid group. Examples of the alkali-soluble resin (2) include the following alkali-soluble resins.
An alkali-soluble resin obtained by obtaining a polymer using a polymerizable monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate as an essential component and then adding an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, or maleic anhydride.
An alkali-soluble resin obtained by adding a compound having an amino group and an acid group, such as N-methylaminobenzoic acid or N-methylaminophenol, to a polymer obtained from a polymerizable monomer having an epoxy group, such as glycidyl (meth) acrylate, as an essential component.
An alkali-soluble resin obtained by adding a compound having a hydroxyl group and an acid group, such as 2-hydroxybutyric acid, to a polymer obtained by using, as an essential component, a polymerizable monomer having an isocyanate group, such as 2-isocyanatoethyl (meth) acrylate.
The weight average molecular weight of the alkali-soluble resin (2) is preferably in the range of 1,000 to 200,000, more preferably in the range of 2,000 to 10,000, and even more preferably in the range of 2,000 to 50,000 in terms of polystyrene as measured by GPC, since a coating film having excellent heat resistance can be obtained with good formation of the coating film. Further, the alkali-soluble resin (2) may be obtained by using the polymerizable monomer used for the preparation of the alkali-soluble resin (1) in combination, as necessary.
The alkali-soluble resin (3) used in the present invention is obtained by subjecting a copolymer of an epoxy group-containing (meth) acrylate and another polymerizable monomer to addition reaction of an unsaturated monocarboxylic acid to at least a part of the epoxy groups of the copolymer, and further subjecting an anhydride of a polybasic acid to addition reaction of at least a part of the hydroxyl groups generated by the addition reaction of the unsaturated monocarboxylic acid.
Examples of the epoxy group-containing (meth) acrylate include: glycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, (3, 4-epoxycyclohexyl) methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like. Among them, glycidyl (meth) acrylate is preferable. These epoxy group-containing (meth) acrylates may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Further, as for the polymerizable monomer other than the epoxy group-containing (meth) acrylate, which is a raw material of the alkali-soluble resin (3), it is preferable to use a monomer having an alicyclic structure such as a norbornene skeleton or a dicyclopentadiene skeleton because the heat resistance and the mechanical strength of the cured product can be improved.
Examples of the polymerizable monomer include styrene, and vinyl aromatics such as α -, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives of styrene;
dienes such as butadiene, 2, 3-dimethylbutadiene, isoprene and chloroprene;
methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, propynyl (meth) acrylate, phenyl (meth) acrylate, n-propyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (, Naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraquinonyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, methylphenyl (meth) acrylate, 1,1, 1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro-N-propyl (meth) acrylate, perfluoroisopropyl (meth) acrylate, triphenylmethyl (meth) acrylate, isopropylphenyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, piperonyl (meth) acrylate, (meth) acrylates such as 2-hydroxypropyl (meth) acrylate;
(meth) acrylic acid amides such as (meth) acrylic acid amide, N-dimethylamide (meth) acrylic acid, N-diethylamide (meth) acrylic acid, N-dipropylamide (meth) acrylic acid, N-diisopropylamide (meth) acrylic acid, and anthracylamide (meth) acrylic acid; vinyl compounds such as aniline (meth) acrylate, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine and vinyl acetate;
unsaturated dicarboxylic diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate and diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide; n- (meth) acryloylphthalimide, and the like.
Among the other polymerizable monomers, at least 1 monomer selected from styrene, benzyl (meth) acrylate and monomaleimide is preferably used because the heat resistance and mechanical strength of the cured product can be improved. The ratio of styrene, benzyl (meth) acrylate, and monomaleimide is preferably 1 to 70 mol%, more preferably 3 to 50 mol%, based on the total amount of other polymerizable monomers.
The copolymerization reaction of the epoxy group-containing (meth) acrylate and the other polymerizable monomer may be carried out by a known polymerization method such as a solution polymerization method using a radical polymerization initiator. The solvent used is not particularly limited as long as it is inactive to radical polymerization, and a commonly used organic solvent can be used.
The copolymer of the epoxy group-containing (meth) acrylate and the other polymerizable monomer is preferably a copolymer composed of 5 to 90 mol% of a repeating unit derived from the epoxy group-containing (meth) acrylate and 10 to 95 mol% of a repeating unit derived from the other radically polymerizable monomer, more preferably a copolymer composed of 20 to 80 mol% of the former and 80 to 20 mol% of the latter, and still more preferably a copolymer composed of 30 to 70 mol% of the former and 70 to 30 mol% of the latter.
The alkali-soluble resin (3) is obtained by, for example, reacting an epoxy group portion of the copolymer of the epoxy group-containing (meth) acrylate and the other polymerizable monomer with an unsaturated monocarboxylic acid (polymerizable component) and an acid anhydride (alkali-soluble component) of a polybasic acid.
Examples of the unsaturated monocarboxylic acid include monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, and (meth) acrylic acid substituted at the α -position with a halogenated alkyl group, an alkoxy group, a halogen atom, a nitro group, a cyano group, etc., among these, (meth) acrylic acid is preferable, only 1 kind of the unsaturated monocarboxylic acid may be used, or 2 or more kinds may be used in combination, and the use of the unsaturated monocarboxylic acid can impart polymerizability to the alkali-soluble resin (3).
The unsaturated monocarboxylic acid is preferably added to 10 to 100 mol%, more preferably 30 to 100 mol%, and still more preferably 50 to 100 mol% of the epoxy group in the copolymer.
Examples of the acid anhydride of the polybasic acid include: anhydrides of dibasic acids such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride; anhydrides of carboxylic acids having 3 or more carboxyl groups such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, and biphenyl tetracarboxylic anhydride. Among these, tetrahydrophthalic anhydride and succinic anhydride are preferable. The acid anhydride of these polybasic acids may be used alone in 1 kind, or may be used in combination in 2 or more kinds. By using the acid anhydride of the polybasic acid, the alkali-solubility can be imparted to the alkali-soluble resin (3).
The acid anhydride of the polybasic acid is preferably added to 10 to 100 mol%, more preferably 20 to 90 mol%, and still more preferably 30 to 80 mol% of hydroxyl groups formed by adding an unsaturated monocarboxylic acid to the epoxy group of the copolymer.
The weight average molecular weight (Mw) of the alkali-soluble resin (3) in terms of polystyrene, as measured by a permeation gel chromatography (GPC), is preferably within a range of 3,000 to 100,000, and more preferably within a range of 5,000 to 50,000. The dispersity (Mw/Mn) of the alkali-soluble resin (3) is preferably in the range of 2.0 to 5.0.
The aforementioned epoxy (meth) acrylate resin (4) is obtained, for example, by adding α -unsaturated monocarboxylic acid or α -unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety to an epoxy resin and further reacting with a polybasic acid anhydride.
Examples of the epoxy resin include bisphenol A type epoxy resins ("EPIKOTE 828", manufactured by Mitsubishi chemical corporation "," EPIKOTE 1001 "," EPIKOTE 1002 ", and" EPIKOTE 1004 ", and the like), epoxy resins obtained by the reaction of an alcoholic hydroxyl group of a bisphenol A type epoxy resin with epichlorohydrin (as a commercially available product," NER-1302 "(epoxy equivalent 323, softening point 76 ℃") manufactured by Mitsubishi chemical corporation, bisphenol F type resins ("EPIKOTE", "EP-4001", "EP-4002", "EP-4004", and the like), epoxy resins obtained by the reaction of an alcoholic hydroxyl group of a bisphenol F type epoxy resin with epichlorohydrin (as a commercially available product, "NER-7406" (epoxy equivalent 350, softening point 66 ℃), and the like), bisphenol S type epoxy resins, and biphenyl glycidyl ethers ("EPIKOKARIC", manufactured by Mitsubishi chemical corporation, TEXO-PTN-7453 ", and epoxy resins obtained by EPIKOKANZHIZO-N-400", "EPIKOKATE-O-K-O-400", as a commercially available products, EPIKOKATE-NO-P-400 ", and EPIKOKATE-NO-P-NO-P-400", and EPIKOKAT-NO-P-NO-P-NO-P-NO-P-NO-P-NO-.
Examples of the copolymerized epoxy resin include copolymers obtained by copolymerizing a monomer having an epoxy group such as glycidyl (meth) acrylate, (meth) acryloyl methylcyclohexene oxide, or vinylcyclohexene oxide, with a polymerizable monomer having no epoxy group such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, meth) acrylic acid, styrene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, α -methylstyrene, glycerol mono (meth) acrylate, or (meth) acrylate having a polyoxyalkylene chain.
Examples of the (meth) acrylate having a polyoxyalkylene chain include: polyethylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and tetraethylene glycol mono (meth) acrylate; alkoxy polyethylene glycol (meth) acrylates such as methoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, and methoxy tetraethylene glycol (meth) acrylate.
The molecular weight of the copolymerized epoxy resin is preferably in the range of 1,000 to 200,000. The amount of the monomer having an epoxy group used as a raw material of the copolymerized epoxy resin is preferably 10 to 70% by mass, and more preferably 20 to 50% by mass, based on the monomer having no epoxy group.
Examples of commercially available products of the above-mentioned copolymerized epoxy resin include: "CP-15", "CP-30", "CP-50", "CP-20 SA", "CP-510 SA", "CP-50S", "CP-50M", and "CP-20 MA", manufactured by Nikkiso K.K.
The molecular weight of the epoxy resin is preferably in the range of 200 to 200,000, more preferably in the range of 300 to 100,000, in terms of weight average molecular weight in terms of polystyrene measured by GPC, because the coating film formation is good and the gelation of α -unsaturated monocarboxylic acid during the addition reaction can be prevented.
Examples of the α -unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid, etc., preferably acrylic acid and methacrylic acid, and more preferably acrylic acid due to good reactivity.examples of the α -unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion include 2-succinoxyethyl acrylate, 2-maleoxyethyl acrylate, 2-phthalooxyethyl acrylate, 2-hexahydrophthaloyloxyethyl acrylate, 2-succinoxyethyl methacrylate, 2-maleoxyethyl methacrylate, 2-phthaloyloxyethyl methacrylate, 2-hexahydrophthaloyloxyethyl methacrylate, 2-succinoxyethyl crotonate, etc., preferably 2-maleoxyethyl acrylate and 2-phthaloyloxyethyl acrylate, more preferably 2-maleoxyethyl acrylate, and these α -unsaturated monocarboxylic acid and α -unsaturated monocarboxylic acid ester may be used alone or in combination of 1 kind.
α -unsaturated monocarboxylic acid or an ester thereof can be added to an epoxy resin by a known method, and examples thereof include a method of reacting at 50 to 150 ℃ in the presence of an esterification catalyst, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride can be used as the esterification catalyst.
α -unsaturated monocarboxylic acid or its ester is used in an amount of preferably 0.5 to 1.2 equivalents, more preferably 0.7 to 1.1 equivalents, based on 1 equivalent of epoxy group in the epoxy resin as a raw material.
Examples of the polybasic acid anhydride to which the α -unsaturated carboxylic acid or its ester is further added to the epoxy resin to which the acid is added include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic dianhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, biphenyl tetracarboxylic dianhydride, and the like, and among these, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, biphenyl tetracarboxylic dianhydride, and tetrahydrophthalic anhydride and biphenyl tetracarboxylic dianhydride are preferable, and these polybasic acid anhydrides may be used alone in 1 kind or in combination of 2 or more kinds.
The addition reaction of the polybasic add anhydride may be carried out continuously by a known method under the same conditions as the addition reaction of α -unsaturated carboxylic acid or ester thereof, and the amount of the polybasic add anhydride is preferably an amount in the range of 10 to 150, more preferably an amount in the range of 20 to 140, in view of the alkali developability and the good coating film formation.
Further, as the epoxy (meth) acrylate resin having a carboxyl group, a naphthalene-containing resin described in Japanese patent laid-open No. 6-49174, a fluorene-containing resin described in Japanese patent laid-open Nos. 2003-89716, 2003-165830, 2005-325331, 2001-354735, a resin described in Japanese patent laid-open Nos. 2005-126674, 2005-55814, 2004-295084, and the like, and "ACA-200M" manufactured by Daicel Chemical Industries, L td., and the like can be exemplified.
The Cardo resin (5) has a carboxyl group and a polymerizable unsaturated group. Generally, Cardo type resin is a polymer material having various properties such as high heat resistance, solvent solubility, high transparency, high refractive index, low birefringence, high air permeability, and the like, and is used as a binder resin in forming each pixel of a color filter and a black matrix (black matrix), and particularly, can be preferably used as a binder resin in forming a black matrix.
The Cardo type resin is a generic term for a resin having a structure in which a cyclic group is directly bonded to a polymer main chain, and it is considered that the following is expressed by the presence of a bulky substituent on the main chain: (1) rotational constraint of the polymer main chain, (2) morphological control of the main chain and the side chain (constraint), (3) inhibition of intermolecular deposition, (4) increase in aromaticity by introduction of aromatic substituent of the side chain, and the like, and further, as a characteristic of physical properties, higher air permeability is exhibited in addition to high heat resistance, solvent solubility, high transparency, high refractive index, low birefringence, and the like.
The Cardo resin (5) is preferably a resin represented by the following general formula, for example.
Figure BDA0002513854360000481
Wherein X is a group represented by the following chemical formula, Y is a residue obtained by removing a carboxylic anhydride group (-CO-O-CO-) from a dicarboxylic anhydride, and Z is a residue obtained by removing 2 carboxylic anhydride groups from a tetracarboxylic dianhydride. n is an integer of 0 to 20. )
Figure BDA0002513854360000491
Specific examples of the dicarboxylic anhydride from which the above-mentioned Y is derived (the dicarboxylic anhydride before removal of the carboxylic anhydride group) include: maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, and the like.
Specific examples of the tetracarboxylic dianhydride from which Z is derived (tetracarboxylic dianhydride from which 2 carboxylic anhydride groups have not been removed) include: tetracarboxylic acid dianhydrides such as pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyl tetracarboxylic acid dianhydride, and biphenyl ether tetracarboxylic acid dianhydride.
The Cardo resin preferably has a weight average molecular weight (Mw) of 1,000 to 1,000,000, more preferably 3,000 to 50,000, and most preferably 5,000 to 15,000 in terms of polystyrene as measured by weight permeation gel chromatography (GPC).
The alkali-soluble resin may be used alone or in combination of 2 or more of the alkali-soluble resins (1) to (5). The alkali-soluble resin is preferably used in combination with a pigment dispersant described later, because it can form a high-concentration color pixel having excellent adhesion to a substrate without leaving undissolved matter in a non-pixel portion on the substrate. Specifically, a part of the alkali-soluble resin is preferably used in the dispersion treatment step together with a pigment dispersant described later. In this case, the alkali-soluble resin is preferably used in a range of 5 to 200 mass%, more preferably 10 to 100 mass%, with respect to the pigment.
Further, as the alkali-soluble resin, alkali-soluble resins other than the above alkali-soluble resins (1) to (5) can be used. Examples of such resins include: an alkali-soluble resin obtained by using a polymerizable monomer having a phenolic hydroxyl group as an acid group as an essential component, an alkali-soluble resin obtained by using a polymerizable monomer having a sulfonic acid group as an acidic group as an essential component, and the like. Examples of the polymerizable monomer having a phenolic hydroxyl group include: o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, and the like. Further, there may be mentioned: and compounds obtained by substituting 1 or more hydrogen atoms other than the phenolic hydroxyl group and the vinyl group, bonded to the aromatic ring of these monomers, with an alkyl group, an alkoxy group, a halogen atom, a nitro group, a cyano group, or an amide group. Further, examples of the polymerizable monomer having a sulfonic acid group as an acid group include: vinylsulfonic acid, styrenesulfonic acid, (meth) allylsulfonic acid, 2-hydroxy-3- (meth) allyloxypropanesulfonic acid, 2-sulfoethyl (meth) acrylate, or a salt thereof.
When the composition of the present invention is used in a resist composition, the content of the alkali-soluble resin in the composition is preferably in the range of 0.1 to 80% by mass, and more preferably in the range of 1 to 60% by mass, based on the total solid content, because the cured film has good appearance and good adhesion to a substrate.
The radiation-sensitive material (photosensitive material) used in the resist composition may be any material that changes the solubility of the alkali-soluble resin in a developer by mixing with the alkali-soluble resin and irradiating with ultraviolet rays, far ultraviolet rays, excimer laser beams, X-rays, electron rays, ion beams, molecular beams, γ rays, or the like.
Examples of the radiation-sensitive substance include: quinone diazide compounds, diazo compounds, diazide compounds, onium salt compounds, halogenated organic compounds, mixtures of halogenated organic compounds and organometallic compounds, organic acid ester compounds, organic acid amide compounds, organic acid imide compounds, poly (alkylene sulfone) compounds described in Japanese patent application laid-open No. Sho 59-152, and the like.
Examples of the quinonediazide compound include: sulfonyl chlorides of quinone diazide derivatives such as 1, 2-benzoquinone diazide-4-sulfonate, 1, 2-naphthoquinone diazide-5-sulfonate, 2, 1-naphthoquinone diazide-4-sulfonate, 2, 1-naphthoquinone diazide-5-sulfonate, 1, 2-benzoquinone diazide-4-sulfonyl chloride, 1, 2-naphthoquinone diazide-5-sulfonyl chloride, 2, 1-naphthoquinone diazide-4-sulfonyl chloride, and 2, 1-naphthoquinone diazide-5-sulfonyl chloride.
Examples of the diazo compound include: salts of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde, for example, diazonium resin inorganic salts which are reaction products of hexafluorophosphate, tetrafluoroborate, perchlorate or periodate with the above condensates, diazonium resin organic salts which are reaction products of the above condensates with sulfonic acids as described in specification of USP3,300,309, and the like.
Examples of the azide compound and the diazide compound include: azido chalcone, diazido benzylidenemethylcyclohexanone, and azidocinnamylidenephenylacetophenone, as described in Japanese patent application laid-open No. 58-203438, and aromatic azide compounds or aromatic diazide compounds described in Japanese Kokai publication No.12, p1708-1714 (1983).
The halogenated organic compound may be used as long as it is a halide of an organic compound, and specific examples thereof include: halogen-containing oxadiazole compounds, halogen-containing triazine compounds, halogen-containing acetophenone compounds, halogen-containing benzophenone compounds, halogen-containing sulfoxide compounds, halogen-containing sulfone compounds, halogen-containing thiazole compounds, halogen-containing oxazole compounds, halogen-containing triazole compounds, halogen-containing 2-pyrone compounds, halogen-containing aliphatic hydrocarbon compounds, halogen-containing aromatic hydrocarbon compounds, halogen-containing heterocyclic compounds, sulfenyl halide (sulfenyl halide) compounds and the like, and further, for example, there are: compounds used as halogen flame retardants such as tris (2, 3-dibromopropyl) phosphate, tris (2, 3-dibromo-3-chloropropyl) phosphate, chlorotetrabromomethane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenyl allyl ether, tetrachlorobisphenol a, tetrabromobisphenol a, bis (bromoethyl ether) tetrabromobisphenol a, bis (chloroethyl ether) tetrachlorobisphenol a, tris (2, 3-dibromopropyl) isocyanurate, 2-bis (4-hydroxy-3, 5-dibromophenyl) propane, 2-bis (4-hydroxyethoxy-3, 5-dibromophenyl) propane, and compounds used as organochlorine pesticides such as dichlorophenyl trichloroethane.
Examples of the organic acid ester include carboxylic acid esters and sulfonic acid esters. Examples of the organic acid amide include carboxylic acid amides and sulfonic acid amides. Further, examples of the organic acid imide include carboxylic acid imide and sulfonic acid imide. These radiation-sensitive substances may be used alone, or 2 or more kinds may be used in combination.
In the resist composition, the compounding ratio of the radiation-sensitive material is preferably in the range of 10 to 200 parts by mass, more preferably in the range of 50 to 150 parts by mass, relative to 100 parts by mass of the alkali-soluble resin.
Examples of the solvent used in the resist composition include: ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, butyrolactone, etc.; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, pentanol, heptanol, octanol, nonanol, decanol and the like; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dioxane;
alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl ether; esters such as ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, propyl butyrate, ethyl lactate, and butyl lactate; monocarboxylic acid esters such as methyl 2-oxopropionate, ethyl 2-oxopropionate, propyl 2-oxopropionate, butyl 2-oxopropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, and butyl 2-methoxypropionate;
cellosolve esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, and butyl cellosolve acetate, propylene glycols such as propylene glycol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate, diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether, halogenated hydrocarbons such as trichloroethylene, chlorofluorocarbon solvents, HCFC, and HFC, perfluorinated solvents such as perfluorooctane, aromatic solvents such as toluene and xylene, polar solvents such as dimethylacetamide, dimethylformamide, N-methylacetamide, and N-methylpyrrolidone, and the like, and solvents described in published books "solvent handbook" (solvented ポケットハンドブック, eds, Ohmsha, L td.) may be used alone or in combination of 2 or more.
A color resist composition as another specific form of the resist composition is formed, for example, from the fluorine-containing active energy ray-curable resin (I) of the present invention and a color resist containing, for example, an alkali-soluble resin, a polymerizable compound, a colorant.
As the alkali-soluble resin used in the color resist composition, for example, the alkali-soluble resin used in the aforementioned photoresist composition and the like can be used.
The polymerizable compound is not particularly limited as long as it has a photopolymerizable functional group capable of undergoing polymerization or crosslinking reaction by irradiation with active energy rays such as ultraviolet rays. Examples of such polymerizable compounds include: unsaturated carboxylic acids such as (meth) acrylic acid, esters of monohydroxy compounds and unsaturated carboxylic acids, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, esters obtained by esterification of unsaturated carboxylic acids and polycarboxylic acids with the aforementioned aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds and other polyhydroxy compounds, and polymerizable compounds having a urethane skeleton obtained by reacting polyisocyanate compounds with (meth) acryloyl group-containing hydroxy compounds.
Examples of the ester of the aliphatic polyhydric compound and the unsaturated carboxylic acid include: (meth) acrylates such as ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and glycerol (meth) acrylate. Further, there may be mentioned: itaconate esters obtained by substituting itaconic acid for a (meth) acrylic acid moiety of these acrylates, crotonate esters obtained by substituting crotonic acid, maleate esters obtained by substituting maleic acid, and the like.
Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include: hydroquinone di (meth) acrylate, resorcinol di (meth) acrylate, pyrogallol tri (meth) acrylate, and the like. The ester obtained by the esterification reaction of the unsaturated carboxylic acid, the polycarboxylic acid and the polyhydric hydroxyl compound may be a single substance or a mixture. Examples of such esters include: esters derived from (meth) acrylic acid, phthalic acid and ethylene glycol, esters derived from (meth) acrylic acid, maleic acid and diethylene glycol, esters derived from (meth) acrylic acid, terephthalic acid and pentaerythritol, esters derived from (meth) acrylic acid, adipic acid, butanediol and glycerol, and the like.
The polymerizable compound having a urethane skeleton obtained by reacting the polyisocyanate compound with the (meth) acryloyl group-containing hydroxyl compound includes: aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; a reaction product of an aromatic diisocyanate such as tolylene diisocyanate or diphenylmethane diisocyanate and a hydroxyl compound having a (meth) acryloyl group such as 2-hydroxyethyl (meth) acrylate or 3-hydroxy [1,1, 1-tri (meth) acryloyloxymethyl ] propane.
Examples of the polymerizable compound other than the above-mentioned compounds include: (meth) acrylamides such as ethylenebis (meth) acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate.
Further, as the polymerizable compound, a polymerizable compound having an acid group can be used. The polymerizable compound having an acid group is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and is preferably a polyfunctional monomer having an acid group obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. Further, pentaerythritol and dipentaerythritol are particularly preferably used as the aliphatic polyhydric compound. These monomers may be used alone in 1 kind, or may be used in combination in 2 or more kinds. Further, a monomer having an acid group and a monomer having no acid group may be used in combination.
Further, preferable specific examples of the polyfunctional polymerizable compound having an acid group include: a mixture comprising dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and succinate of dipentaerythritol pentaacrylate as the main components is commercially available from Toyo Synthesis Co., Ltd. "ARONIX TO-1382". The polyfunctional polymerizable compound may be used in combination with other polyfunctional polymerizable compounds.
The acid value of the polyfunctional polymerizable compound having an acid group is preferably in the range of 0.1 to 40, more preferably in the range of 5 to 30, because of its favorable developability, curability, and the like. In the case where 2 or more kinds of polyfunctional polymerizable compounds having different acid values are used in combination, or in the case where a polyfunctional polymerizable compound having no acid group is used in combination, it is preferable that the acid value of a mixture obtained by mixing all the polyfunctional polymerizable compounds is within the above range.
In the color resist composition, the content ratio of the polymerizable compound in the total solid content is preferably in the range of 5 to 80% by mass, more preferably in the range of 10 to 70% by mass, and still more preferably in the range of 20 to 50% by mass. The ratio of the polymerizable compound to the colorant described later is preferably 5 to 200% by mass, more preferably 10 to 100% by mass, and still more preferably 20 to 80% by mass.
The colorant may be any pigment or dye, as long as it can be colored. As the pigment, any of an organic pigment and an inorganic pigment can be used. As the organic pigment, pigments having various hues such as a red pigment, a green pigment, a blue pigment, a yellow pigment, a violet pigment, an orange pigment, and a brown pigment can be used. Further, the chemical structure of the organic pigment includes, for example: azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, perylene, etc. The following "c.i." indicates a dye index number.
Examples of the red pigment include: c.i. pigment red 1,2,3,4, 5, 6, 7,8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48: 1. 48: 2. 48: 3. 48: 4. 49, 49: 1. 49: 2. 50: 1. 52: 1. 52: 2. 53, 53: 1. 53: 2. 53: 3. 57 and 57: 1. 57: 2. 58: 4. 60, 63: 1. 63: 2. 64, 64: 1. 68, 69, 81: 1. 81: 2. 81: 3. 81: 4. 83, 88, 90: 1. 101, 101: 1. 104, 108: 1. 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, and the like. Of these, c.i. pigment red 48: 1. 122, 168, 177, 202, 206, 207, 209, 224, 242 or 254, more preferably c.i. pigment red 177, 209, 224 or 254.
Examples of the green pigment include: c.i. pigment green 1,2,4, 7,8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, etc. Of these, c.i. pigment green 7, 36 or 58 is preferable.
Examples of the blue pigment include: c.i. pigment blue 1, 1: 2. 9, 14, 15: 1. 15: 2. 15: 3. 15: 4. 15: 6. 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56: 1. 60, 61: 1. 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc. Of these, c.i. pigment blue 15, 15: 1. 15: 2. 15: 3. 15: 4 or 15: 6, more preferably c.i. pigment blue 15: 6.
examples of the yellow pigment include: c.i. pigment yellow 1, 1: 1.2, 3,4, 5, 6, 9,10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35: 1. 36, 36: 1. 37, 37: 1. 40, 41, 42, 43, 48, 53, 55, 61, 62: 1. 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127: 1. 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191: 1. 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, etc. Of these, c.i. pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, or 185 is preferable, and c.i. pigment yellow 83, 138, 139, 150, or 180 is more preferable.
Examples of the violet pigment include: c.i. pigment violet 1, 1: 1.2, 2: 2. 3, 3: 1. 3: 3. 5, 5: 1. 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc. Among these, c.i. pigment violet 19 or 23 is preferable, and c.i. pigment violet 23 is more preferable.
Examples of the orange pigment include: pigment orange 1,2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 and the like. Of these, c.i. pigment orange 38 or 71 is preferred.
Since each pixel of the 3 primary colors of the color filter used in the liquid crystal display device and the organic E L display device is red (R), green (G), and blue (B), an organic pigment of a color such as yellow, violet, or orange can be used for hue adjustment to improve color reproducibility, with the red pigment, the green pigment, and the blue pigment as main components.
Examples of the inorganic pigment include: barium sulfate, lead sulfate, titanium oxide, yellow lead, indian red, chromium oxide, and the like.
In order to improve the luminance of a color liquid crystal display device and an organic E L display device, the average particle size of the organic pigment is preferably 1 μm or less, more preferably 0.5 μm or less, even more preferably 0.3 μm or less, and the organic pigment is preferably dispersed so as to have the average particle size, and the organic pigment is preferably used, and the average primary particle size of the organic pigment is preferably 100nm or less, more preferably 50nm or less, even more preferably 40nm or less, and particularly preferably in the range of 10 to 30 nm.
The colorant used when the color resist composition is used to form a Black Matrix (BM) is not particularly limited as long as it is black, and examples thereof include: carbon black, lamp black, acetylene black, bone carbon, thermal black, channel black, furnace black, graphite, iron black, titanium black, and the like. In addition, a combination of mixing 2 or more kinds of organic pigments and forming black by color mixing may be used. Among these, carbon black and titanium black are preferable from the viewpoint of light-shielding rate and image characteristics.
Examples of commercially available products of the carbon Black include, for example, MA100, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, #960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #3050, #3150, #3250, # 370, #3750, #3950, #4000, #4010, OI 7 VEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEL 130B, etc., as commercially available products of the carbon Black, such as, Monte VEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVEVELVEVELVEVELVEFAN 200, Sin 300, SinceV 200, SinceRAVELVEVELVEVELVEVELVEVELVEVELVEVELVEFAN 200, Sin VEFAW, Sin 300, Sin VEVELVEVELVEFAN 150, Sin VEFAW, Sin VEFAN 400, Sin VEFAN 150, Sing 200, Sing, SinceV, Sing 300, SinceRAFAN 150, SinceV, SinceRAFAN 400, SinceV 400, SinceRAFAN 400, SinceV 150, SinceV 400, SinceV 150, SinceV 400, SinceV, Since.
Among the above carbon blacks, carbon black coated with a resin is preferably used as a material having a high optical density and a high surface resistivity required for a black matrix of a color filter. The resin-coated carbon black can be obtained by treating a known carbon black by the method described in, for example, Japanese patent application laid-open Nos. 9-26571, 9-71733, 9-95625, 9-238863 and 11-60989.
Further, examples of the method for producing the titanium black include: a method of heating a mixture of titanium dioxide and metallic titanium in a reducing atmosphere for reduction as described in Japanese patent application laid-open No. 49-5432, a method of reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride in a reducing atmosphere containing hydrogen as described in Japanese patent application laid-open No. 57-205322, a method of reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia as described in Japanese patent application laid-open Nos. 60-65069 and 61-201610, and a method of reducing a vanadium compound to titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia as described in Japanese patent application laid-open No. 61-201610. Commercially available titanium blacks include, for example, titanium blacks 10S, 12S, 13R, 13M and 13M-C manufactured by Mitsubishi corporation.
Examples of colorants that can be used to prepare the black pigment include pure victoria Blue (c.i.42595), auramine O (c.i.41000), Cationic Brilliant Yellow (c.i.flavin, basic 13), rhodamine 6GCP (c.i.45160), rhodamine B (c.i.45170), safranine OK 70: 100(c.i.50240), papaver X (c.i.42080), No. 120/raninols Yellow (c.i.21090), raninols Yellow (L ionow) GRO (c.i.90), sy L ER Yellow GF 8 (c.i.05), benzidine Yellow 4-T Yellow (L ionol Yellow) GRO (c.i.21090), and quino Yellow 3655 (c.i.g. 7) and rylol Blue (e.r 7450), Blue pigment (e.g. 7) and orc Blue (r 7450), and orc Blue pigment (e) 11 g. 7 r 3655 g. 7 r 7460).
Examples of other coloring materials that can be mixed and used for the preparation of the black pigment include: c.i. yellow pigment 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, c.i. orange pigment 36, 43, 51, 55, 59, 61, c.i. red pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, c.i. violet pigment 19, 23, 29, 30, 37, 40, 50, c.i. blue pigment 15, 15: 1. 15: 4. 22, 60, 64, c.i. green pigment 7, c.i. brown pigment 23, 25, 26, etc.
When carbon black is used as the black pigment, the average primary particle diameter is preferably in the range of 0.01 to 0.08. mu.m, and more preferably in the range of 0.02 to 0.05. mu.m, because of good developability. Further, the dibutyl phthalate (hereinafter abbreviated as "DBP") absorption amount of the carbon black to be used is preferably 40 to 100cm3A content of 100g, more preferably 50 to 80cm, because of good dispersibility and developability3A range of/100 g. Further, the carbon black used preferably has a specific surface area of 50 to 120m by the BET method2The range of the amount of the polymer is more preferably 60 to 95m in view of good dispersion stability2(ii) a range of/g.
In addition, unlike organic pigments and the like, carbon black exists in a state of a so-called structure in which 1-time particles are fused, and fine pores are sometimes formed on the particle surface by post-treatment. Therefore, in order to express the particle shape of the carbon black, it is generally preferable to measure the DBP absorption amount (JIS K6221) and the specific surface area (JIS K6217) obtained by the BET method as indexes of the structure and the pore size, in addition to the average particle diameter of 1-time particles obtained by the same method as the organic pigment.
Further, as the colorant, a dye may also be used. Examples of such dyes include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, xanthene dyes, triarylmethane dyes, coumarin dyes, tricresyl dyes, anthraquinone dyes, and other dyes.
Examples of the other dyes include: oil-soluble dyes, acid dyes, amine salts of acid dyes, sulfone amide derivatives of acid dyes, and the like, and specific examples thereof include: compounds classified as dyes in The dye index (published by The Society of dyers and Colourists), various dyes described in The notes on dyeing ("dyeing ノート", chromo), and The like.
Examples of the other dyes include: c.i. solvent yellow 4 (hereinafter, the description of c.i. solvent yellow is omitted, and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99; c.i. solvent red 45, 49, 125, 130; c.i. solvent orange 2, 7, 11, 15, 26, 56; c.i. solvent dyes;
c.i. acid yellow 1,3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
c.i. acid red 1,4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
c.i. acid orange 6, 7,8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
c.i. acid violet 6B, 7, 9, 17, 19; and c.i. acid dyes;
c.i. direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
c.i. direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
c.i. direct oranges 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; c.i. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; c.i. direct dyes;
c.i. mordant yellow 5,8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
c.i. mordant red 1,2,3,4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
c.i. mordant oranges 3,4, 5,8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
c.i. mordant violet 1,2,4,5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; and c.i. mordant dyes, and the like.
Among the above-listed colorants, pigments are preferably used in terms of excellent light resistance, weather resistance and fastness of the finally obtained cured film, and pigments and dyes may be used in combination as needed for hue adjustment.
The content ratio of the foregoing pigment to dye is in terms of mass ratio [ pigment: dye ], preferably 1: 99-99: 1, preferably 99: 1-40: 60, more preferably 95: 5-60: 40. by containing the pigment and the dye in such a ratio, a cured film which is easy to optimize the transmission spectrum is easily obtained. Further, a cured film having excellent heat resistance and chemical resistance is easily formed.
The content ratio of the colorant in the color resist composition is preferably 1% by mass or more, more preferably 5 to 80% by mass, and still more preferably 5 to 70% by mass, based on the total solid content.
In addition, when the color resist composition is used for each pixel of red (R), green (G), and blue (B) forming a color filter, the content ratio of the colorant in the color resist composition is preferably in the range of 5 to 60 mass%, and more preferably in the range of 10 to 50 mass% in all solid components.
Further, when the color resist composition is used for forming a black matrix of a color filter, the content ratio of the colorant in the color resist composition is preferably in the range of 20 to 80% by mass, and more preferably in the range of 30 to 70% by mass, in all solid components.
The organic pigment may be subjected to, if necessary, rosin treatment, surface treatment using a pigment derivative or the like having an acidic group or a basic group introduced thereto, grafting treatment on the pigment surface with a polymer compound or the like, micronization treatment by a sulfuric acid micronization method or the like, washing treatment with an organic solvent, water or the like for removing impurities, removal treatment by an ion exchange method or the like for removing ionic impurities, or the like. More preferably, the organic pigment having a uniform particle size can be obtained by, for example, a dispersion treatment with a pigment dispersant.
When the pigment dispersant is used, the amount thereof is preferably 1 part by mass or less, more preferably 0.05 part by mass or more and 0.5 part by mass or less, relative to 1 part by mass of the pigment. When the amount of the pigment dispersant used is within this range, a pigment dispersion liquid (liquid obtained by dispersing in an organic solvent) in a uniformly dispersed state tends to be obtained, and therefore, the amount is preferable.
Examples of the pigment dispersant include: a surfactant; an intermediate or derivative of a pigment; intermediates or derivatives of dyes; and resin dispersants such as polyamide resins, polyurethane resins, polyester resins, and acrylic resins. Among these, graft copolymers having a nitrogen atom, acrylic block copolymers having a nitrogen atom, urethane resin dispersants, and the like are preferable. These dispersants have nitrogen atoms, and therefore the nitrogen atoms have affinity for the pigment surface, and the portion other than the nitrogen atoms increases the affinity for the medium, thereby improving dispersion stability. These dispersants may be used alone, or 2 or more kinds may be used in combination.
Commercially available pigment dispersants include "Efka" series ("Efka 46" and the like) "manufactured by Efka Chemicals B.V., a" Disperbyk "series," BYK "series (" BYK-160 "," BYK-161 "," BYK-2001 "and the like") manufactured by BYK Japan KK, a "SO L SPERSE" series manufactured by L ubrizol Japan L td., a "KP" series manufactured by shin-Etsu chemical Co., Ltd, a "PO L YF L OW" series manufactured by Kyoho chemical Co., Ltd, a "DISPAR L ON" series manufactured by Nanhua chemical Co., Ltd, an "Ajinomoto Fine-Techno Co., Inc." AJIR SPER "series (" AJIR JIR PB-814 "and the like).
Examples of the organic solvent used in the preparation of the pigment dispersion include: acetic acid ester solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxypropionate; aromatic solvents such as toluene, xylene, and methoxybenzene; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether and the like; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic hydrocarbon solvents such as hexane; nitrogen compound solvents such as N, N-dimethylformamide, γ -butyrolactam, and N-methyl-2-pyrrolidone; lactone solvents such as γ -butyrolactone; carbamates and the like. These solvents may be used alone, or 2 or more of them may be used in combination.
Examples of the method for producing the pigment dispersion include: a method in which the colorant is kneaded and dispersed and a method in which the colorant is finely dispersed only, and the like. In the kneading and dispersing step, the colorant, a part of the alkali-soluble resin, and the dispersant as required are mixed and kneaded. The equipment used for kneading may be: the colorant can be dispersed by using a two-roll mill, a three-roll mill, a ball mill, a roller mill (trommel), a dispersing machine, a kneader, a co-kneader, a homogenizer, a mixer, a single-screw or twin-screw extruder, or the like, and dispersing is performed while applying a strong shearing force using these kneading machines. The colorant is preferably prepared by previously pulverizing the particle size by salt milling or the like before the above-mentioned kneading.
On the other hand, in the microdispersion step, the colorant particles can be dispersed to a fine state close to the primary particles by mixing and dispersing a substance obtained by adding a solvent to the composition containing the colorant obtained in the kneading and dispersing step or a substance obtained by mixing a colorant, an alkali-soluble resin, a solvent and, if necessary, the dispersant, with a dispersion medium for fine particles of glass, zirconia or ceramics using a disperser.
In addition, the average particle diameter of the primary particles of the colorant is preferably 10 to 100nm, more preferably 10 to 60nm, from the viewpoint of improving the transmittance, contrast, and the like of the color filter. The average particle diameter of the colorant is measured by a dynamic light scattering particle size distribution meter, and can be measured, for example, by a Nanotrac particle size distribution measuring instrument "UPA-EX 150" or "UPA-EX 250" manufactured by Nikkiso K.K.
The resist composition may contain a photopolymerization initiator.
Examples of the photopolymerization initiator include a bisimidazole compound, an alkylbenzene compound, a triazine compound, an acylphosphine oxide compound, and an oxime compound. Further, the photo cation polymerization initiator (for example, one composed of an onium cation and an anion derived from a Lewis acid) described in Japanese patent application laid-open No. 2008-181087 can be used. Among them, oxime compounds are preferable from the viewpoint of sensitivity.
Examples of the bisimidazole compound include: 2,2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenyl biimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4 ', 5, 5' -tetraphenyl biimidazole (see, for example, Japanese patent application laid-open No. 6-75372, Japanese patent application laid-open No. 6-75373, etc.), 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenyl biimidazole, 2' -bis (2-chlorophenyl) -4,4 ', 5, 5' -tetrakis (alkoxyphenyl) biimidazole, 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetrakis (dialkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4,4 ', 5, 5' -tetrakis (trialkoxyphenyl) biimidazole (see, for example, Japanese patent publication No. 48-38403 and Japanese patent application laid-open No. 62-174204), and imidazole compounds in which the phenyl group at the 4,4 ', 5, 5' -position is substituted with a carbonylalkoxy group (see, for example, Japanese patent application laid-open No. 7-10913). Preferred examples are: 2,2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenylbiimidazole, 2 ' -bis (2, 3-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenylbiimidazole, 2 ' -bis (2, 4-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenylbiimidazole.
Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylmercaptophenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzil dimethyl ketal, oligomers of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, and preferably include 2-methyl-2-morpholino-1- (4-methylmercaptophenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, and so on (BASF 35907, BASF L td. or more.
Examples of the triazine compound include: 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine, and the like.
Examples of the acylphosphine oxide initiator include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide and the like. Commercially available products such as IRGACURE 819 (manufactured by Ciba Japan k.k.) can be used.
Examples of the oxime compound include N-benzoyloxy-1- (4-phenylmercaptophenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylmercaptophenyl) oct-1-one-2-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- { 2-methyl-4- (3, 3-dimethyl-2, 4-dioxopentylmethoxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, and commercially available products such as IRGACURE OXE-01, OXE-02 (manufactured by BASF Japan L td.) and N-1919 (manufactured by ADEKACORPORATION).
Further, as the polymerization initiator having a group capable of initiating chain transfer, a photopolymerization initiator described in Japanese patent application laid-open No. 2002-544205 can be used. Examples of the polymerization initiator having a group capable of initiating chain transfer include compounds represented by the following formulae.
Figure BDA0002513854360000651
Further, as the polymerization initiator, there can be mentioned: benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone, etc.; 10-butyl-2-chloroacridone, benzil, methyl benzoylformate, titanocene compounds, and the like. These are preferably used in combination with a polymerization initiation aid (particularly an amine) described later.
The resist composition may further comprise a polymerization initiation aid. The polymerization initiation aid is a compound used in combination with a photopolymerization initiator to promote polymerization of a polymerizable compound whose polymerization is initiated by the polymerization initiator, or a sensitizer.
Examples of the polymerization initiation aid include: amine compounds, thiazoline compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and the like. Examples of the amine compound include: triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, 4 '-bis (dimethylamino) benzophenone (commonly known as michelsone), 4' -bis (diethylamino) benzophenone, 4 '-bis (ethylmethylamino) benzophenone, and the like, and among them, 4' -bis (diethylamino) benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Baotu chemical Co., Ltd.) can be used.
Examples of the thiazoline compound include the compounds shown below.
Figure BDA0002513854360000661
Examples of the alkoxyanthracene compound include: 9, 10-dimethoxyanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 2-ethyl-9, 10-diethoxyanthracene, 9, 10-dibutoxyanthracene, 2-ethyl-9, 10-dibutoxyanthracene, and the like.
Examples of the thioxanthone compound include: 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.
Examples of the carboxylic acid compound include: phenyl thioglycolic acid, methyl phenyl thioglycolic acid, ethyl phenyl thioglycolic acid, methyl ethyl phenyl thioglycolic acid, two methyl phenyl thioglycolic acid, methoxy phenyl thioglycolic acid, two methoxy phenyl thioglycolic acid, chlorophenyl thioglycolic acid, dichlorophenyl thioglycolic acid, N-phenyl glycine, phenoxy acetic acid, naphthyl thioglycolic acid, N-naphthyl glycine, naphthyloxy acetic acid.
In addition, the resist composition may further contain a polyfunctional thiol compound. The polyfunctional thiol compound is a compound having 2 or more mercapto groups in the molecule. Among these, it is preferable to use a compound having 2 or more mercapto groups adjacent to the aliphatic hydrocarbon group because a pattern can be formed with high sensitivity.
The solvent contained in the resist composition is not particularly limited, and a solvent generally used in this field can be used. For example, the solvent may be selected from ester solvents (solvents containing-COO-, ether solvents other than ester solvents (solvents containing-O-), ether ester solvents (solvents containing-COO-and-O-), ketone solvents other than ester solvents (solvents containing-CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like. These solvents may be used alone, or 2 or more kinds thereof may be used in combination.
Examples of the ester solvent include: methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ -butyrolactone, and the like.
Examples of the ether solvent include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1, 4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.
Examples of the ether ester solvent include: methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, Ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.
Examples of the ketone solvent include: 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone, and the like.
Examples of the alcohol solvent include: methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerol, and the like.
Examples of the aromatic hydrocarbon solvent include: benzene, toluene, xylene, mesitylene, and the like.
Examples of the amide solvent include: n, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and the like.
Among the solvents, organic solvents having a boiling point of 120 ℃ or more and 180 ℃ or less under 1atm are preferable from the viewpoint of coatability and drying property. Of these, propylene glycol monomethyl ether acetate and the like are preferable.
The content of the solvent is preferably 60 to 95% by mass, and more preferably 70 to 90% by mass, based on the resist composition. In other words, the solid content of the resist composition is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass. If the content of the solvent is within the above range, the flatness during coating tends to be good.
In addition, a surfactant other than the fluorine-containing active energy ray-curable resin (I) may be contained within a range not to impair the effects of the present invention. Examples of the surfactant include: silicone surfactants, fluorine surfactants, silicone surfactants having a fluorine atom, surfactants having a fluorine atom and an ethylenically unsaturated bond, and the like.
The resist composition may further contain various additives such as a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, an organic amine compound, and a curing agent, as required.
Examples of the filler include: fine particles of glass, alumina, etc.
Examples of the adhesion promoter include: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxymethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.
Examples of the antioxidant include: 4, 4' -thio-bis (6-tert-butyl-3-methylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], 1, 6-hexanediol-bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 2, 6-di-tert-butyl-4-methylphenol, 2, 6-di-tert-butyl-4-ethylphenol, 2 ' -methylenebis (4-methyl-6-tert-butylphenol), 4 ' -thio-bis (3-methyl-6-tert-butylphenol), 4 ' -butylidene-bis (3-methyl-6-tert-butylphenol), 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3, 5-tris (4-hydroxybenzyl) benzene, and tetrakis [ methylene-3- (3,5 ' -di-tert-butyl-4 ' -hydroxyphenyl propionate) ] methane, and the like.
Examples of the ultraviolet absorber include: benzotriazoles such as 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole; benzophenones such as 2-hydroxy-4-octyloxybenzophenone; benzoates such as 2, 4-di-tert-butylphenyl-3, 5-di-tert-butyl-4-hydroxybenzoate; triazines such as 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-hexyloxyphenol and the like.
Examples of the aggregation inhibitor include sodium polyacrylate and the like.
By adding the organic amine compound, a pixel having excellent adhesion to the substrate can be provided without causing residue on the substrate in the unexposed portion during development. Examples of the organic amine compound include: monoalkylamines such as n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, and n-dodecylamine;
monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, and 4-methylcyclohexylamine; dialkylamines such as methylethylamine, diethylamine, methyl-n-propylamine, ethyl-n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, di-n-pentylamine, and di-n-hexylamine;
monoalkylmonocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine; dicycloalkylamines such as dicyclohexylamine; trialkylamines such as dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyl-di-n-propylamine, ethyl-di-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n-pentylamine, and tri-n-hexylamine;
dialkyl monocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine; monoalkyl dicyclohexylamines such as methyldicyclohexylamine, ethyldicyclohexylamine, and tricyclohexylamine; monoalkylamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, and 6-amino-1-hexanol; monocycloalkylolamines such as 4-amino-1-cyclohexanol; dialkanolamines such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine, etc.;
dicycloalkanolamines such as di (4-cyclohexanol) amine; trialkanolamines such as triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine, and the like; tricycloalkanolamines such as tris (4-cyclohexanol) amine; aminoalkane diols such as 3-amino-1, 2-propanediol, 2-amino-1, 3-propanediol, 4-amino-1, 2-butanediol, 4-amino-1, 3-butanediol, 3-dimethylamino-1, 2-propanediol, 3-diethylamino-1, 2-propanediol, 2-dimethylamino-1, 3-propanediol, and 2-diethylamino-1, 3-propanediol;
aminocycloalkane diols such as 4-amino-1, 2-cyclohexanediol and 4-amino-1, 3-cyclohexanediol, aminocycloalkane carbinols such as 1-aminocyclopentanone methanol and 4-aminocyclopentanone methanol, aminocycloalkane carbinol such as 1-aminocyclohexanone methanol, 4-dimethylaminocyclopentanone methanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol and 4-diethylaminocyclohexanemethanol, aminocarboxylic acids such as β -alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoiso-acetic acid, 3-aminoiso-acetic acid, 2-aminopentanoic acid, 5-aminopentanoic acid, 6-aminocaproic acid, 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid and 4-aminocyclohexanecarboxylic acid;
aromatic amines such as aniline, o-methylaniline, m-methylaniline, p-ethylaniline, p-N-propylaniline, p-isopropylaniline, p-N-butylaniline, p-tert-butylaniline, 1-naphthylamine, 2-naphthylamine, N-dimethylaniline, N-diethylaniline, and p-methyl-N, N-dimethylaniline; aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, and p-diethylaminobenzyl alcohol; aminophenols such as o-aminophenol, m-aminophenol, p-dimethylaminophenol, and p-diethylaminophenol; aminobenzoic acids such as m-aminobenzoic acid, p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid.
When a resin having a carboxyl group is used as the alkali-soluble resin, the curing agent may be a compound that can react with the carboxyl group by heating to crosslink the alkali-soluble resin. Further, a compound which can be polymerized alone to form a cured film can be mentioned. Examples of the compound include an epoxy compound and an oxetane compound.
Examples of the epoxy compound include: bisphenol a-based epoxy resins, hydrogenated bisphenol a-based epoxy resins, bisphenol F-based epoxy resins, hydrogenated bisphenol F-based epoxy resins, novolac-type epoxy resins, aromatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester-based resins, glycidyl amine-based resins, epoxy resins such as epoxy oils, brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than the epoxy resins and the brominated derivatives, epoxides of (co) polymers of butadiene, epoxides of (co) polymers of isoprene, (co) polymers of glycidyl (meth) acrylate, triglycidyl isocyanurate, and the like.
Examples of the oxetane compound include: carbonate dioxetane, xylylene dioxetane, adipate dioxetane, terephthalate dioxetane, cyclohexanedicarboxylic acid dioxetane, and the like.
When an epoxy compound, an oxetane compound or the like is contained as the curing agent, a compound obtained by ring-opening polymerization of an epoxy group of the epoxy compound or an oxetane skeleton of the oxetane compound may be contained. Examples of the compound include: polycarboxylic acids, polycarboxylic acid anhydrides, acid generators, and the like.
Examples of the polycarboxylic acids include: aromatic polycarboxylic acids such as phthalic acid, 3, 4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5, 8-naphthalene tetracarboxylic acid, and 3,3 ', 4, 4' -benzophenone tetracarboxylic acid; aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3, 4-butanetetracarboxylic acid, maleic acid, fumaric acid, and itaconic acid;
alicyclic polycarboxylic acids such as hexahydrophthalic acid, 3, 4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2, 4-cyclopentanetricarboxylic acid, 1,2, 4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid and 1,2,4, 5-cyclohexanetetracarboxylic acid.
Examples of the polycarboxylic acid anhydride include: aromatic polycarboxylic acid anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride; aliphatic polycarboxylic acid anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarboxylic anhydride, maleic anhydride and 1,2,3, 4-butanetetracarboxylic dianhydride; alicyclic polycarboxylic acid anhydrides such as hexahydrophthalic anhydride, 3, 4-dimethyltetrahydrophthalic anhydride, 1,2, 4-cyclopentanetricarboxylic anhydride, 1,2, 4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, nadic anhydride (HIMICANHYDRIDE), 3, 6-endomethylenetetrahydrophthalic anhydride (dianhydro ナジン acid); and carboxylic acid anhydrides containing an ester group such as ethylene glycol bistrimellitic acid and glycerol tristrimellitic anhydride.
As the carboxylic acid anhydrides, those commercially available as curing agents for epoxy resins can be used. Examples of the epoxy resin curing agent include: ADEKA HARDENER EH-700 (manufactured by Asahi Denka Co., Ltd.), RIKACID HH, MH-700 (manufactured by New Japan chemical and physical Co., Ltd.), and the like.
The curing agents may be used alone, or 2 or more kinds thereof may be used in combination.
Further, the resist composition may contain an organic acid having a molecular weight of 1,000 or less. Examples of the organic acid include those disclosed in Japanese patent application laid-open No. 5-343631. Specific examples thereof include: malonic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, citraconic acid, itaconic acid, mesaconic acid, fumaric acid, phthalic acid, acrylic acid, methacrylic acid, preferably listed: malonic acid, oxalic acid, fumaric acid, phthalic acid.
The content of the fluorine-containing active energy ray-curable resin (I) in the resist composition varies depending on the type of the resist composition, the coating method, the target film thickness, and the like, and the above-described effects of the present invention can be exhibited by adding a small amount, and is preferably 0.0001 to 10 parts by mass, more preferably 0.00001 to 5 parts by mass, and further preferably 0.01 to 2 parts by mass, based on 100 parts by mass of the solid content in the resist composition.
The coating method of the resist composition varies depending on the application, and examples thereof include: a coating method using a gravure coater, a roll coater, a comma coater, a knife coater, an air knife coater, a curtain coater, a kiss coater, a spray coater, a wheel coater, a spin coater, dipping, screen printing, spraying, an applicator, a bar coater, electrostatic spraying, or the like, or a forming method using various dies, or the like.
The resist composition is irradiated with light such as visible light or ultraviolet light, whereby the resin changes in physical properties such as solubility, viscosity, transparency, refractive index, conductivity, and ion permeability. Among the active energy ray-curable compositions, resist compositions (such as photoresist compositions and color resist compositions for color filters) are required to have high leveling property. Generally, in photolithography for semiconductors and liquid crystals, a resist composition is applied to a silicon wafer or a glass substrate on which various metals are deposited so as to have a thickness of about 0.01 to 5 μm by spin coating or slit coating. In this case, the variation in the coating film thickness may cause a reduction in the quality of the semiconductor or liquid crystal device or a defect, and the use of the fluorine-containing active energy ray-curable resin (I) of the present invention as an additive for the composition can form a uniform coating film due to its high leveling property, and therefore, the productivity of the semiconductor or liquid crystal device can be improved, and the high functionality can be realized.
From such a viewpoint, the fluorine-containing active energy ray-curable resin (I) of the present invention can be suitably used as a liquid repellent. When used as a liquid repellent, the fluorine-containing active energy ray-curable resin (I) of the present invention is preferably used in a negative resist composition (photosensitive resin composition) containing the alkali-soluble resin as a main component, and is preferably used in an amount of 0.01 to 5.0% by mass based on the total solid content in the composition.
A cured film having a pattern can be obtained by applying a negative resist composition using the fluorine-containing active energy ray-curable resin (I) as a liquid repellent to the surface of a substrate, and exposing and developing the resist composition. The pattern is also referred to as a partition wall, and the fluorine-containing active energy ray-curable resin (I) of the present invention is segregated on the upper portion thereof and cured to exhibit ink repellency, so that when pattern printing is performed by an Inkjet (IJ) method, ink can be uniformly applied to a region surrounded by the partition wall, and moreover, injection of ink into an undesired region beyond the partition wall can be suppressed, and ink can be printed satisfactorily in a desired pattern.
The optical element thus obtained by printing by the IJ method using the partition wall can be suitably used as an organic E L element, a color filter of a liquid crystal element, an organic TFT array element, or the like.
Examples
The present invention will be described below with reference to some examples, but the present invention is not intended to be limited to the embodiments shown in the examples. In the following description and tables, "part" and "%" are based on mass and represent solid components or effective components unless otherwise specified.
Example 1: production of fluorine-containing active energy ray-curable resin (I-I)
A glass flask equipped with a stirrer, a thermometer, a condenser and a dropping device was charged with 50 parts of a perfluoropolyether compound having hydroxyl groups at both ends represented by the following formula (hereinafter abbreviated as "compound (1)", hydroxyl equivalent of 740g/eq, a representing the number of repetitions was 5, b was 7.), 62.5 parts of epichlorohydrin and 20 parts of ethanol. Then, 8.3 parts of a 49% aqueous solution of sodium hydroxide was added dropwise over 2 hours while stirring was started under a nitrogen stream and the internal temperature of the flask was kept at 50 ℃. After the end of the dropwise addition, the temperature was raised to 60 ℃ and stirred for 3 hours, and then, the temperature was returned to room temperature.
Figure BDA0002513854360000741
Subsequently, the reaction solution returned to room temperature was washed with ion-exchanged water. Washing was performed by repeating 2 times an operation of adding 50 parts of ion-exchanged water to the reaction solution, stirring, standing, and separating an aqueous layer by liquid separation. Unreacted epichlorohydrin was distilled off from the washed reaction solution by distillation under reduced pressure, and the filtrate was taken out to obtain 52.2 parts of a compound having a poly (perfluoroalkylene ether) chain represented by the following formula (a1-1) and epoxy groups at both ends thereof (hereinafter, abbreviated as "compound (a 1-1)"). This compound (a1-1) was a transparent liquid, had an epoxy equivalent of 1,112g/eq, and the average value of the number n of repeating units in the following compound (a1-1) was 0.4.
Figure BDA0002513854360000751
Subsequently, 47.4 parts of compound (A1-1), 17.2 parts of bisphenol A diglycidyl ether, 16.0 parts of bisphenol A, and 1000ppm of tetrabutylphosphonium hydroxide (TBPH) were added to a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, and the mixture was heated at 150 ℃ for 40 hours to obtain compound (2) having Mw 28,000. Next, to 161 parts of a solution having NV of 50% obtained by diluting the compound (2) with Propylene Glycol Monomethyl Ether Acetate (PGMEA), 0.03 parts of dibutyltin dilaurate as a urethane-forming catalyst and 0.1 parts of p-methoxyphenol as a polymerization inhibitor were added, stirring was started under an air stream, the temperature was raised to 75 ℃, 19.4 parts of 2-acryloyloxyethyl acrylate was added dropwise over 1 hour, the mixture was stirred at 75 ℃ for 30 minutes, the temperature was raised to 80 ℃ and further stirred for 2 hours, and thereby a reaction was carried out, and as a result, disappearance of an absorption peak near 2360cm "1 derived from an isocyanate group was confirmed by IR spectroscopy. Subsequently, PGMEA was added to obtain a PGMEA solution containing 10% of the fluorine-containing active energy ray-curable resin (1-i).
Example 2: production of fluorine-containing active energy ray-curable resin (2-i)
50 parts of a compound (3) having a hydroxyl equivalent of 754g/eq, wherein a is 5 and b is 7, represented by the same chemical formula as in the above-mentioned compound (1), and 6.5 parts of maleic anhydride were charged into a glass flask equipped with a stirrer, a thermometer, a condenser and a dropping device. Then, stirring was started under a nitrogen stream, and the temperature in the flask was raised to 160 ℃ and stirred for 1 hour. Then, 0.01 part of dibutyltin dilaurate as an esterification catalyst was added thereto, and the temperature in the flask was raised to 170 ℃ and stirred for 5 hours. Then, the temperature was returned to room temperature, whereby 56.5 parts of a compound having a poly (perfluoroalkylene ether) chain represented by the following formula (a5-1) and having carboxyl groups at both ends thereof (hereinafter, abbreviated as "compound (a 5-1)") was obtained. This compound (a5-1) was a transparent liquid and had an acid value of 64.0 mgKOH/g.
Figure BDA0002513854360000752
Subsequently, 50 parts of compound (a5-1), 23 parts of bisphenol A epoxy resin (epoxy equivalent 485g/eq), and 1000ppm of tetrabutylphosphonium hydroxide (TBPH) were added to a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, and heated at 150 ℃ for 30 hours to obtain compound (4) having Mw 53,000. Next, to 146 parts of a 60% NV solution obtained by diluting compound (4) with Propylene Glycol Monomethyl Ether Acetate (PGMEA), 0.02 part of dibutyltin dilaurate as a urethane-forming catalyst, 0.03 part of p-methoxyphenol as a polymerization inhibitor, and 0.20 part of 2, 6-di-t-butyl-p-cresol were added, and stirring was started under an air stream, and the temperature was increased to 75 ℃. Then, 6.7 parts of 2-acryloyloxyethyl acrylate was added dropwise over 1 hour, and after stirring at 75 ℃ for 1 hour, the temperature was raised to 80 ℃ and further stirring was carried out for 4 hours, whereby disappearance of the absorption peak near 2270cm-1 derived from the isocyanate group was confirmed by IR spectroscopy. Finally, PGMEA was added to obtain a PGMEA solution containing 10% of the fluorine-containing active energy ray-curable resin (2-i).
Example 3: production of fluorine-containing active energy ray-curable resin (1-ii)
49.0 parts of compound (a1-1), 16.3 parts of bisphenol F diglycidyl ether, 14.6 parts of bisphenol F, and 1000ppm of tetrabutylphosphonium hydroxide (TBPH) were added to a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, and heated at 150 ℃ for 40 hours to obtain compound (5) having Mw 26,000. Next, to 160 parts of a 50% NV solution obtained by diluting the compound (5) with Propylene Glycol Monomethyl Ether Acetate (PGMEA), 0.03 part of dibutyltin dilaurate as a urethane esterification catalyst and 0.1 part of p-methoxyphenol as a polymerization inhibitor were added, stirring was started under an air stream, the temperature was raised to 75 ℃, 20.1 parts of 2-acryloyloxyethyl acrylate was added dropwise over 1 hour, the mixture was stirred at 75 ℃ for 30 minutes, the temperature was raised to 80 ℃ and further stirred for 2 hours, and thereby a reaction was performed, and as a result, disappearance of an absorption peak near 2360cm "1 derived from an isocyanate group was confirmed by IR spectroscopy. Subsequently, PGMEA was added to obtain a PGMEA solution containing 10% of the fluorine-containing active energy ray-curable resin (1-ii).
Example 4: production of fluorine-containing active energy ray-curable resin (1-iii)
51.4 parts of compound (a1-1), 15.2 parts of 1, 6-naphthalene diglycidyl ether, 12.2 parts of 1, 6-naphthalene diol, and 1000ppm of tetrabutylphosphonium hydroxide (TBPH) were added to a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, and the mixture was heated at 150 ℃ for 40 hours to obtain compound (6) having Mw 27,000. Next, to 158 parts of a 50% NV solution prepared by diluting the compound (6) with Propylene Glycol Monomethyl Ether Acetate (PGMEA), 0.03 parts of dibutyltin dilaurate as a urethane esterification catalyst and 0.1 parts of p-methoxyphenol as a polymerization inhibitor were added, stirring was started under an air stream, the temperature was raised to 75 ℃, then 21.1 parts of 2-acryloyloxyethyl acrylate was added dropwise over 1 hour, the mixture was stirred at 75 ℃ for 30 minutes, the temperature was raised to 80 ℃ and further stirred for 2 hours, and the reaction was carried out, whereby disappearance of an absorption peak near 2360cm "1 derived from an isocyanate group was confirmed by IR spectroscopy. Subsequently, PGMEA was added to obtain a PGMEA solution containing 10% of the fluorine-containing active energy ray-curable resin (1-iii).
Example 5: production of fluorine-containing active energy ray-curable resin (1-iv)
Into a glass flask equipped with a stirrer, thermometer, condenser and dropping device were charged 48.4 parts of compound (A1-1), 17.6 parts of bisphenol A diglycidyl ether, 16.4 parts of bisphenol A and 1000ppm of tetrabutylphosphonium hydroxide (TBPH), and the mixture was heated at 150 ℃ for 40 hours to obtain compound (7) having Mw 28,000. Next, to 165 parts of a solution having NV 50% obtained by diluting compound (7) with Propylene Glycol Monomethyl Ether Acetate (PGMEA), 5.7 parts of succinic anhydride and 3000ppm of triphenylphosphine were added, and the mixture was heated to 110 ℃ and held for 4 hours. After the completion of the reaction was confirmed by the acid value, the reaction mixture was cooled to 75 ℃ and 0.03 part of dibutyltin dilaurate as a urethane catalyst and 0.1 part of p-methoxyphenol as a polymerization inhibitor were added thereto, 19.4 parts of 2-acryloyloxyethyl acrylate was added dropwise under an air stream over 1 hour, the mixture was stirred at 75 ℃ for 30 minutes, and the temperature was increased to 80 ℃ and further stirred for 2 hours, whereby the reaction was carried out, and as a result, disappearance of an absorption peak around 2360cm-1 derived from the isocyanate group was confirmed by IR spectroscopy. Subsequently, PGMEA was added to obtain a PGMEA solution containing 10% of the fluorine-containing active energy ray-curable resin (1-iv).
Comparative Synthesis example 1
20 parts of the above-mentioned compound (a1-1-1), 20 parts of diisopropyl ether as a solvent, 0.02 part of p-methoxyphenol as a polymerization inhibitor and 3.1 parts by mass of triethylamine as a neutralizing agent were put into a glass flask equipped with a stirrer, a thermometer, a condenser and a dropping device, and 2.7 parts by mass of acryloyl chloride was dropped over 1 hour while keeping the temperature in the flask at 10 ℃ with starting stirring under an air stream. After completion of the dropwise addition, the mixture was stirred at 10 ℃ for 1 hour, heated and stirred at 30 ℃ for 1 hour, and then heated to 50 ℃ and stirred for 10 hours to effect a reaction, and disappearance of acryloyl chloride was confirmed by gas chromatography measurement. Then, after adding 40 parts of diisopropyl ether as a solvent, washing was repeated 3 times by the following method: 80 parts of ion-exchanged water was mixed and stirred, and then, the mixture was allowed to stand, and the aqueous layer was separated and removed. Subsequently, 0.02 part of p-methoxyphenol as a polymerization inhibitor and 8 parts of magnesium sulfate as a dehydrating agent were added and the mixture was allowed to stand for 1 day to completely dehydrate the mixture, and then the dehydrating agent was filtered off. Then, the solvent was distilled off under reduced pressure, whereby 21.5 parts of a compound (8) having acryloyl groups at both ends of a perfluoropolyether chain represented by the following formula was obtained.
Figure BDA0002513854360000781
(wherein a is 5 on average and b is 8 on average; it is to be noted that the oxyperfluoromethylene unit and the oxyperfluoroethylene unit are randomly bonded.)
Then, 63 parts by mass of methyl isobutyl ketone as a solvent was put into a glass flask equipped with a stirrer, a thermometer, a condenser and a dropping device, and the temperature was raised to 105 ℃ under stirring in a nitrogen gas stream. Then, 21.5 parts of the compound (8) obtained above, 41.3 parts of 2-hydroxyethyl methacrylate, and 135.4 parts of a polymerization initiator solution prepared by dissolving 9.4 parts of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator in 126 parts of methyl isobutyl ketone were added dropwise to each of the dropping apparatuses, and the flask was kept at 105 ℃ and the solution was dropped over 2 hours. After completion of the dropwise addition, the mixture was stirred at 105 ℃ for 10 hours, and then the solvent was distilled off under reduced pressure, whereby 67.5 parts of a polymer was obtained. Then, 74.7 parts of methyl ethyl ketone as a solvent, 0.1 part of p-methoxyphenol as a polymerization inhibitor, and 0.06 part of dibutyltin dilaurate as a urethane-forming catalyst were added to the polymer obtained above, and 44.8 parts of 2-acryloyloxyethyl acrylate was added dropwise over 1 hour while keeping the temperature at 60 ℃ with stirring under an air stream. After completion of the dropwise addition, the mixture was stirred at 60 ℃ for 1 hour, and then heated to 80 ℃ and stirred for 10 hours, whereby the reaction was carried out, and as a result, disappearance of an absorption peak near 2360cm-1 derived from the isocyanate group was confirmed by IR spectroscopy. Then, 37.4 parts of methyl ethyl ketone was added as a solvent to obtain 224.6 parts of a methyl ethyl ketone solution containing 50% of a polymerizable fluorine-based compound. The molecular weight of the polymerizable fluorine-based compound was measured by GPC (polystyrene equivalent molecular weight), and as a result, the number average molecular weight was 2,200 and the weight average molecular weight was 6,500. The fluorine content was 11%.
< method for Forming coating film >
The coating film of comparative example 2 was prepared in the same manner as in comparative example 1 except that no fluorine-based surfactant was used, except that the coating film of comparative example 2 was prepared in examples 6 to 10 and comparative example 1 by adding UNIDIC RS 20-1603.0 parts by DIC corporation and ARONIX M-4021.2 parts by Toyo Synthesis chemical Co., Ltd, adding the resins obtained in examples and comparative example at solid content ratios of 0.1%, 0.5%, 1.0% and 2.0%, and diluting with PGMEA to prepare a solution of NV 19.5%, dropping the prepared solution 1M L on the center of a 7cm × 7cm glass substrate, spin-coating at 1000rpm for 10 seconds, and then heat-drying at 80 ℃ for 3 minutes to volatilize the solvent, followed by irradiating the dried solution with Ultraviolet (UV) using an ultraviolet curing apparatus (air atmosphere, high pressure mercury lamp, and UV irradiation amount of 0.5 kJ/M2).
< measurement of contact Angle of PGMEA >
The contact angle of PGMEA was measured on the surface of the coating film using a contact angle measuring apparatus ("MODE L CA-W701" manufactured by Kyowa interface science Co., Ltd.) and the results are shown in Table 1, and the contact angle of comparative example 2 (blank) was 15 °.
[ Table 1]
Figure BDA0002513854360000791

Claims (19)

1. A fluorine-containing active energy ray-curable resin characterized by having the following structural unit in 1 molecule: having at least one residue of an alkylene chain (A) having hydroxyl groups at both ends and at least 1 of hydrogen atoms substituted by fluorine atoms, and
at least one residue of a 2-valent phenolic hydroxyl group-containing compound (B) other than the above (A) and/or a residue of a 2-valent carboxylic acid (C),
wherein the alkylene chain includes a chain having an etheric oxygen atom,
the residues are connected by a connecting group shown in the following structural formula (1),
Figure FDA0002513854350000011
in the formula (1), X is a hydrogen atom, a 1-valent organic group (X1) having a polymerizable group, or a 1-valent organic group (X2) having an acid group,
and at least one of the linking groups represented by the structural formula (1) contained in the molecule 1 is a 1-valent organic group (x1) having a polymerizable group.
2. A fluorine-containing active energy ray-curable resin characterized by having the following structural unit in 1 molecule: having at least one residue of an alkylene chain (D) having carboxyl groups at both ends and at least 1 of hydrogen atoms substituted by fluorine atoms or
At least one residue of a reactant of an alkylene chain (A) having hydroxyl groups at both terminals and at least 1 of hydrogen atoms substituted by a fluorine atom and a dicarboxylic anhydride (E), and
at least one residue of a 2-valent hydroxyl group-containing compound (F) other than the (A),
wherein the alkylene chain of the alkylene chain (D) includes a chain having an etheric oxygen atom, the alkylene chain of the alkylene chain (A) includes a chain having an etheric oxygen atom,
the residues are connected by a connecting group shown in the following structural formula (1),
Figure FDA0002513854350000012
in the formula (1), X is a hydrogen atom, a 1-valent organic group (X1) having a polymerizable group, or a 1-valent organic group (X2) having an acid group,
and at least one of the linking groups represented by the structural formula (1) contained in the molecule 1 is a 1-valent organic group (x1) having a polymerizable group.
3. The fluorine-containing active energy ray-curable resin according to claim 1 or 2, wherein the terminal group is a hydrogen atom, a carboxyl group or a glycidyl group.
4. The fluorine-containing active energy ray-curable resin according to any one of claims 1 to 3, wherein a fluorine atom content of the fluorine-containing active energy ray-curable resin is in a range of 3 to 40 mass%.
5. The fluorine-containing active energy ray-curable resin according to any one of claims 1 to 4, wherein a weight average molecular weight of the fluorine-containing active energy ray-curable resin is in a range of 5,000 to 200,000.
6. The fluorine-containing active energy ray-curable resin according to any one of claims 1 to 5, wherein an active energy ray-curable functional group concentration of the fluorine-containing active energy ray-curable resin is in a range of 0.5 to 3.0 mmol/g.
7. The fluorine-containing active energy ray-curable resin according to any one of claims 1 to 6, wherein the alkylene chain (A) having hydroxyl groups at both ends and at least 1 of hydrogen atoms substituted with a fluorine atom, and the alkylene chain (D) having carboxyl groups at both ends and at least 1 of hydrogen atoms substituted with a fluorine atom have a perfluoroalkylene ether chain, wherein the alkylene chain of the alkylene chain (A) includes a chain having an etheric oxygen atom, and the alkylene chain of the alkylene chain (D) includes a chain having an etheric oxygen atom.
8. The fluorine-containing active energy ray-curable resin according to any one of claims 1 to 7, wherein the 2-valent phenolic hydroxyl group-containing compound (B) and the 2-valent hydroxyl group-containing compound (F) are biphenol, bisphenol, binaphthol, or naphthalene diol having a substituent optionally on an aromatic ring.
9. The fluorine-containing active energy ray-curable resin according to any one of claims 1 to 8, wherein the structural formula (1) is a structure represented by the following structural formula (2):
Figure FDA0002513854350000031
in the formula (2), Y is a linking group having a valence of 2, and R is a hydrogen atom or a methyl group.
10. A method for producing a fluorine-containing active energy ray-curable resin, characterized by reacting a compound (a1) having an alkylene chain and an epoxy group, at least 1 of the hydrogen atoms of which is substituted with a fluorine atom, and a 2-valent phenolic hydroxyl group-containing compound (a2) and/or a 2-valent carboxylic acid (a3) as essential raw materials to obtain a reactant, and reacting a compound (a4) having an isocyanate group and an active energy ray-curable functional group with a secondary hydroxyl group in the reactant, wherein the alkylene chain includes a chain having an etheric oxygen atom.
11. A method for producing a fluorine-containing active energy ray-curable resin, characterized by reacting a compound (a5) having an alkylene chain containing an etheric oxygen atom and having at least 1 of hydrogen atoms substituted with a fluorine atom and a carboxyl group or a hydroxyl group, with a 2-valent epoxy compound (a6) as essential raw materials to obtain a reactant, and reacting a compound (a4) having an active energy ray-curable functional group and an isocyanate group with a secondary hydroxyl group in the reactant.
12. The method for producing a fluorine-containing active energy ray-curable resin according to claim 10 or 11, wherein the acid anhydride group-containing compound (a7) is further reacted with a secondary hydroxyl group.
13. A liquid repellent comprising the fluorine-containing active energy ray-curable resin according to any one of claims 1 to 9.
14. An active energy ray-curable resin composition comprising the fluorine-containing active energy ray-curable resin according to any one of claims 1 to 9, and an active energy ray-curable resin (II) or an active energy ray-curable monomer (III) other than the fluorine-containing active energy ray-curable resin.
15. The active energy ray-curable resin composition according to claim 14, wherein the active energy ray-curable resin (II) and the active energy ray-curable monomer (III) are alkali-soluble.
16. The active energy ray-curable resin composition according to claim 14 or 15, further comprising a polymerization initiator.
17. The active energy ray-curable resin composition according to any one of claims 14 to 16, which is a resist composition.
18. A cured film obtained from the active energy ray-curable resin composition according to any one of claims 14 to 17.
19. The cured film of claim 18, which is a partition.
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