TWI796387B - Fluorine-containing active energy ray curable resin, production method thereof, liquid repellant, resin composition containing same, and cured film - Google Patents

Abstract

The present invention provides a fluorine-containing active energy ray curable resin having a resin structure that can easily adjust the fluorine atom content and excellent surface segregation properties, a liquid repellant, a resin composition containing the same, and a cured film. Specifically, a fluorine-containing active energy ray-curable resin having in one molecule a residue of an alkylene chain (A) whose both ends are hydroxyl groups and at least one hydrogen atom is substituted with a fluorine atom, and the aforementioned ( The residue of the divalent phenolic hydroxyl-containing compound (B) and/or the residue of the divalent carboxylic acid (C) other than A); they have the following formula (1) [X is a hydrogen atom, and have polymerizability Organic group (x1) having an acid group or organic group having an acid group (x2)]. At least one is a monovalent organic group (x1) having a polymerizable group.

Description

Fluorine-containing active energy ray curable resin, production method thereof, liquid repellant, resin composition containing same, and cured film

The present invention relates to a fluorine-containing active energy ray curable resin applicable as a surface modifier for surface smoothness or water and oil repellency of a cured film, or as a liquid repellant, a resin composition containing the same, and a cured film.

In the past, fluorine-based surfactants or fluorine-based surface modifiers were used because of their excellent leveling properties, wettability, penetrability, anti-adhesion, sliding properties, water and oil repellency, and antifouling properties. Widely used in various coating materials, surface modifiers, etc.

Applying a coating composed of an active energy ray-curable composition blended with this fluorine-based surfactant or a fluorine-based surface modifier (hereinafter, these are collectively referred to as "fluorine-based surfactant"), The cured film obtained by curing it exhibits excellent surface properties, but on the other hand, due to heating, humidification, exposure to chemicals such as acids and alkalis, cleaning for dirt removal, etc., fluorine-based surfactants One part is easy to detach or volatilize from the surface of the cured film, and as a result, there is a problem of polluting the production line or reducing the antifouling property of the coating film surface.

As a means to solve such a problem, there is provided a fluorine-based surfactant containing an active energy ray hardening function in its structure. A method for firmly bonding the base to the surface of the cured film (for example, refer to Patent Document 1). The fluorine-containing polymerizable resin provided by this patent document 1 is used as a component of the active energy ray-curable resin composition, which reduces problems such as detachment from the surface of the cured film, and can maintain functions such as antifouling properties on the surface for a long period of time. However, in order to make a fluorine-based surfactant with an excellent balance of various properties, in the acrylic copolymer such as the aforementioned Patent Document 1, there is an upper limit to the content of fluorine atoms that can be contained in one molecule, and it is necessary to increase the amount of fluorine to the composition. Add amount.

Furthermore, in recent years, liquid repellents have been known as one use of fluorine-based surfactants. The liquid repellent is used in the manufacture of optical components such as organic EL (Electro-Luminescence, electroluminescent) components, quantum dot displays, TFT (Thin Film Transistor, thin film transistor) arrays, and thin film solar cells. When the organic layer is regarded as dots and pattern printing is performed by the inkjet (IJ) method, a photosensitive resin composition is used to prevent ink mixing between adjacent dots and to uniformly coat ink when dots are formed. , When forming partition walls by lithography, the additive contained in the photosensitive resin composition is also called ink repelling agent (for example, refer to Patent Document 2).

The partition wall must exhibit sufficient liquid repellency on its upper surface, so a fluorine-based surfactant is blended into the photosensitive resin composition, but on the other hand, it is formed through the points surrounded by the partition wall including the side of the partition wall The opening used must have ink affinity. Although the film obtained from the resist composition containing a liquid-repellent agent provided by the aforementioned Patent Document 2 can form such a partition wall, when it is desired to perform finer pattern printing, the liquid-repellent property of the upper surface is insufficient. In addition, due to the transfer of components from the fluorine-based surfactant on the side of the partition wall, the ink affinity of the opening may become insufficient, and higher performance (higher liquid repellency, less addition) is required. The effect shown below) is a liquid repellent.

prior art literature patent documents

Patent Document 1 Japanese Unexamined Patent Application Publication No. 2012-092308

Patent Document 2 Japanese Unexamined Patent Publication No. 2010-140043

In view of the above-mentioned actual situation, the problem to be solved by the present invention is to provide a resin structure with an easily adjusted fluorine atom content, and excellent surface segregation when used as a component of an active energy ray-curable composition, even when used in a small amount. A fluorine-containing active energy ray curable resin capable of exhibiting sufficient leveling properties, water and oil repellency, liquid repellency, etc., a liquid repellant, a resin composition containing the same, and a cured film.

The inventors of the present invention conducted intensive examinations to solve the above-mentioned problems, and as a result found that by using a fluorine-containing active energy ray-curable resin, which has a structural unit having a fluorine-containing alkylene chain connected in a straight chain and composed of other A structural unit composed of a divalent hydrocarbon group, and a structure that includes an active energy ray-curable functional group in the linking part can solve the aforementioned problems and finally complete the present invention.

That is, the present invention provides a fluorine-containing active energy ray-curable resin, a production method thereof, a liquid-repellent agent, a resin composition containing the same, and a cured film thereof. The fluorine-containing active energy ray-curable resin is characterized by having : at least one: a residue of an alkylene chain whose both ends are hydroxyl groups and at least one of the hydrogen atoms is substituted with a fluorine atom (provided that the aforementioned alkylene chain contains an etheric oxygen atom) (A), and At least one: the residue of a divalent phenolic hydroxyl-containing compound (B) other than the aforementioned (A) and/or the residue of a divalent carboxylic acid (C); A structural unit formed by linking groups,

[In formula (1), X is a hydrogen atom, a monovalent organic group (x1) having a polymerizable group, or a monovalent organic group (x2) having an acidic group], and the aforementioned structural formula (1) contained in one molecule At least one of the linking groups shown is a monovalent organic group (x1) having a polymerizable group.

Furthermore, the present invention provides a fluorine-containing active energy ray-curable resin, a production method thereof, a liquid-repellent agent, a resin composition containing the same, and a cured film thereof. The fluorine-containing active energy ray-curable resin is characterized by having A residue having: at least one: an alkylene chain whose both ends are carboxyl groups and at least one of the hydrogen atoms is substituted with a fluorine atom (provided that the aforementioned alkylene chain contains an etheric oxygen atom) (D), Or an alkylene chain whose both ends are hydroxyl groups and at least one of the hydrogen atoms is substituted with a fluorine atom (provided that the aforementioned alkylene chain contains an etheric oxygen atom) (A) and dicarboxylic anhydride (E) The residue of the reactant, and at least one: the residue of the divalent hydroxyl-containing compound (F) other than the aforementioned (A); having a structure in which they are bonded by a linking group represented by the following structural formula (1) unit,

[In formula (1), X is a hydrogen atom, a monovalent organic group (x1) having a polymerizable group, or a monovalent organic group (x2) having an acidic group], and the aforementioned structural formula (1) contained in one molecule At least one of the linking groups shown is a monovalent organic group (x1) having a polymerizable group.

According to the present invention, it is possible to provide a fluorine-containing active energy ray-curable resin that is suitable for obtaining a cured film having a surface excellent in leveling properties, water and oil repellency, and liquid repellency. In addition, the fluorine-containing active energy ray-curable resin system of the present invention can be used as a liquid-repellent agent, and is suitable for the manufacture of optical components such as organic EL elements, quantum dot displays, TFT arrays, and thin-film solar cells that have become increasingly refined in recent years It is a material of active energy ray curable resin composition used for pattern formation.

Fig. 1 is a GPC chart of the fluorine-containing active energy ray curable resin (1-i) obtained in Example 1.

form for carrying out the invention

The fluorine-containing active energy ray-curable resin of the present invention is characterized by having, in one molecule, at least one: an alkylene chain whose both ends are hydroxyl groups and at least one of the hydrogen atoms is substituted with a fluorine atom (but, the above-mentioned alkylene chains) The base chain includes the residue of (A) having an etheric oxygen atom, and at least one: the residue of a divalent phenolic hydroxyl-containing compound (B) other than the aforementioned (A) and/or a divalent carboxylic acid (C ) residues; have their structural units bonded by the linking group shown in the following structural formula (1),

[In formula (1), X is a hydrogen atom, a monovalent organic group (x1) having a polymerizable group, or a monovalent organic group (x2) having an acidic group], and the aforementioned structural formula (1) contained in one molecule At least one of the linking groups shown is a monovalent organic group (x1) having a polymerizable group. Hereinafter, this is also called a fluorine-containing active energy ray curable resin (I-1).

Furthermore, the fluorine-containing active energy ray-curable resin of the present invention is characterized in having, in one molecule: at least one: an alkylene chain whose both ends are carboxyl groups and at least one of the hydrogen atoms is substituted with a fluorine atom (except, The above-mentioned alkylene chain contains an etheric oxygen atom) (D), or an alkylene chain with hydroxyl groups at both ends and at least one of the hydrogen atoms is substituted with a fluorine atom (however, the above-mentioned alkylene chain contains etheric oxygen atom) (A) and the residue of the reactant of dicarboxylic anhydride (E), and at least one: the residue of the divalent hydroxyl-containing compound (F) other than the aforementioned (A); A structural unit bonded by a linking group shown in the following structural formula (1),

[In formula (1), X is a hydrogen atom, a monovalent organic group (x1) having a polymerizable group, or a monovalent organic group (x2) having an acidic group], and the aforementioned structural formula (1) contained in one molecule At least one of the linking groups shown is a monovalent organic group (x1) having a polymerizable group. Hereinafter, this is also called a fluorine-containing active energy ray curable resin (I-2).

In the past, as fluorine-containing compounds such as fluorine-based surfactants, perfluoroalkyl chains (except that the aforementioned alkyl chains include those with etheric oxygen atoms) or perfluoroalkylene chains (except that the aforementioned alkylene groups Many acrylic monomers obtained by copolymerizing an acrylic monomer having an etheric oxygen atom in its chain with a monomer that can be copolymerized with it are provided. In addition, there are also difunctional monomers and other polymerizable monomers having (meth)acryloyl groups at both ends of the perfluoroalkylene chain (however, the aforementioned alkylene chain contains etheric oxygen atoms). Copolymer of monomers. Among them, there is also provided a fluorine-containing active energy ray-curable resin by introducing an active energy ray-curable functional group into a portion corresponding to a side chain in the molecular structure.

The fluorine-containing compound obtained by applying such acrylic copolymerization method has (meth)acrylic acid at both ends of the perfluoroalkylene chain (except that the aforementioned alkylene chain contains an etheric oxygen atom). Since it is a difunctional monomer with an acyl group, gelation will occur if the content of fluorine atoms contained in 1 molecule is increased. Therefore, there is an upper limit to the atomic weight of fluorine that can be introduced in one molecule, and the degree of freedom in design is low. In addition, in order to exhibit a certain effect on the water and oil repellency and leveling properties originally possessed by fluorine atoms, it is necessary to increase the blending amount of the fluorine-containing compound (fluorine-based surfactant) in the composition. Furthermore, since a bifunctional monomer is used and the copolymerization method of an acrylic monomer is adopted, it is necessary to use a production method capable of suppressing gelation, and as a result, the problem of easily including a low molecular weight copolymer also occurs.

In the present invention, in order to solve these problems, a fluorine-containing active energy ray-curable resin having a new structure is designed using industrially easily available raw materials. Furthermore, the so-called "(meth)acryl" in the present invention refers to one or both of methacryl and acryl, and the so-called "(meth)acrylate" refers to nail One or both of acrylate and acrylate, the so-called "(meth)acrylic acid" refers to one or both of methacrylic acid and acrylic acid.

Moreover, the residue in the present invention is specifically an alkylene chain in which both terminals are hydroxyl groups and at least one of the hydrogen atoms is substituted with a fluorine atom (provided that the aforementioned alkylene chain contains an etheric oxygen atom). ) (A), the residue of the divalent phenolic hydroxyl-containing compound (B), and the residue of the divalent hydroxyl-containing compound (F), all refer to the structure in which the hydrogen atom of the hydroxyl group in the structure is removed, that is, the chain Like structural units, and both ends are "O-", as raw materials, each is not limited to the use of alkylene chains whose both ends are hydroxyl groups and at least one of the hydrogen atoms is substituted with a fluorine atom (however, the above-mentioned alkylene chains The base chain contains an etheric oxygen atom) (A), a divalent phenolic hydroxyl-containing compound (B), and a divalent hydroxyl-containing compound (F). Similarly, the residue of a divalent carboxylic acid (C), an alkylene chain in which both ends are carboxyl groups and at least one of the hydrogen atoms is substituted with a fluorine atom (provided that the aforementioned alkylene chain contains an etheric oxygen atom) Those) residues of (D), alkylene chains with hydroxyl groups at both ends and at least one of the hydrogen atoms replaced by fluorine atoms (provided that the aforementioned alkylene chains contain an etheric oxygen atom) (A) The residue of the reactant with dicarboxylic acid anhydride (E) refers to the structure in which the hydrogen atom of the carboxyl group is removed, that is, a chain-like structural unit, and the two ends are "C(=O)O-".

Alkylene chains with hydroxyl groups at both ends and at least one of the hydrogen atoms substituted with fluorine atoms (provided that the alkylene chains contain etheric oxygen atoms) (A), carboxyl groups at both ends and hydrogen atoms An alkylene chain in which at least one of the atoms is substituted with a fluorine atom (provided that the aforementioned alkylene chain contains an etheric oxygen atom) (D) the alkylene chain has a substructure of a fluorine atom, which At least one of the hydrogen atoms in the alkylene chain is replaced by a fluorine atom. It can be a fluoroalkylene chain or a fluoroalkylene ether chain connected through oxygen atoms. In addition, it can be used as an alkene chain The base chain may include a linear, branched or cycloalkylene structure in which a part thereof forms a ring.

Among them, from the viewpoint of ease of handling, a perfluoroalkylene chain having 1 to 6 carbon atoms or a perfluoroalkylene chain having 1 to 6 carbon atoms separated by a perfluoroalkylene chain is preferable. The perfluoroalkylene ether chain in which a plurality of oxygen atoms are linked is preferably a perfluoroalkylene ether chain from the viewpoint of ease of adjustment of the fluorine atom content. Furthermore, it may be a structure in which hydroxyl groups are directly bonded to both ends of the perfluoroalkylene ether chain, or a structure in which hydroxyl groups are bonded via an alkylene chain not having a fluorine atom.

Furthermore, the number of carbon atoms directly bonded to the fluorine atoms contained in one molecule is preferably in the range of 1 to 100. In the case of a perfluoroalkylene chain, the number of carbon atoms is preferably 1 to 6. The range, especially the range of 4~6. In the case of perfluoroalkylene ether chains, the number of carbon atoms directly bonded to the fluorine atoms is preferably 1 to 6, and the number of repetitions is in the range of 1 to 50, especially those with 1 to 3 carbon atoms. The alkylene chain is used as a repeating unit, and the repeating number is a perfluoroalkylene ether chain in the range of 1 to 50.

The residues of (A) in which both ends are hydroxyl groups and at least one of the hydrogen atoms is substituted with fluorine atoms (provided that the alkylene chain contains an etheric oxygen atom) (A) are as described above, and the two When the terminal is "O-", for example, when an alkylene chain in which at least one hydrogen atom is substituted with a fluorine atom is taken as "Rf", this residue is a structural unit represented by "-O-Rf-O-" .

Similarly, the residues of the above-mentioned alkylene chains having carboxyl groups at both ends and at least one of the hydrogen atoms being substituted with fluorine atoms (provided that the aforementioned alkylene chains contain etheric oxygen atoms) (D) are as follows: As mentioned above, if both ends are "C(=O)O-", if the same Rf as above is used, it will have a structure represented by "-O-C(=O)-Rf-C(=O)-O-" unit.

The fluorine-containing active energy ray-curable resin (I-1) of the present invention has a structural unit represented by "-O-Rf-O-" as described above, and a divalent phenolic hydroxyl-containing compound other than the aforementioned (A) (B) residue and/or divalent carboxylic acid (C) residue.

The residue of the divalent phenolic hydroxyl-containing compound (B) is a structural unit represented by "-O-Φ-O-" when the aromatic ring part is taken as "Φ".

The aromatic ring part is composed of a single benzene ring or condensed rings such as naphthalene, anthracene, phenanthrene, acenaphthaphthalene, stilbene, 1,2-benzoacenaphthylene, pyrene, etc. It can also be directly composed of two or more benzene rings or condensed rings. Bonding, or branched or linear alkylene chains (part or all of the hydrogen atoms may be replaced by fluorine atoms), oxygen atoms, sulfur atoms, -NR- (except that R is a hydrogen atom or A structure in which a divalent linking group such as an alkyl group is bonded, and a benzene ring or condensed ring may have a monovalent substituent other than a hydroxyl group. In addition, the residues of the divalent phenolic hydroxyl-containing compound (B) which exist in 1 molecule may all be the same, and may have a different thing.

As the aforementioned substituent, any one is sufficient as long as it is monovalent, and examples thereof include bromine atom, chlorine atom, iodine atom, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, and alkyldisulfide group. group, aryldithio group, amino group, N-alkylamino group, N,N-dialkylamino group, N-arylamino group, N,N-diarylamino group, N-alkyl- N-Arylamino, Acyloxy, Aminoformyloxy, N-Alkylaminoformyloxy, N-Arylaminoformyloxy, N,N-Dialkylaminoformyloxy, N,N-diarylaminoformyloxy, N-alkyl-N-arylaminoformyloxy, alkylendylidene, arylsulfylidene, acylthio, acylamino, N -Alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N',N'-dialkylureido group, N'-arylureido group, N',N'-diaryl ureido, N'-alkyl-N'-aryl ureido, N-alkyl ureido, N-aryl ureido, N'-alkyl-N-aryl ureido , N'-alkyl-N-aryl ureido, N',N'-dialkyl-N-alkyl ureido, N',N'-dialkyl-N-aryl ureido, N' -aryl-N-alkylureido, N'-aryl-N-arylureido, N',N'-diaryl-N-alkylureido, N',N'-diaryl -N-aryl ureido, N'-alkyl-N'-aryl-N-alkyl ureido, N'-alkyl-N'-aryl-N-aryl ureido, alkoxycarbonyl Amine, aryloxycarbonylamine, N-alkyl-N-alkoxycarbonylamine, N-alkyl-N-aryloxycarbonylamine, N-aryl-N-alkoxycarbonylamine Base, N-aryl-N-aryloxycarbonylamino, formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, aminoformyl, N-alkylaminoformyl, N , N-dialkylaminoformyl, N-arylaminoformyl, N,N-diarylaminoformyl, N-alkyl-N-arylaminoformyl, alkylsulfinyl Acyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonic acid group (-SO ₃ H) and its conjugate base (called sulfonate group), alkoxysulfonyl group group, aryloxysulfonyl group, aminosulfinyl group, N-alkylaminesulfinyl group, N,N-dialkylaminesulfinyl group, N-arylaminesulfinyl group, N, N-diarylamine sulfinyl, N-alkyl-N-arylamine sulfinyl, sulfamoyl, N-alkylsulfamoyl, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N,N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphonoyl group (-PO ₃ H ₂ ) and its co- Conjugate base (called phosphonic acid group), dialkylphosphonyl group (-PO ₃ (alkyl) ₂ ) "alkyl = alkyl, the same below", diarylphosphonyl group (-PO ₃ (aryl) ₂ ) "aryl = aryl, the same below", alkyl aryl phosphinoyl (-PO ₃ (alkyl)(aryl)), monoalkyl phosphinoyl (-PO ₃ (alkyl)) and their conjugate bases (called alkylphosphonate), monoarylphosphonyl (-PO ₃ H(aryl)) and its conjugate base (called arylphosphonate), phosphonyloxy (-OPO ₃ H ₂ ) and its conjugated base (called phosphonyloxy group), dialkylphosphonyloxy group (-OPO ₃ H(alkyl) ₂ ), diarylphosphonyloxy group (-OPO ₃ (aryl) ₂ ), alkylarylphosphonyloxy (-OPO ₃ (alkyl)(aryl)), monoalkylphosphonyloxy (-OPO ₃ H(alkyl)) and their conjugate bases (called alkylphosphine Acyloxy), monoarylphosphonyloxy (-OPO ₃ H(aryl)) and its conjugated base (called arylphosphonyloxy), cyano, nitro, aryl, heterocyclyl , silyl, vinyl, 1-propenyl, 1-butenyl, cinnamonyl, 2-chloro-1-vinyl and other alkenyl, ethynyl, 1-propynyl, 1-butynyl, tri Alkynyl groups such as methylsilylethynyl groups, etc.

Among these, structural units derived from biphenol, bisphenol, binaphthol, or naphthalenediol, which may have a substituent on the ring, are preferred from the viewpoint of industrial ease of production by the production method described later. , particularly preferably a structural unit derived from biphenol or bisphenol, most preferably a structural unit derived from bisphenol A or bisphenol F.

Also, the residue of the divalent carboxylic acid (C) in the fluorine-containing active energy ray-curable resin (I- ¹ ) of the present invention is as described above. A structural unit represented by =O)-R ¹ -C(=O)-O-".

The part of ^R1 is not particularly limited, and may be derived from an aliphatic compound or may have an aromatic ring. Examples include malic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, cyclohexane dicarboxylic acid, Aliphatic divalent carboxylic acids such as carboxylic acid, dimer acid, fumaric acid, maleic acid, etc., phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acids, and aromatic rings in these A structural unit of a compound having the aforementioned monovalent substituent, etc., the residues of the divalent carboxylic acid (C) present in one molecule may be composed of the same one, or may have a plurality of different residues. Among them, from the viewpoint of the ease of obtaining industrial raw materials in the production method described later and the excellent balance of properties such as heat resistance and surface segregation of the obtained fluorine-containing active energy ray-curable resin, preferred is Structural units [residues] derived from succinic acid, maleic acid.

The fluorine-containing active energy ray-curable resin (I-2) of the present invention has a structural unit represented by "-O-C(=O)-Rf-C(=O)-O-" or hydroxyl groups at both ends as described above. Residue of a reaction product of an alkylene chain in which at least one of the hydrogen atoms is substituted with a fluorine atom (provided that the aforementioned alkylene chain contains an etheric oxygen atom) (A) and dicarboxylic anhydride (E) , and the residue of a divalent hydroxyl-containing compound (F) other than the aforementioned (A).

The above-mentioned alkylene chain having hydroxyl groups at both ends and at least one of the hydrogen atoms being substituted with fluorine atoms (provided that the above-mentioned alkylene chain contains an etheric oxygen atom) (A) and dicarboxylic anhydride (E) The residue of the reactant is represented by "-OC(=O)-R ² -C(=O)-O-Rf-O-" when the skeleton part of the dicarboxylic acid anhydride (E) is regarded as R ² or a structural unit represented by "-OC(=O)-R ² -C(=O)-O-Rf-OC(=O)-R ² -C(=O)-O-".

The part of ^R2 in the foregoing is not particularly limited, and may be derived from an aliphatic compound, or may have an aromatic ring. For example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride , hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc., may have a plurality of R's in one molecule having the same structure, or may include a plurality of different structures. Among them, from the viewpoint of the ease of obtaining industrial raw materials in the production method described later and the excellent balance of properties such as heat resistance and surface segregation of the obtained fluorine-containing active energy ray-curable resin, preferred is Structural units derived from succinic anhydride, maleic anhydride.

The residue of the divalent hydroxyl-containing compound (F) other than the aforementioned (A) includes the residue of the aforementioned divalent phenolic hydroxyl-containing compound (B) and the residue of the aliphatic diol, and the skeleton part is regarded as In the case of "R ³ ", it is a structural unit represented by "-OR ³ -O-".

The moiety of ^R3 in the foregoing can be exemplified by the same Φ listed as the residue of the aforementioned divalent phenolic hydroxyl-containing compound (B), or an alkylene chain, an oxyalkylene chain, cyclopentane, Cyclic rings such as cyclohexane may have a plurality of R ³ in one molecule may have the same structure, or may include a plurality of different structures. Among them, from the viewpoint of the ease of obtaining industrial raw materials in the production method described later and the excellent balance of properties such as heat resistance and surface segregation of the obtained fluorine-containing active energy ray-curable resin, preferred is An alkylene chain with 1 to 6 carbons.

The fluorine-containing active energy ray-curable resin of the present invention has a linear structure as described above, and is characterized in that it has a structural unit with an oxygen atom forming an ether bond at the end as described in detail above, represented by the following structural formula (1) The structural unit formed by the linking group,

[In formula (1), X is a hydrogen atom, a monovalent organic group (x1) having a polymerizable group, or a monovalent organic group (x2) having an acidic group], and the aforementioned structural formula (1) contained in 1 molecule At least one of the linking groups shown is a monovalent organic group (x1) having a polymerizable group.

Examples of the polymerizable group included in the aforementioned organic group (x1) include a vinyl group or a (meth)acryl group, and from the viewpoint of polymerizability when forming an active energy ray-curable resin composition described later, it is relatively An organic group containing a (meth)acryl group is preferable.

In the above-mentioned structural formula (1), as a method of making X a monovalent organic group (x1) having a polymerizable group, for example, for a secondary hydroxyl group that is a hydrogen atom for X, making an isocyanate group, a carboxyl group, or a carboxyl group A method of reacting an acid halide-based compound with a vinyl or (meth)acryl-based compound.

Among them, from the viewpoint of ease of reaction, a group obtained by reacting a (meth)acrylate having an isocyanate group with respect to the secondary hydroxyl group is preferable, and a group containing the following structural formula (2) is particularly preferable. The linker of the structure shown,

[In the formula (2), Y is a divalent linking group, and R is a hydrogen atom or a methyl group].

Examples of the (meth)acrylate having an isocyanate group include the compounds shown below, including monomers having one isocyanate group and one (meth)acryl group, and monomers having one isocyanate group. A monomer with 2 (meth)acryl groups, a monomer with 1 isocyanate group and 3 (meth)acryl groups, a monomer with 1 isocyanate group and 4 (meth)acryl groups Monomers, monomers having one isocyanate group and five (meth)acryl groups, etc.

[In the formula (3), R' is an alkylene chain with 2 to 4 carbon atoms, R is a hydrogen atom or a methyl group, and n is an integer of 1 to 5].

Specific examples of such isocyanate-containing (meth)acrylate products include: 2-acryloxyethyl isocyanate (trade name: "Karenz AOI" manufactured by Showa Denko Co., Ltd., etc.), 2 -Methacryloxyethyl isocyanate (trade name: "Karenz MOI" manufactured by Showa Denko Co., Ltd., etc.), 1,1-bis(acryloxymethyl)ethyl isocyanate (trade name: Showa Denko Co., Ltd. Co., Ltd. "Karenz BEI", etc.).

Furthermore, the compound which added the hydroxyl group containing (meth)acrylate compound to one isocyanate group of a diisocyanate compound is mentioned. The diisocyanate compounds used in this reaction include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4- Aliphatic diisocyanates such as trimethylhexamethylene diisocyanate, xylylene diisocyanate, m-tetramethyl xylylene diisocyanate, etc.; cyclohexane-1,4-diisocyanate, isophorone diisocyanate Alicyclic diisocyanates such as isocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, etc.; 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyl diisocyanate Aromatic diisocyanates such as phenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluene diisocyanate, etc. These systems may be used alone or in combination of two or more.

X in the aforementioned general formula (1) is at least one of which is a monovalent organic group (x1) having a polymerizable group as described above, but among the plural linking groups present in one molecule, a monovalent organic group having an acidic group is further used in combination. The group (x2) is suitable for use as a curable composition described later, especially a resist composition.

The acid group is not particularly limited, and examples thereof include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and the like. In particular, a linking group having a carboxyl group is preferred from the viewpoint of good alkali solubility and ease of raw material acquisition.

The method for introducing the acid group is not particularly limited, and examples include a method of reacting a compound having an acid anhydride group with respect to a secondary hydroxyl group in which X is a hydrogen atom.

When the fluorine-containing active energy ray-curable resin of the present invention is used as a negative resist composition, the introduction of acid groups is better in alkali developability, and is more suitable for high-definition pattern formation. From such a point of view, although the amount of acid groups introduced is appropriately set according to the application or its performance level, the acid value is preferably in the range of 5~120mgKOH/g, more preferably 7~100mgKOH/g range, and more preferably in the range of 10~80mgKOH/g.

The fluorine-containing active energy ray-curable resin of the present invention has a chain-like structural unit as described above, but its terminal is not particularly limited as it is derived from a compound used as a raw material, but the production method described below When synthesized, the terminal is a hydrogen atom, epoxy propyl group or carboxyl group. These terminal structures are naturally determined according to the feed ratio of raw materials or the reaction sequence, and the plural compounds contained in the resin may be composed of only those having the same terminal structure, or different terminal structures may be used as appropriate. A mixture of compounds of the structure.

Examples of the fluorine-containing active energy ray-curable resin of the present invention include those represented by the following formulae. In addition, in the following formulae, m and n each represent the number of repetitions and are integers of 1 or more. Also, PFPE represents a perfluoroalkylene ether chain.

The content of fluorine atoms in the fluorine-containing active energy ray-curable resin of the present invention can be easily set according to the application or the desired water and oil repellency, liquid repellency, leveling property, etc. In the case of a permanent resin composition, from the viewpoint of compatibility with other resins, compounds, solvents, etc., it is preferably in the range of 1 to 45% by mass, particularly preferably in the range of 3 to 40% by mass.

This fluorine atom content is calculated from the types of raw materials and their ratios when designing the resin, but it may be actually measured by combustion ion chromatography. In the present invention, the latter measured value is preferably within the aforementioned range.

In addition, the number average molecular weight (Mn) and weight average molecular weight (Mw) of the fluorine-containing active energy ray curable resin of the present invention are good in compatibility with other blending components when it becomes a curable resin composition, and it is easy to achieve a high degree of In terms of leveling, water and oil repellency, and liquid repellency, the number average molecular weight (Mn) is preferably in the range of 500 to 100,000, more preferably in the range of 1,000 to 50,000. In addition, the weight average molecular weight (Mw) is preferably in the range of 5,000 to 200,000, more preferably in the range of 10,000 to 100,000. In addition, the number average molecular weight (Mn) and weight average molecular weight (Mw) are based on the gel permeation chromatography (henceforth abbreviated as "GPC") measurement, and are the value of polystyrene conversion. In addition, the measurement conditions of GPC are as follows.

[GPC measurement conditions]

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Co., Ltd.,

Column: Guard column "HHR-H" manufactured by Tosoh Co., Ltd. (6.0mmI.D.×4cm)

+ Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8mmI.D.×30cm)

+ Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8mmI.D.×30cm)

+ Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8mmI.D.×30cm)

+ Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8mmI.D.×30cm)

Detector: ELSD ("ELSD2000" manufactured by ALLTECH)

Data processing: "GPC-8020 Type II data analysis version 4.30" manufactured by Tosoh Co., Ltd.

Sample: what filtered the tetrahydrofuran solution of 1.0 mass % in terms of resin solid content with a microfilter (5 microliters).

Standard sample: According to the aforementioned "GPC-8020 Type II Data Analysis Version 4.30" measurement manual, use the following monodisperse polystyrene with known molecular weight.

(monodisperse polystyrene)

"A-500" manufactured by Tosoh Co., Ltd.

"A-1000" manufactured by Tosoh Co., Ltd.

"A-2500" manufactured by Tosoh Co., Ltd.

"A-5000" manufactured by Tosoh Co., Ltd.

"F-1" manufactured by Tosoh Co., Ltd.

"F-2" manufactured by Tosoh Co., Ltd.

"F-4" manufactured by Tosoh Co., Ltd.

"F-10" manufactured by Tosoh Co., Ltd.

"F-20" manufactured by Tosoh Co., Ltd.

"F-40" manufactured by Tosoh Co., Ltd.

"F-80" manufactured by Tosoh Co., Ltd.

"F-128" manufactured by Tosoh Co., Ltd.

"F-288" manufactured by Tosoh Co., Ltd.

"F-550" manufactured by Tosoh Co., Ltd.

In addition, as the fluorine-containing active energy ray curable resin of the present invention, it is excellent in curability when it becomes a curable resin composition described later, and has excellent long-term water and oil repellency and liquid repellency on the surface of the cured film. The active energy ray-curable functional group concentration is preferably in the range of 0.5 to 3.0 mmol/g.

The method for producing the fluorine-containing active energy ray-curable resin of the present invention is not particularly limited, but from the viewpoint of ease of industrial acquisition of raw materials and excellent production efficiency in production, the following method is preferred. .

Preparation method 1: For a compound (a1) having at least one alkylene chain having a hydrogen atom substituted with a fluorine atom (except that the aforementioned alkylene chain contains an etheric oxygen atom) and an epoxy group (a1), and A compound having an active energy ray hardening functional group and an isocyanate group ( a4) The method of reaction.

Preparation method 2: For the compound (a5) having at least one alkylene chain having a hydrogen atom substituted with a fluorine atom (except that the aforementioned alkylene chain contains an oxygen atom having an etheric nature) and a carboxyl group or a hydroxyl group, and A method in which a compound (a4) having an active energy ray-curable functional group and an isocyanate group is reacted with a secondary hydroxyl group in a reactant obtained by reacting a divalent epoxy compound (a6) as an essential raw material.

First, Preparation Method 1 will be described in detail.

The alkylene chain system in the compound (a1) having at least one hydrogen atom substituted with a fluorine atom (provided that the aforementioned alkylene chain contains an etheric oxygen atom) and an epoxy group Synonymous with the above, that is, preferably a perfluoroalkylene chain with 1 to 6 carbon atoms, or a perfluoroalkylene chain with a repeating structure of perfluoroalkylene chains with 1 to 6 carbon atoms linked by oxygen atoms. Alkyl ether chain.

Examples of the aforementioned compound (a1) include those represented by the following structural formula.

Due to the excellent reactivity of the terminal epoxy group in the aforementioned compound (a1), a linear compound, and at the same time generate a secondary hydroxyl group from the epoxy group in its linking group.

As for the secondary hydroxyl group, a fluorine-containing active energy ray-curable resin can be easily obtained by reacting a compound (a4) having an active energy ray-curable functional group with an isocyanate group as described above.

In this reaction, divalent epoxy compounds (a6) other than the above-mentioned compound (a1) may be used in combination in order to adjust to a desired molecular weight, or to adjust heat resistance, fluorine atom content, and the like.

The terminal structure of the resin obtained in this way, that is, the terminal of the fluorine-containing active energy ray curable resin, can be any one of hydrogen atom, glycidyl group and carboxyl group according to the ratio of the raw materials used.

The usage ratio of the aforementioned compound (a1) to the aforementioned divalent phenolic hydroxyl-containing compound (a2) or divalent carboxylic acid (a3), or the usage ratio of the combined divalent epoxy compound (a6) is not particularly limited. However, for example, the total molar number of the phenolic hydroxyl group or carboxyl group is relatively small relative to the total molar number of the epoxy group in the aforementioned compound (a1) and the epoxy group of the divalent epoxy compound (a6) used in combination if necessary. It is better to use in the range of 0.9~1.1. Since this reaction is a common ring-opening reaction of epoxy groups, it can be easily obtained by stirring at 150~180°C in solvent-free or organic solvents, using catalysts such as quaternary onium salts, imidazoles, TPP, etc. things.

烷、1,3-二

烷、二乙氧基乙烷等之醚化合物、乙腈、二甲亞碸、二甲基甲醯胺等之非質子性極性溶劑等。此等之有機溶劑係可各自單獨使用，另外為了調整極性，亦可適宜併用2種以上。 The organic solvent usable here is not particularly limited, and examples thereof include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, methanol, ethanol, 1-propanol, isopropanol, 1 -Alcohol compounds such as butanol, 2-butanol, 3-butanol, methyl cellosolve, ethyl cellosolve, glycol ethers such as propylene glycol monomethyl ether acetate, tetrahydrofuran, 1,4 -two

Alkane, 1,3-bis

Ether compounds such as alkanes and diethoxyethane, aprotic polar solvents such as acetonitrile, dimethylsulfoxide, and dimethylformamide, etc. These organic solvents can be used individually, respectively, and can also use 2 or more types together suitably in order to adjust polarity.

Examples of the divalent phenolic hydroxyl-containing compound (a2) include resorcinol, catechol, hydroquinone, biphenol, bisphenol A, bisphenol F, bisphenol S, bisphenol AP, bisphenol Phenol AF, bisphenol B, bisphenol BP, bisphenol Z, binaphthol, dihydroxynaphthalene, and compounds having the aforementioned monovalent substituents on these aromatic rings, and the like.

In addition, it may be a compound represented by the following structural formula.

(In the formula, ^R1 is each independently a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, an aryl group, or an aralkyl group, and p is one of 1 to 4 Integer, l is 0 or 1, q is 1 or 2).

These systems may be used alone or in combination of two or more. Among them, it is preferable to use biphenol, bisphenol , binaphthol or naphthalenediol, particularly preferably bisphenol A and bisphenol F.

The aforementioned divalent carboxylic acid (a3) may be either aliphatic or aromatic, and examples thereof include malic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and pimelic acid. , suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, fumaric acid, maleic acid and other aliphatic divalent carboxylic acids, o-phthalic acid Dicarboxylic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acids, and compounds having the aforementioned monovalent substituents on their aromatic rings, and the like. These systems may be used alone or in combination of two or more. Among these, it is preferable to use succinic acid, maleic acid, acid.

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)acryl group is preferably used from the viewpoint of good reactivity, and the above-mentioned Either of them is preferably 2-ethylisocyanate acrylic acid or 2-ethylisocyanate methacrylate. In addition, these systems may be used alone or in combination of two or more. Since this reaction is a reaction between an isocyanate group and a hydroxyl group, for example, amines such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; phosphines such as triphenylphosphine and triethylphosphine can be used. Organotin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate, tin octoate, etc.; urethanization catalysts such as organometallic compounds such as zinc octylate, It is carried out by a method such as adding dropwise the aforementioned compound (a4) to the product having a secondary hydroxyl group obtained above, and heating to 50 to 120°C.

The usage ratio of the aforementioned compound (a4) having active energy ray hardening functional groups and isocyanate groups can be appropriately set according to the target functional group concentration. For example, relative to the secondary hydroxyl group, the molar number of isocyanate groups is better It is used in the range of 0.3~1.0.

Also, the divalent epoxy compound (a6) that can be used together for molecular weight adjustment etc. is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol F type epoxy Benzene type epoxy resin, tetramethylbiphenyl type epoxy resin, dihydroxynaphthalene type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, etc. In addition, an epoxidized compound of an alkylene oxide adduct of bisphenols may be used.

Furthermore, when it becomes the curable composition for resists mentioned later, it is preferable to further introduce an acid group. This acid group can be obtained easily by reacting an acid anhydride group-containing compound (a7) with respect to the secondary hydroxyl group which has not reacted with an isocyanate group, for example.

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, etc. may be used alone or in combination of two or more. From the viewpoint of ease of reaction, it is preferable to use succinic anhydride and maleic anhydride.

Next, Manufacturing Method 2 will be described in detail.

In Preparation Method 2, for the compound (a5) having at least one alkylene chain having a hydrogen atom substituted with a fluorine atom (provided that the aforementioned alkylene chain contains an etheric oxygen atom) and a carboxyl group or a hydroxyl group , The secondary hydroxyl group in the reactant obtained by reacting with divalent epoxy compound (a6) as an essential raw material, reacts the compound (a4) having active energy ray hardening functional group and isocyanate group, and introduces active energy ray hardening However, the divalent epoxy compound used at this time, the compound (a4) having an active energy ray-curable functional group and an isocyanate group can include the same compounds as those used in Preparation Method 1, and the preferred ones are also the same.

The alkylene chain system in the compound (a5) having at least one alkylene chain substituted with a fluorine atom (provided that the aforementioned alkylene chain contains an etheric oxygen atom) and a carboxyl group or a hydroxyl group Synonymous with the above, that is, preferably a perfluoroalkylene chain with 1 to 6 carbon atoms, or a perfluoroalkylene chain with a repeating structure of perfluoroalkylene chains with 1 to 6 carbon atoms linked by oxygen atoms. Alkyl ether chain.

Examples of the aforementioned compound (a5) include those represented by the following structural formula. In the following formula, PFPE is the same as above. As a method of introducing a carboxyl group at the terminal, it can be easily obtained by reacting a dicarboxylic anhydride with respect to a compound having a hydroxyl group at the terminal.

The reaction between the carboxyl group or hydroxyl group in the compound (a5) and the divalent epoxy compound (a6) is the usual ring-opening reaction of the epoxy group. Through this reaction, the compound (a5) is obtained by linking the linking group with the secondary hydroxyl group. A reactant with the structure of compound (a6). For this secondary hydroxyl group, active energy ray-curable functional groups and acid groups can be introduced by the same raw materials and reactions as in Preparation method 1.

In addition, in order to adjust to a desired molecular weight, or to adjust heat resistance, fluorine atom content, etc., the aforementioned divalent carboxylic acid (a3) other than the aforementioned compound (a5) or the aforementioned divalent phenolic hydroxyl group may be used in combination. Compound (a2).

The terminal structure of the resin obtained in this way, that is, the terminal of the fluorine-containing active energy ray curable resin, can be any one of hydrogen atom, glycidyl group and carboxyl group according to the ratio of the raw materials used.

Since this reaction is a common ring-opening reaction of epoxy groups, it can be easily obtained by stirring at 150~180°C in solvent-free or organic solvents, using catalysts such as quaternary onium salts, imidazoles, TPP, etc. things.

烷、1,3-二

烷、二乙氧基乙烷等之醚化合物、乙腈、二甲亞碸、二甲基甲醯胺等之非質子性極性溶劑等。此等之有機溶劑係可各自單獨使用，另外為了調整極性，亦可適宜併用2種以上。 The organic solvent usable here is not particularly limited, and examples thereof include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, methanol, ethanol, 1-propanol, isopropanol, 1 -Alcohol compounds such as butanol, 2-butanol, 3-butanol, methyl cellosolve, ethyl cellosolve, glycol ethers such as propylene glycol monomethyl ether acetate, tetrahydrofuran, 1,4 -two

Alkane, 1,3-bis

Ether compounds such as alkanes and diethoxyethane, aprotic polar solvents such as acetonitrile, dimethylsulfoxide, and dimethylformamide, etc. These organic solvents can be used individually, respectively, and can also use 2 or more types together suitably in order to adjust polarity.

The subsequent reaction system is the same as that of Preparation method 1. Each of the above-mentioned reactions proceeds stoichiometrically, and the compounds used as raw materials hardly remain in the system in an unreacted state, so it is characteristic that low-molecular-weight compounds are less likely to be contained in the obtained resin. Therefore, when the obtained resin is used in the same manner as conventional fluorine-based surfactants, volatilization during curing, detachment from the surface of the cured film, and the like can be effectively suppressed.

Although the fluorine-containing active energy ray-curable resin of the present invention can be used as the main ingredient of an active energy ray-curable composition, it can be used as an active energy ray-curable composition in order to have extremely excellent surface modification performance. The use of fluorine-based surfactants (fluorine-based surface modifiers) added to the cured film can give the cured film excellent water repellency, oil repellency, liquid repellency (ink repellency) and other antifouling properties or excellent leveling properties .

The active energy ray-curable composition of the present invention is blended with the fluorine-containing active energy ray-curable resin of the present invention, but contains active energy ray-curable resins other than the aforementioned fluorine-containing active energy ray-curable resin as its main component. Resin (II) or active energy ray-curable monomer (III). Furthermore, 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. Furthermore, the fluorine-containing active energy ray-curable resin of the present invention [hereinafter, also referred to as fluorine-containing active energy ray-curable resin (I)] is contained in the active energy ray-curable composition as a surface modifying agent. Have an effect.

The aforementioned active energy ray curable resin (II) includes, for example, urethane (meth)acrylate resin, unsaturated polyester resin, epoxy (meth)acrylate resin, acryl acrylate resin, Resins, maleimide group-containing resins, cardo-type resins, and the like.

The aforementioned urethane (meth)acrylate resins include, for example, urethane-containing resins obtained by reacting aliphatic polyisocyanate compounds or aromatic polyisocyanate compounds with hydroxyl-containing (meth)acrylate compounds. Ester bond and (meth)acryl resin, etc.

烷二異氰酸酯、氫化二苯基甲烷二異氰酸酯、氫化甲苯二異氰酸酯、氫化苯二甲基二異氰酸酯、氫化四甲基苯二甲基二異氰酸酯、環己基二異氰酸酯等，另外作為芳香族聚異氰酸酯化合物，可舉出：甲苯二異氰酸酯、4,4’-二苯基甲烷二異氰酸酯、苯二甲基二異氰酸酯、1,5-萘二異氰酸酯、甲苯二異氰酸酯、對伸苯基二異氰酸酯等。 Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, Methyl diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate Isocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, nor

Alkane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate, cyclohexyl diisocyanate, etc., and as aromatic polyisocyanate compounds, Examples thereof include toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, toluene diisocyanate, and p-phenylene diisocyanate.

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, etc.

Examples of the hydroxyl group-containing (meth)acrylate compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 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 ) acrylates, mono(meth)acrylates of dihydric alcohols such as hydroxytrimethylacetate neopentyl glycol mono(meth)acrylate; trimethylolpropane di(meth)acrylate, ethoxy Propoxylated trimethylolpropane (meth)acrylate, propoxylated trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, bis(2-(meth)acryloxy Mono- or di-(meth)acrylates of trihydric alcohols such as ethyl ethyl)hydroxyethyl isocyanurate, or hydroxyl-containing hydroxyl groups modified by ε-caprolactone in part of such alcoholic hydroxyl groups Mono- and di(meth)acrylates; pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc. have a functional hydroxyl group and Compounds with (meth)acrylyl groups with more than 3 functions, or hydroxyl-containing polyfunctional (meth)acrylates whose compounds are further modified by ε-caprolactone; dipropylene glycol mono(meth)acrylates, Diethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, etc. (meth)acrylate compounds having an oxyalkylene chain; Polyethylene glycol-polypropylene glycol mono(meth)acrylate, polyoxybutylene-polyoxypropylene mono(meth)acrylate, etc. (meth)acrylate compounds having an oxyalkylene chain with a block structure ; Poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate, poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate, etc. have lactamide structure oxygen extension Alkyl chain (meth)acrylate compounds, etc.

The reaction of the above-mentioned aliphatic polyisocyanate compound or aromatic polyisocyanate compound and the hydroxyl group-containing (meth)acrylate compound can be carried out, for example, in the presence of a urethanization catalyst according to a common method. Urethane catalysts that can be used here include, specifically, amines such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; triphenylphosphine, triethylphosphine Phosphines, etc.; organotin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate, tin octoate, etc.; organometallic compounds such as zinc octoate.

Among such urethane (meth)acrylate resins, those obtained by reacting an aliphatic polyisocyanate compound with a hydroxyl group-containing (meth)acrylate compound are excellent in transparency of the cured film, In addition, it is preferable in terms of good sensitivity to active energy rays and excellent curability.

Examples of the unsaturated polyester resin include curable resins obtained by polycondensation of α,β-unsaturated dibasic acids or their anhydrides, dibasic acids other than the dibasic acids or their anhydrides, and diols. wait. Examples of the α,β-unsaturated dibasic acid or its anhydride include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof.

Examples of dibasic acids or their anhydrides other than the aforementioned α,β-unsaturated dibasic acids or their anhydrides include aromatic saturated dibasic acids, aliphatic dibasic acids, alicyclic saturated dibasic acids, and the like. Anhydrides, etc. Examples of aromatic saturated dibasic acids or their anhydrides include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, and tetrahydrophthalic acid. Acid anhydride, endomethylene tetrahydrophthalic anhydride, halogenated phthalic anhydride, and esters thereof. Examples of aliphatic dibasic acids, alicyclic saturated dibasic acids, and their anhydrides include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, Hexahydrophthalic anhydride and its esters, etc. Examples of glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol Alcohol, neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2, Oxides of 2-bis-(4-hydroxypropoxydiphenyl)propane, ethylene oxide, propylene oxide, etc. can also be used in the same manner.

Examples of the aforementioned epoxy (meth)acrylate resins include bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, phenol novolak-type epoxy resins, cresol novolak-type epoxy resins, etc. The epoxy group of the epoxy resin is obtained by reacting (meth)acrylic acid, etc.

The aforementioned acryl acrylate resin is an acrylic resin containing an acryl group. Specifically, a compound in which acrylic acid is added to an acrylic resin in which glycidyl methacrylate is copolymerized, a compound in which acrylic acid is added to an acrylic resin in which 2-acryloxyethyl isocyanate is copolymerized, Compounds such as 2-hydroxyethyl acrylate or 4-hydroxybutyl acrylate, pentaerythritol triacrylate, etc., resins in which 2-acryloxyethyl isocyanate is added to acrylic resins copolymerized with hydroxyl-containing monomers, etc.

The aforementioned maleimide group-containing resins include, for example, bifunctional maleimide obtained by urethanizing N-hydroxyethylmaleimide and isophorone diisocyanate. Amino urethane compounds, bifunctional maleimide ester compounds obtained by esterifying maleimidoacetic acid and polytetramethylene glycol, maleimidocaproic acid and pentaerythritol Tetrafunctional maleimide ester compound obtained by esterifying tetraoxirane adduct, polyfunctional maleimide ester compound obtained by esterifying maleimide acetic acid and polyol compound wait. These active energy ray-curable resins may be used alone or in combination of two or more.

The above-mentioned cardo resin is generally a general term for resins having a structure in which a cyclic group is directly bonded to a polymer chain, for example, resins having the following structures can be exemplified.

(In the formula, R represents a hydrogen atom or an alkyl group; R' represents a hydrogen atom or a methyl group; n is an integer from 0 to 20).

As said active energy ray curable monomer (III), the compound which has one or more ethylenically unsaturated bonds can be illustrated, for example.

酯、(甲基)丙烯酸2-羥基乙酯、甘油單(甲基)丙烯酸酯、(甲基)丙烯酸四氫糠酯等之(甲基)丙烯酸酯；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸4-羥基丁酯等之(甲基)丙烯酸羥基 烷酯、甘油單(甲基)丙烯酸酯等之具有羥基的(甲基)丙烯酸酯；苯乙烯及其衍生物等之芳香族乙烯基化合物；N-乙烯基吡咯啶酮等之乙烯基化合物；N-環己基馬來醯亞胺、N-苯基馬來醯亞胺、N-苄基馬來醯亞胺等之N-取代馬來醯亞胺；(甲基)丙烯酸、馬來酸、巴豆酸、伊康酸、富馬酸、桂皮酸、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基己二酸、2-(甲基)丙烯醯氧基乙基馬來酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基琥珀酸、2-(甲基)丙烯醯氧基丙基己二酸、2-(甲基)丙烯醯氧基丙基馬來酸、2-(甲基)丙烯醯氧基丙基氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基鄰苯二甲酸、2-(甲基)丙烯醯氧基丁基琥珀酸、2-(甲基)丙烯醯氧基丁基己二酸、2-(甲基)丙烯醯氧基丁基馬來酸、2-(甲基)丙烯醯氧基丁基氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丁基鄰苯二甲酸等之聚合性單體；於丙烯酸上加成有ε-己內酯、β-丙內酯、γ-丁內酯、δ-戊內酯等的內酯之聚合性單體；於(甲基)丙烯酸羥基烷酯上加成有琥珀酸、馬來酸、鄰苯二甲酸或此等的酸酐之聚合性單體；(甲基)丙烯酸-2-磺基乙酯、(甲基)丙烯酸-2-磺基丙酯、2-羥基-3-(甲基)丙烯醯氧基丙烷磺酸、2-(甲基)丙烯醯胺-2-甲基丙烷磺酸或此等之鹽等； 聚(甲基)丙烯酸甲酯巨單體、聚苯乙烯巨單體、聚(甲基)丙烯酸2-羥基乙酯巨單體、聚乙二醇巨單體、聚丙二醇巨單體、聚己內酯巨單體等之巨單體等。 Examples of compounds having one ethylenically unsaturated bond include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate Base) butyl acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate , phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, iso(meth)acrylate

Esters, 2-hydroxyethyl (meth)acrylate, glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, etc. (meth)acrylates; 2-hydroxyethyl (meth)acrylate Hydroxyalkyl (meth)acrylates such as hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc., (meth)acrylates having a hydroxyl group such as glycerol mono(meth)acrylate ; Aromatic vinyl compounds such as styrene and its derivatives; Vinyl compounds such as N-vinylpyrrolidone; N-cyclohexylmaleimide, N-phenylmaleimide, N- N-substituted maleimides such as benzylmaleimide; (meth)acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, cinnamic acid, 2-(meth)acrylic acid Oxyethylsuccinic acid, 2-(meth)acryloxyethyl adipic acid, 2-(meth)acryloxyethylmaleic acid, 2-(meth)acryloxyethyl Hexahydrophthalic acid, 2-(meth)acryloxyethylphthalic acid, 2-(meth)acryloxypropylsuccinic acid, 2-(meth)acryloxy Propyl adipic acid, 2-(meth)acryloxypropylmaleic acid, 2-(meth)acryloxypropylhydrophthalic acid, 2-(meth)acryloxypropyl Propylphthalate, 2-(meth)acryloxybutylsuccinic acid, 2-(meth)acryloxybutyladipate, 2-(meth)acryloxybutyl Polymerizable monomers such as maleic acid, 2-(meth)acryloxybutylhydrophthalic acid, 2-(meth)acryloxybutylphthalic acid, etc.; added to acrylic acid Polymerizable monomers of lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, etc.; succinic acid, Polymerizable monomers of maleic acid, phthalic acid or their anhydrides; 2-sulfoethyl (meth)acrylate, 2-sulfopropyl (meth)acrylate, 2-hydroxy-3 -(meth)acryloxypropanesulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid or their salts; poly(methyl)acrylate macromonomer, poly Macromonomers such as styrene macromonomer, poly(2-hydroxyethyl meth)acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, polycaprolactone macromonomer, etc.

Examples of active energy ray-curable monomers having two ethylenically unsaturated bonds include 1,3-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylic acid ester, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate ester, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bis(acryloxyethyl)ether of bisphenol A, ethyl Oxylated Bisphenol A Di(meth)acrylate, Propoxylated Neopentyl Glycol Di(meth)acrylate, Ethoxylated Neopentyl Glycol Di(meth)acrylate, 3-Methyl Pentylene glycol di(meth)acrylate, etc.

Examples of active energy ray-curable monomers having three ethylenically unsaturated bonds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ginseng (2-hydroxy Ethyl)isocyanurate tri(meth)acrylate, Ethoxylated trimethylolpropane tri(meth)acrylate, Propoxylated trimethylolpropane tri(meth)acrylate , The reactant of pentaerythritol tri(meth)acrylate and acid anhydride, caprolactone modified pentaerythritol tri(meth)acrylate, caprolactone modified ginseng (2-hydroxyethyl) isocyanurate tri( Meth)acrylate, reactants of caprolactone-modified pentaerythritol tri(meth)acrylate and acid anhydride, reactants of caprolactone-modified dipentaerythritol penta(meth)acrylate and acid anhydride, etc.

Examples of active energy ray-curable monomers having four ethylenically unsaturated bonds include pentaerythritol tetra(meth)acrylate, tripentaerythritol tetra(meth)acrylate, caprolactone-modified tripentaerythritol tetra(meth)acrylate, (meth)acrylate, etc.

Examples of active energy ray-curable monomers having five or more ethylenically unsaturated bonds include dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol penta(meth)acrylate, and tripentaerythritol penta(meth)acrylate. base) acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, dipentaerythritol penta(meth)acrylate and acid anhydride reactant, Tripentaerythritol hepta(meth)acrylate and 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 Acrylate, caprolactone-modified tripentaerythritol hepta(meth)acrylate, caprolactone-modified tripentaerythritol octa(meth)acrylate, caprolactone-modified tripentaerythritol hepta(meth)acrylate and anhydride, etc. .

Among these, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(methyl)acrylate are preferable especially from the viewpoint of excellent hardness of the cured coating film. ) acrylates, pentaerythritol tetra(meth)acrylates and other trifunctional or more polyfunctional (meth)acrylates. These active energy ray-curing monomers (III) may be used alone or in combination of two or more.

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 a surface modifier, it is easy to improve the leveling and water repellency of the obtained cured film. From the viewpoint of excellent balance between oiliness and antifouling properties, and sufficient hardness and transparency after curing, the active energy ray-curable resin (II) and the active energy ray-curable resin (II) The amount used 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, based on 100 parts by mass of the total monomer (III).

The fluorine-containing active energy ray-curable resin (I) of the present invention alone or the aforementioned active energy ray-curable composition can be formed into a cured film by irradiating active energy rays after coating on a substrate. Examples of such active energy rays include ionizing radiation rays such as ultraviolet rays, electron beams, α-rays, β-rays, and γ-rays. When irradiating ultraviolet rays as active energy rays to form a cured film, it is preferable to add a photopolymerization initiator to improve curability. Also, if necessary, a photosensitizer may be further added to improve curability. On the other hand, when using ionizing radiation such as electron beams, α rays, β rays, and γ rays, since even without using a photopolymerization initiator or a photosensitizer, it can be hardened rapidly, so especially without adding a photopolymerization initiator. It is not necessary for an initiator or a photosensitizer, but there is no problem even if it is added.

啉基(4-硫基甲基苯基)丙-1-酮、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)丁酮等之苯乙酮系化合物；苯偶姻、苯偶姻甲基醚、苯偶姻異丙基醚等之苯偶姻類；2,4,6-三甲基苯偶姻二苯基膦氧化物、雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物等之醯基膦氧化物系化合物；二苯乙二酮、甲基苯基乙醛酸酯等。 As said photoinitiator, an intramolecular cleavage type photoinitiator and a hydrogen extraction type photoinitiator are mentioned. Examples of intramolecular cleavage photopolymerization initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal , 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone , 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-

Linyl (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1-(4-

Acetophenone series compounds such as linylphenyl) butanone; Benzoins such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; 2,4,6-trimethylbenzene Acylphosphine oxide-based compounds such as azoindiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; benzidine, methylphenyl Glyoxylate etc.

Examples of hydrogen-extraction type photopolymerization initiators include diphenyl ketone, o-benzoylbenzoic acid methyl-4-phenyl diphenyl ketone, 4,4'-dichloro diphenyl ketone , Hydroxydiphenyl ketone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated diphenyl ketone, 3,3',4,4'-tetra(tert-butyl Peroxycarbonyl) diphenyl ketone, 3,3'-dimethyl-4-methoxydiphenyl ketone and other diphenyl ketone compounds; 2-isopropyl thioxanthone, 2,4-di Thioxanthone compounds such as methylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; Michelerone, 4,4'-diethylamino di Amino diphenyl ketone compounds such as phenyl ketones; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, etc.

Among the above-mentioned photopolymerization initiators, it is excellent in compatibility with the aforementioned active energy ray-curable resin (II) and active energy ray-curable monomer (III) in the active energy ray-curable composition. See, 1-hydroxycyclohexyl phenyl ketone and diphenyl ketone are preferred, and 1-hydroxy cyclohexyl phenyl ketone is particularly preferred. These photopolymerization initiators may be used alone or in combination of two or more.

In addition, examples of the photosensitizer include amines such as aliphatic amines and aromatic amines, ureas such as o-tolylthiourea, sodium diethyldithiophosphate, S -benzylisothiourea, etc. Sulfur compounds such as uronium p-toluenesulfonate, etc.

The amount of these photopolymerization initiators and photosensitizers used is preferably 0.01-20 parts by mass, more preferably 0.1-20 parts by mass, relative to 100 parts by mass of non-volatile components in the active energy ray-curable composition. 15 parts by mass, preferably 0.3 to 7 parts by mass.

Furthermore, the active energy ray-curable composition of the present invention can be adjusted by adjusting the viscosity or refractive index, adjusting the color tone of the coating film, or other methods according to the purpose of use, characteristics, etc., within the range that does not impair the effect of the present invention. Various blending materials can be used together for the purpose of adjusting the properties of paint, shape or film properties, such as various organic solvents, acrylic resins, phenol resins, polyester resins, polystyrene resins, urethane resins, and urea resins , various resins such as melamine resin, alkyd resin, epoxy resin, polyamide resin, polycarbonate resin, petroleum resin, fluororesin, PTFE (polytetrafluoroethylene), polyethylene, polypropylene, carbon, titanium oxide , various organic or inorganic particles such as alumina, copper, silica particles, other polymerization initiators, polymerization inhibitors, antistatic agents, defoamers, viscosity modifiers, light-resistant stabilizers, weather-resistant stabilizers, heat-resistant stabilizers agent, antioxidant, antirust agent, slip agent, wax, gloss modifier, mold release agent, compatibilizer, conductivity modifier, pigment, dye, dispersant, dispersion stabilizer, silicone-based, hydrocarbon-based interface Active agents, etc.

Among the above-mentioned blending components, the organic solvent is useful for appropriately adjusting the solution viscosity of the active energy ray-curable composition of the present invention, and it is especially easy to adjust the film thickness for thin film coating. Examples of organic solvents usable here include: aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, and tertiary butanol; ethyl acetate and propylene glycol monomethyl ether Esters such as acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. These solvents may be used alone or in combination of two or more.

As the active energy rays for curing the active energy ray-curable composition of the present invention, as mentioned above, there are ionizing radiation rays such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays, but as a specific energy source or curing device, Examples include germicidal lamps, fluorescent lamps for ultraviolet rays, carbon arcs, xenon lamps, high-pressure mercury lamps for photocopying, medium-pressure or high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, metal halide lamps, and ultraviolet rays that use natural light as a light source. , or the electron beam of the scanning type, curtain type electron beam accelerator, etc.

Among them, ultraviolet rays are particularly preferable, and it is preferable to irradiate with ultraviolet rays under an inert gas atmosphere such as nitrogen gas in order to avoid hardening hindrance by oxygen or the like. In addition, if necessary, heat may be used in combination as an energy source, and heat treatment may be performed after curing with ultraviolet rays.

The coating method of the active energy ray-curable composition of the present invention varies depending on the application. Curtain coater, kiss coater, spray coater, wheel coater, spin coater, dipping, screen printing, spray, coater, rod coater, etc., or forming methods using various molds, etc.

Since the cured film of the present invention has excellent antifouling properties, scratch resistance, etc., it is possible to impart antifouling properties, scratch resistance, etc. to the surface of the article by coating and curing on the surface of the article. In addition, the cured film of the present invention can maintain the antifouling property of the cured film surface even after wiping off the dirt adhering to the surface of the cured film. In addition, since the fluorine-containing active energy ray-curable resin (I) of the present invention can also be added to a coating material as a surface modifier to impart leveling properties to the coating material, the active energy ray-curable resin of the present invention The active composition has high leveling properties.

Examples of articles to which antifouling properties can be imparted by using the fluorine-containing active energy ray-curable resin (I) or active energy ray-curable composition of the present invention include TAC films and other polarizers for liquid crystal displays (LCDs) Films; various display screens such as plasma displays (PDPs), organic EL displays, etc.; touch panels; casings or screens of electronic terminals such as mobile phones; color filters for liquid crystal displays (hereinafter referred to as "CF") Transparent protective film; organic insulating film for liquid crystal TFT array; optical recording media of CD, DVD, Blu-ray disc, etc.; transfer film for insert molding (IMD, IMF); rubber roller for OA machines such as photocopiers and printers ; The glass surface of the reading part of OA equipment such as photocopiers and scanners; the optical lens of cameras, video cameras, glasses, etc.; the windshield and glass surface of clocks such as watches; the windows of various vehicles such as automobiles and railway vehicles; Cover glass or film for solar cells; various building materials such as cosmetic panels; window glass for houses; woodworking materials such as furniture, artificial and synthetic leather, various plastic molded products such as shells of home appliances, FRP baths, etc. By coating the active energy ray-curable composition of the present invention on the surface of these articles and irradiating with active energy rays such as ultraviolet rays to form a cured film, antifouling properties can be imparted to the surface of the article. In addition, by adding the fluorine-containing active energy ray-curable resin (I) of the present invention to various paints suitable for each article, and performing coating and drying, antifouling properties can also be imparted to the surface of the article.

In addition, as a coating material that adds the fluorine-containing active energy ray-curable resin (I) of the present invention to improve leveling properties and impart antifouling properties or chemical resistance to the coating film, TAC film, etc. Hard coating materials for polarizing plates of LCDs, anti-glare (AG: anti-glare) coating materials or anti-reflection (LR) coating materials; hard coatings for various display screens such as plasma displays (PDP) and organic EL displays Materials; hard coating materials for touch panels; printing inks, inkjet inks or coatings; coatings or hard coating materials for electronic terminal casings such as mobile phones; hard coating materials for mobile phone screens; transparency to protect CF surfaces Coatings for protective films; coatings for organic insulating films of liquid crystal TFT arrays; hard coating materials for optical recording media such as CD, DVD, and Blu-ray discs; hard coating materials for transfer films for insert molding (IMD, IMF); photocopiers, Coating materials for rubber rollers of OA equipment such as printers; Coating materials for glass of reading parts of OA equipment such as photocopiers and scanners; Coating materials for optical lenses of cameras, video cameras, glasses, etc.; Watches Coating materials for windshields and glass of watches and clocks; Coating materials for windows of various vehicles such as automobiles and railway vehicles; Coatings for cover glass or film anti-reflection film for solar cells; Printing for various building materials such as cosmetic panels Ink or paint; Coating materials for residential window glass; Woodworking coatings for furniture, etc.; Coating materials for artificial and synthetic leather; Coatings or coating materials for various plastic moldings such as housings of home appliances; or coating materials, etc.

Furthermore, examples of articles capable of imparting scratch resistance (scratch resistance) and antifouling properties using the fluorine-containing active energy ray-curable resin (I) or active energy ray-curable composition of the present invention include Diffusion sheet or diffusion sheet of LCD backlight components, etc. In addition, by adding the fluorine-containing active energy ray-curable resin (I) of the present invention to the coating material for a sheet or diffusion sheet, the leveling property of the coating material can be improved, and the scratch resistance (scratch resistance) can be improved at the same time. damage) and anti-fouling properties are imparted to the coating film of the coating material.

Also, since the cured film of the fluorine-containing active energy ray curable resin (I) of the present invention has a low refractive index, it can also be used as an antireflection layer that can prevent fluorescent lamps from being reflected on the surface of various displays such as LCDs. Coating material for low refractive index layer. In addition, by adding the fluorine-containing active energy ray curable resin (I) of the present invention to the coating material for the antireflection layer, especially the coating material for the low refractive index layer in the antireflection layer, it is also possible to maintain the coating. The low refractive index of the film imparts antifouling properties to the surface of the coating film.

Furthermore, other applications in which the fluorine-containing active energy ray-curable resin (I) or active energy ray-curable composition of the present invention can be used include cladding materials for optical fibers, waveguides, sealing materials for liquid crystal panels, and various optical components. Use sealing materials, optical adhesives, etc.

In particular, when using the active energy ray-curable composition of the present invention as an anti-glare coating material in the application of a coating material for a protective film of a polarizing plate for LCD, among the above-mentioned compositions, by being In the active energy ray-curable composition of the present invention, inorganic or organic fine particles such as silica fine particles, acrylic resin fine particles, polystyrene resin fine particles, etc. are blended in an amount of 0.1 to 0.5 times the total mass of the hardening components, because it becomes Those with excellent anti-glare properties are preferred.

Furthermore, when the fluorine-containing active energy ray-curable resin (I) or 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 LCD, it can also be applied to: Before the coating material is hardened, it is brought into contact with a mold with a concave-convex surface shape, and then irradiated with active energy rays from the opposite side of the mold to harden and emboss the surface of the coating to impart anti-glare properties.

The curable composition containing the fluorine-containing active energy ray curable resin (I) of the present invention is suitable as a resist composition. As a resist composition, a photoresist composition, a color resist composition, etc. are mentioned, for example. The aforementioned photoresist composition is composed of, for example, the fluorine-containing active energy ray curable resin (I) of the present invention and a photoresist, such as an alkali-soluble resin, a radiation-sensitive substance (photosensitive substance), and a solvent.

Here, the term "alkali solubility" refers to the property of dissolving in an aqueous solution (developing solution) of an alkali compound. Specifically, for example, a resin film with a film thickness of 1 μm is formed on a substrate with a resin solution having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate), and dipped in a KOH aqueous solution with a concentration of 0.05% by mass. After 1 minute, it can show the property of dissolving when the film thickness is more than 0.01μm.

The aforementioned alkali-soluble resin is not particularly limited as long as it is soluble in an alkaline developer, but is preferably a resin having at least one acid group selected from the group consisting of carboxyl group, phenolic hydroxyl group, and sulfonic acid group or a salt thereof .

As the aforementioned alkali-soluble resin, for example, a non-photocurable alkali-soluble resin (alkali-soluble resin not containing a photocurable group) or a photocurable alkali-soluble resin (alkali-soluble resin containing a photocurable group) can be exemplified. wait.

As an alkali-soluble resin which does not contain the said photocurable group, the following resin etc. are mentioned, for example.

‧Alkali-soluble resin (1) obtained by polymerizing a (meth)acrylic polymerizable monomer having an acidic group as an essential component.

‧Polymerizing a (meth)acrylic polymerizable monomer having a reactive group as an essential component without an acidic group, and a reactive group and an acidic group that are reactive to the reactive group Alkali-soluble resin (2)

As the alkali-soluble resin containing the said photocurable group, the following resin etc. are mentioned, for example.

‧For a copolymer of epoxy group-containing (meth)acrylate and other polymerizable monomers, adding unsaturated monocarboxylic acid to at least a part of the epoxy group of the copolymer An alkali-soluble resin (3) obtained by adding at least a part of hydroxyl groups formed by the addition reaction of a saturated monocarboxylic acid to an anhydride of a polycarboxylic acid.

‧Epoxy (meth)acrylate resin with carboxyl group and polymerizable unsaturated group(4)

‧Cardo type resin with carboxyl group and polymerizable unsaturated group(5)

Hereinafter, the above (1) to (5) will be described in detail.

As the aforementioned alkali-soluble resin (1), for example, an alkali-soluble resin obtained by polymerizing a (meth)acrylic polymerizable monomer having a carboxyl group as an essential component or a (meth)acrylic monomer having a sulfonic acid group Alkali-soluble resins obtained by polymerizing polymerizable monomers as an essential component. 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)acrylic acid, )acryloxyethylsuccinic acid, 2-(meth)acryloxyethyladipic acid, 2-(meth)acryloxyethylmaleic acid, 2-(meth)acrylyl Oxyethylhexahydrophthalic acid, 2-(meth)acryloxyethylphthalic acid, 2-(meth)acryloxypropylsuccinic acid, 2-(meth)propene Acyloxypropyl adipic acid, 2-(meth)acryloxypropylmaleic acid, 2-(meth)acryloxypropylhydrophthalic acid, 2-(meth)propene Acyloxypropyl phthalic acid, 2-(meth)acryloxybutyl succinic acid, 2-(meth)acryloxybutyl adipate, 2-(meth)acryloxy Polymerizable monomers such as butyl butylmaleic acid, 2-(meth)acryloxybutylhydrophthalic acid, 2-(meth)acryloxybutyl phthalic acid, etc.; in acrylic acid Polymerizable monomers of lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, etc.; added to hydroxyalkyl (meth)acrylate Polymerizable monomers of succinic acid, maleic acid, phthalic acid or their anhydrides, etc. These carboxyl group-containing (meth)acrylic polymerizable monomers may be used alone or in combination of two or more. Among the (meth)acrylic polymerizable monomers having a carboxyl group, (meth)acrylic acid and 2-(meth)acryloxyethylsuccinic acid are preferred.

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)acryloxypropanesulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, or salts thereof.

酯、(甲基)丙烯酸2-羥基乙酯、甘油單(甲基)丙烯酸酯、(甲基)丙烯酸四氫糠酯等之(甲基)丙烯酸酯；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸4-羥基丁酯等之(甲基)丙烯酸羥基烷酯、甘油單(甲基)丙烯酸酯等之具有羥基的(甲基)丙烯酸酯；苯乙烯及其衍生物等之芳香族乙烯基化合物；N-乙烯基吡咯啶酮等之乙烯基化合物；N-環己基馬來醯亞胺、N-苯基馬來醯亞胺、N-苄基馬來醯亞胺等之N-取代馬來醯亞胺；聚(甲基)丙烯酸甲酯巨單體、聚苯乙烯巨單體、聚(甲基)丙烯酸2-羥基乙酯巨單體、聚乙二醇巨單體、聚丙二醇巨單體、聚己內酯巨單體等之巨單體等。其它的聚合性單體係可以僅使用1種，也可以併用2種以上。 When preparing the alkali-soluble resin (1), other polymerizable monomers may be used in combination within the range not impairing the effect of the present invention. Examples of other monomers include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate ester, isobutyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, (meth)acrylate ) phenoxymethyl acrylate, 2-ethylhexyl (meth)acrylate, iso(meth)acrylate

Esters, 2-hydroxyethyl (meth)acrylate, glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, etc. (meth)acrylates; 2-hydroxyethyl (meth)acrylate Hydroxyalkyl (meth)acrylates such as hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc., (meth)acrylates having a hydroxyl group such as glycerol mono(meth)acrylate ; Aromatic vinyl compounds such as styrene and its derivatives; Vinyl compounds such as N-vinylpyrrolidone; N-cyclohexylmaleimide, N-phenylmaleimide, N- N-substituted maleimide such as benzylmaleimide; poly(methyl)acrylate macromonomer, polystyrene macromonomer, poly(meth)acrylate 2-hydroxyethyl ester macromonomer Macromonomers such as polyethylene glycol macromonomers, polypropylene glycol macromonomers, polycaprolactone macromonomers, etc. Other polymerizable monomers may be used alone or in combination of two or more.

Among the above-mentioned other polymerizable monomers, styrene, methyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth) base) benzyl acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylic acid Isobutyl ester, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide.

The usage-amount of these other polymerizable monomers is preferably 95 mass % or less of the total polymerizable monomer component, More preferably, it is 85 mass % or less.

Specific examples of the alkali-soluble resin (1) include (meth)acrylic acid, methyl (meth)acrylate, benzyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylate ) isobutyl acrylate, (meth)cyclohexyl acrylate, cyclohexylmaleimide and other polymerizable monomers without hydroxyl groups, and 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid Copolymers of hydroxyl-containing polymerizable monomers such as hydroxypropyl ester and 4-hydroxybutyl (meth)acrylate; (meth)acrylic acid and methyl (meth)acrylate, benzyl (meth)acrylate, ( Copolymers of (meth)acrylates such as butyl methacrylate, isobutyl (meth)acrylate, and 2-hydroxyethyl methacrylate; copolymers of (meth)acrylic acid and styrene; (meth)acrylic acid and styrene; Base) copolymer of acrylic acid, styrene and α-methylstyrene; copolymer of (meth)acrylic acid and cyclohexylmaleimide, etc. Among the alkali-soluble resins (1), an alkali-soluble resin using benzyl (meth)acrylate is preferable.

The acid value of the aforementioned alkali-soluble resin (1) is preferably in the range of 10-300, more preferably in the range of 20-350, and most preferably in the range of 30-300. In addition, the polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin (1) 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, most preferably in the range of 4,000 to 50,000 range.

In addition, in the alkali-soluble resin (1), an epoxy group-containing resin is added to the carboxyl group of the carboxyl group-containing alkali-soluble resin obtained by polymerizing a (meth)acrylic polymerizable monomer having a carboxyl group as an essential component. The alkali-soluble resin (1-1) of an unsaturated compound can also be used as an alkali-soluble resin containing a photocurable group.

Examples of the epoxy group-containing unsaturated compound include glycidyl (meth)acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl ring Oxypropyl ether, (iso)glycidyl crotonate, N-(3,5-dimethyl-4-epoxypropyl) benzyl acrylamide, 4-hydroxybutyl (meth)acrylate Glycidyl ether etc. Moreover, from the viewpoint of improving heat resistance and improving dispersibility when a pigment is used as a colorant, an alicyclic epoxy group-containing unsaturated compound is preferable.

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]dec-2-yl]yl, etc. Moreover, as an ethylenically unsaturated group, a (meth)acryl group is preferable. The alicyclic epoxy group-containing unsaturated compound may be used alone or in combination of two or more.

In order to add the said epoxy group-containing unsaturated compound to the carboxyl part of the said carboxyl group-containing alkali-soluble resin, well-known methods can be used. For example, by combining carboxyl-containing alkali-soluble resins with epoxy-containing unsaturated compounds, in tertiary amines such as triethylamine and benzylmethylamine; dodecyltrimethylammonium chloride, tetramethylammonium Quaternary ammonium salts of ammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride, etc.; in the presence of catalysts such as pyridine, triphenylphosphine, etc., in organic solvents In the process, react at a reaction temperature of 50-150°C for several hours to tens of hours, and the unsaturated compound containing epoxy group can be added to the carboxyl group of the resin.

The acid value of the aforementioned alkali-soluble resin (1-1) is preferably in the range of 10-300, more preferably in the range of 20-250, and most preferably in the range of 30-200. In addition, the weight average molecular weight of the alkali-soluble resin (1-1) measured by GPC in terms of polystyrene is preferably in the range of 2,000 to 100,000, more preferably in the range of 4,000 to 50,000, and most preferably in the range of 5,000 to 30,000 .

Also, among the aforementioned alkali-soluble resins (1), alkali-soluble resins (1) obtained by using ether dimers or (meth)acrylates having alicyclic structures such as adamantyl groups as polymerizable monomers are preferable. -2).

基)-2,2’-[氧基雙(亞甲基)]雙-2-丙酸酯、二金剛烷基-2,2’-[氧基雙(亞甲基)]雙-2-丙酸酯、二(2-甲基-2-金剛烷基)-2,2’-[氧基雙(亞甲基)]雙-2-丙酸酯等。於此等之中，較佳為二甲基-2,2’-[氧基雙(亞甲基)]雙-2-丙酸酯、二乙基-2,2’-[氧基雙(亞甲基)]雙-2-丙酸酯、二環己基-2,2’-[氧基雙(亞甲基)]雙-2-丙酸酯、二苄基-2,2’-[氧基雙(亞甲基)]雙-2-丙酸酯。此等之醚二聚物係可以僅使用1種，也可以併用2種以上。 Examples of the aforementioned ether dimers include dimethyl-2,2'-[oxybis(methylene)]bis-2-propionate, diethyl-2,2'-[oxy Bis(methylene)]bis-2-propionate, bis(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propionate, bis(isopropyl) base)-2,2'-[oxybis(methylene)]bis-2-propionate, bis(n-butyl)-2,2'-[oxybis(methylene)]bis- 2-propionate, bis(isobutyl)-2,2'-[oxybis(methylene)]bis-2-propionate, bis(tert-butyl)-2,2'-[ Oxybis(methylene)]bis-2-propionate, bis(tertiary pentyl)-2,2'-[oxybis(methylene)]bis-2-propionate, bis( Stearyl)-2,2'-[oxybis(methylene)]bis-2-propionate, bis(lauryl)-2,2'-[oxybis(methylene)]bis -2-propionate, bis(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propionate, bis(1-methoxyethyl)- 2,2'-[oxybis(methylene)]bis-2-propionate, bis(1-ethoxyethyl)-2,2'-[oxybis(methylene)]bis -2-propionate, dibenzyl-2,2'-[oxybis(methylene)]bis-2-propionate, diphenyl-2,2'-[oxybis(methylene) base)]bis-2-propionate, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-propionate, bis(tert-butylcyclohexyl)-2, 2'-[oxybis(methylene)]bis-2-propionate, bis(dicyclopentadienyl)-2,2'-[oxybis(methylene)]bis-2- Propionate, bis(tricyclodecanyl)-2,2'-[oxybis(methylene)]bis-2-propionate, bis(iso

base)-2,2'-[oxybis(methylene)]bis-2-propionate, diadamantyl-2,2'-[oxybis(methylene)]bis-2- Propionate, bis(2-methyl-2-adamantyl)-2,2'-[oxybis(methylene)]bis-2-propionate, etc. Among these, dimethyl-2,2'-[oxybis(methylene)]bis-2-propionate, diethyl-2,2'-[oxybis( Methylene)]bis-2-propionate, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-propionate, dibenzyl-2,2'-[ Oxybis(methylene)]bis-2-propionate. These ether dimers may be used alone or in combination of two or more.

烷、乙二醇二甲基醚、二乙二醇二甲基醚等之醚類；丙酮、甲基乙基酮、甲基異丁基酮、環己酮等之酮類；乙酸乙酯、乙酸丁酯、丙二醇單甲基醚乙酸酯、3-甲氧基丁基乙酸酯等之酯類；甲醇、乙醇、異丙醇、正丁醇、乙二醇單甲基醚、丙二醇單甲基醚等之醇類；甲苯、二甲苯、乙苯等之芳香族烴類；氯仿；二甲亞碸等。此等溶劑係可以僅使用1種，也可以併用2種以上。 The solvent system used in the solution polymerization method can be used in the usual free radical polymerization reaction. Specifically, for example, tetrahydrofuran, di

Ethers such as alkane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; ethyl acetate, Esters of butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc.; methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol mono Alcohols such as methyl ether; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform; dimethylsulfoxide, etc. These solvents may be used alone or in combination of two or more.

When polymerizing the aforementioned polymerizable monomer, a polymerization initiator can also be used if necessary. Examples of the polymerization initiator include: cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-tertiary butyl peroxide, lauryl peroxide, benzoyl peroxide Organic peroxides such as oxides, tert-butylperoxyisopropyl carbonate, tert-amylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, etc. ; 2,2'-Azobis(isobutyronitrile), 1,1'-Azobis(cyclohexanecarbonitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile) , Azo compounds such as dimethyl 2,2'-azobis(2-methylpropionate), etc. These polymerization initiators may be used alone or in combination of two or more. The amount of these polymerization initiators used is not particularly limited as long as it is appropriately set according to the combination of monomers used, or reaction conditions, and the molecular weight of the target alkali-soluble resin, but never gels. In order to obtain an alkali-soluble resin having a weight average molecular weight of several thousand to tens of thousands, it is preferably in the range of 0.1 to 15% by mass, more preferably in the range of 0.2 to 10% by mass, based on the total polymerizable monomer components.

Moreover, you may add a chain transfer agent for molecular weight adjustment. Examples of the chain transfer agent include: n-dodecylmercaptan, mercaptoacetic acid, methyl thioglycolate, and other mercaptan-based chain transfer agents; α-methylstyrene dimer, etc., but chain transfer is preferred. High effect, can reduce the remaining polymerizable monomers in the reaction system, and obtain n-dodecyl mercaptan and thioglycolic acid easily. The amount used when using a chain transfer agent is not particularly limited as long as it is appropriately set according to the combination of the monomers used, the reaction conditions, the molecular weight of the target monomer, etc., but the weight is never gelled. The average molecular weight of an alkali-soluble resin having an average molecular weight of several thousand to several tens of thousands is preferably in the range of 0.1 to 15% by mass, more preferably in the range of 0.5 to 10% by mass, based on all monomers.

The alkali-soluble resin (2) used in the present invention is a polymer without an acidic group obtained by polymerizing a (meth)acrylic polymerizable monomer having a reactive group as an essential component, and a polymer having a reactive group for the reactive group. It is obtained by reacting a reactive group with an acid group. As the alkali-soluble resin (2), the following alkali-soluble resins can be illustrated, for example.

‧Obtained by adding acid anhydrides such as succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride, etc. Alkali soluble resin.

‧Glycidyl (meth)acrylate and other polymerizable monomers with epoxy groups are used as essential components to obtain polymers, and N-methylaminobenzoic acid, N-methylaminophenol, etc. are added Alkali-soluble resin obtained from compounds with amine groups and acid groups.

‧Using polymerizable monomers with isocyanate groups such as 2-isocyanatoethyl (meth)acrylate as essential components to obtain polymers, and then adding compounds with hydroxyl groups and acid groups such as 2-hydroxybutyric acid Alkali-soluble resin obtained.

The weight-average molecular weight of the alkali-soluble resin (2) is preferably in the range of 1,000 to 200,000 in terms of weight-average molecular weight in terms of polystyrene as measured by GPC, in terms of forming a good coating film and obtaining a coating film with excellent heat resistance. , more preferably in the range of 2,000~10,000, especially preferably in the range of 2,000~50,000. Moreover, the polymerizable monomer used for preparation of the said alkali-soluble resin (1) can also be used together as needed, and the alkali-soluble resin (2) can also be obtained.

The alkali-soluble resin (3) used in the present invention is a copolymer of epoxy group-containing (meth)acrylate and other polymerizable monomers, and unsaturated monocarboxylic acid is added to the epoxy resin of the copolymer. At least a part of the group is obtained by adding an acid anhydride of a polycarboxylic acid to at least a part of the hydroxyl groups generated by the addition reaction of an unsaturated monocarboxylic acid.

Examples of the aforementioned epoxy group-containing (meth)acrylates include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, (meth)acrylic acid ( 3,4-epoxycyclohexyl)methyl ester, 4-hydroxybutyl (meth)acrylate glycidyl ether, etc. Among them, glycidyl (meth)acrylate is preferred. These epoxy group-containing (meth)acrylates may be used alone or in combination of two or more.

烯骨架、二環戊二烯骨架等之脂環式結構的單體，則可提高硬化物的耐熱性、機械強度而較宜。 Moreover, if other polymerizable monomers other than the epoxy group-containing (meth)acrylate used as the raw material of the aforementioned alkali-soluble resin (3) are used,

Monomers with alicyclic structures such as ene skeleton and dicyclopentadiene skeleton are preferable because they can improve the heat resistance and mechanical strength of the cured product.

酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸丙炔酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸蒽酯、(甲基)丙烯酸胺茴醯酯、(甲基)丙烯酸胡椒酯、(甲基)丙烯酸水楊酯、(甲基)丙烯酸呋喃酯、(甲基)丙烯酸糠酯、(甲基)丙烯酸四氫呋喃酯、(甲基)丙烯酸哌喃酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯乙酯、(甲基)丙烯酸甲苯酚酯、(甲基)丙烯酸-1,1,1-三氟乙酯、(甲基)丙烯酸全氟乙酯、(甲基)丙烯酸全氟正丙酯、(甲基)丙烯酸全氟異丙酯、(甲基)丙烯酸三苯基甲酯、(甲基)丙烯酸異丙苯酯、(甲基)丙烯酸-3-(N,N-二甲基胺基)丙酯、(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯等之(甲基)丙烯酸酯類；(甲基)丙烯酸醯胺、(甲基)丙烯酸N,N-二甲基醯胺、(甲基)丙烯酸N,N-二乙基醯胺、(甲基)丙烯酸N,N-二丙基醯胺、(甲基)丙烯酸-N,N-二異丙基醯胺、(甲基)丙烯酸蒽基醯胺等之(甲基)丙烯酸醯胺；(甲基)丙烯醯苯胺、(甲基)丙烯醯基腈、丙烯醛、氯乙烯、偏二氯乙烯、氟乙烯、偏二氟乙烯、N-乙烯基吡咯啶酮、乙烯基吡啶、乙酸乙烯酯等之乙烯基化合物類；檸康酸二乙酯、馬來酸二乙酯、富馬酸二乙酯、伊康酸二乙酯等之不飽和二羧酸二酯類；N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-月桂基馬來醯亞胺、N-(4-羥基苯基)馬來醯亞胺等之單馬來醯亞胺類；N-(甲基)丙烯醯基鄰苯二甲醯亞胺等。 Moreover, you may use the polymerizable monomer which does not have an alicyclic structure as another polymerizable monomer other than the said epoxy group containing (meth)acrylate. Examples of such polymerizable monomers include vinyl aromatic compounds such as styrene, α-, o-, m-, p-alkyl, nitro, cyano, amide, and ester derivatives of styrene. family; dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene, etc.; methyl (meth)acrylate, ethyl (meth)acrylate, ( n-propyl methacrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, second-butyl (meth)acrylate, third-butyl (meth)acrylate, (meth) Amyl 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 esters, (meth)acrylate iso

ester, adamantyl (meth)acrylate, propynyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, anthracene (meth)acrylate, amine (meth)acrylate Anisyl, Piperonyl (meth)acrylate, Salicyl (meth)acrylate, Fufuryl (meth)acrylate, Furfuryl (meth)acrylate, Tetrahydrofuryl (meth)acrylate, (Meth)acrylate Pyranyl ester, benzyl (meth)acrylate, phenylethyl (meth)acrylate, cresyl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, (methyl ) perfluoroethyl acrylate, perfluoro-n-propyl (meth)acrylate, perfluoroisopropyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, (meth)acrylate-3-(N,N-dimethylamino)propyl, (meth)acrylate-2-hydroxyethyl, (meth)acrylate-2-hydroxypropyl etc. ) acrylates; (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N, (Meth)acrylamide such as N-dipropylamide, (meth)acrylic acid-N,N-diisopropylamide, (meth)acrylic acid anthracenylamide; (meth)acrylamide Vinyl compounds such as aniline, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, etc. Classes; unsaturated dicarboxylic acid diesters such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate, etc.; N-phenylmaleimide, Monomaleimides such as N-cyclohexylmaleimide, N-laurylmaleimide, N-(4-hydroxyphenyl)maleimide, etc.; N-(methyl) Acryl phthalimide, etc.

Among the above-mentioned other polymerizable monomers, it is preferable to use styrene, benzyl (meth)acrylate, and monomaleimide in terms of improving the heat resistance and mechanical strength of the cured product. At least 1 species. The proportion of styrene, benzyl (meth)acrylate and monomaleimide is based on the total amount of other polymerizable monomers, preferably 1-70 mole%, more preferably 3-50 mole %.

In addition, the copolymerization reaction of the said epoxy group containing (meth)acrylate and the said other polymerizable monomer can use well-known polymerization methods, such as the solution polymerization method using the radical polymerization initiator. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and generally used organic solvents can be used.

As the copolymer of the above-mentioned epoxy group-containing (meth)acrylate and the above-mentioned other polymerizable monomers, it is preferably composed of 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth)acrylate, Composed of 10-95 mol% of repeating units from other radically polymerizable monomers, more preferably 20-80 mol% of the former and 80-20 mol% of the latter, especially preferably the former 30~70 mole % and the latter 70~30 mole %.

The above-mentioned alkali-soluble resin (3) can be made, for example, by making unsaturated monocarboxylic acid (polymerizable component) ) and polycarboxylic acid anhydride (alkali-soluble components) reaction.

Examples of the unsaturated monocarboxylic acid include: (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, halogenated alkyl groups at the α-position, alkoxy groups, halogen atoms, Monocarboxylic acids such as (meth)acrylic acid substituted with a nitro group or a cyano group, etc. Among these, (meth)acrylic acid is preferred. These unsaturated monocarboxylic acid systems may use only 1 type, and may use 2 or more types together. By using this unsaturated monocarboxylic acid, polymerizability can be imparted to the said alkali-soluble resin (3).

The above-mentioned unsaturated monocarboxylic acid is generally preferably added to 10-100 mole % of the epoxy groups that the aforementioned copolymer has, more preferably added to 30-100 mole %, especially preferably added to 50 mole %. ~100 mole %.

Examples of the anhydrides of the aforementioned polycarboxylic acids include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorobridge anhydride. Anhydrides of dicarboxylic acids; anhydrides of carboxylic acids having three or more carboxyl groups such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, and biphenyl tetracarboxylic anhydride. Among them, tetrahydrophthalic anhydride and succinic anhydride are preferable. The acid anhydrides of these polycarboxylic acids may be used alone or in combination of two or more. By using the acid anhydride of this polycarboxylic acid, alkali solubility can be provided to the said alkali-soluble resin (3).

The anhydride of the aforementioned polycarboxylic acid is usually preferably added to 10 to 100 mole % of the hydroxyl group formed by adding an unsaturated monocarboxylic acid to the epoxy group of the aforementioned copolymer, more preferably added 20~90 mol%, preferably 30~80 mol%.

The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin (3) measured by gel permeation chromatography (GPC) is preferably in the range of 3,000 to 100,000, more preferably in the range of 5,000 to 50,000. Also, the degree of dispersion (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, for example, obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the epoxy resin. , and further react polybasic anhydrides.

As the epoxy resin, for example, a bisphenol A type epoxy resin (commercially available as "Epikote 828", "Epikote 1001", "Epikote 1002", "Epikote 1004" etc. manufactured by Mitsubishi Chemical Corporation) can be used. , the epoxy resin (commercially available product is " NER-1302 " (epoxy equivalent 323 , softening point 76°C)), bisphenol F resin (commercially available products are "Epikote 807", "EP-4001", "EP-4002", "EP-4004" manufactured by Mitsubishi Chemical Corporation, etc.), The epoxy resin (commercially available product is " NER-7406 " (epoxy equivalent 350, softening point 66°C)), bisphenol S type epoxy resin, biphenyl glycidyl ether (commercially available is "YX-4000" manufactured by Mitsubishi Chemical Co., Ltd.), phenol novolak type epoxy resin ( Commercially available products are "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152" and "EP-154" manufactured by Mitsubishi Chemical Corporation, and "DEN-438" manufactured by Dow Chemical Japan Co., Ltd. ), cresol novolak type epoxy resin (commercially available products are "EOCN-102S", "EOCN-1020", "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isotrimer Cyanate ester (commercially available is "TEPIC" manufactured by Nissan Chemical Industry Co., Ltd.), trisphenolmethane type epoxy resin (commercially available is "EPPN-501" manufactured by Nippon Kayaku Co., Ltd., "EPN- 502", "EPPN-503"), fennel epoxy resin (commercially available is Cardo epoxy resin "ESF-300" manufactured by Nippon Steel Chemical Co., Ltd.), alicyclic epoxy resin (DAICEL Chemical Industry "Celloxide 2021P" and "Celloxide EHPE" manufactured by Co., Ltd.), dicyclopentadiene-type epoxy resins obtained by reacting dicyclopentadiene and phenol with epoxypropylated dicyclopentadiene-type epoxy resins (for example, Nippon Chemical "XD-1000" manufactured by DIC Co., Ltd., "EXA-7200" manufactured by DIC Co., Ltd., "NC-3000" and "NC-7300" manufactured by Nippon Kayaku Co., Ltd.) Oxygen resin (see JP-A-4-355450) and the like. These epoxy resins may be used alone or in combination of two or more.

Copolymerization type epoxy resin is mentioned as another example of an epoxy resin. Examples of copolymerizable epoxy resins include epoxy propyl (meth)acrylate, (meth)acrylmethyl epoxycyclohexane, vinyl epoxycyclohexane, etc. Oxygen monomers, with methyl (meth)acrylate, ethyl (meth)acrylate, butyl (shenyl) acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, ( Meth)acrylic acid, styrene, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, alpha-methylstyrene, glycerol mono(meth)acrylate, with polyoxyalkylene chain A copolymer obtained by copolymerizing polymerizable monomers such as (meth)acrylates without epoxy groups.

Examples of (meth)acrylates having a polyoxyalkylene chain include diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol Polyethylene glycol mono(meth)acrylate such as mono(meth)acrylate; Methoxydiethylene glycol mono(meth)acrylate, Methoxytriethylene glycol mono(meth)acrylate , Alkoxypolyethylene glycol (meth)acrylate such as methoxytetraethylene glycol mono(meth)acrylate, etc.

The molecular weight of the aforementioned copolymerized epoxy resin is preferably in the range of 1,000 to 200,000. In addition, the amount of monomers having epoxy groups used as raw materials for copolymerized epoxy resins is preferably in the range of 10 to 70% by mass, more preferably It is in the range of 20~50% by mass.

Examples of commercially available copolymer epoxy resins include "CP-15", "CP-30", "CP-50", "CP-20SA", "CP -510SA", "CP-50S", "CP-50M", "CP-20MA", etc.

The molecular weight of the above-mentioned epoxy resin is good in coating film formation and can prevent gelation during the addition reaction of α,β-unsaturated monocarboxylic acid. The weight average molecular weight in terms of polystyrene measured by GPC is relatively high. Preferably it is in the range of 200~200,000, more preferably in the range of 300~100,000.

Examples of α,β-unsaturated monocarboxylic acids include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid, etc., preferably acrylic acid and methacrylic acid. Acrylic is preferred. Examples of α,β-unsaturated monocarboxylic acid esters having a carboxyl group in the ester moiety include: 2-succinyloxyethyl acrylate, 2-maleyloxyethyl acrylate, 2-o- Phthalyloxyethyl ester, 2-hexahydrophthalyloxyethyl acrylate, 2-succinyloxyethyl methacrylate, 2-maleyloxyethyl methacrylate ester, 2-phthaloyloxyethyl methacrylate, 2-hexahydrophthaloyloxyethyl methacrylate, 2-succinyloxyethyl crotonate, etc. Preferred are 2-maleyloxyethyl acrylate and 2-phthalyloxyethyl acrylate, more preferably 2-maleyloxyethyl acrylate. These α,β-unsaturated monocarboxylic acids and α,β-unsaturated monocarboxylic acid esters may be used alone or in combination of two or more.

The addition reaction of α,β-unsaturated monocarboxylic acid or its ester and epoxy resin can use well-known methods, for example, the method of reacting at a temperature of 50~150°C in the presence of an esterification catalyst . As an esterification catalyst, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, benzyldiethylamine, etc.; tetramethylammonium chloride, tetraethylammonium chloride, dodecyl Quaternary ammonium salts such as trimethylammonium chloride, etc.

The amount of α,β-unsaturated monocarboxylic acid or its ester used is preferably in the range of 0.5-1.2 equivalents, more preferably 0.7-1.1 equivalents, relative to 1 equivalent of epoxy groups in the epoxy resin used as the raw material range.

Examples of polybasic acid anhydrides added to epoxy resins to which α,β-unsaturated carboxylic acids or esters have been added include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, diphenyl ketone tetracarboxylic dianhydride, methylhexahydrophthalic anhydride, endomethylene Methyltetrahydrophthalic anhydride, chlorine bridge anhydride, methyltetrahydrophthalic anhydride, biphenyltetracarboxylic dianhydride, etc. Among these, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, and trimellitic anhydride are preferred. Triformic anhydride and biphenyltetracarboxylic dianhydride, more preferably tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride. These polybasic acid anhydrides may use only 1 type, and may use 2 or more types together.

A well-known method can also be used about the addition reaction of polybasic acid anhydride, and it can make it react continuously under the same conditions as the addition reaction of α,β-unsaturated carboxylic acid or its ester. The amount of polybasic acid anhydride used is preferably an amount in which the acid value of the epoxy (meth)acrylate resin to be formed is in the range of 10 to 150, more preferably It becomes the amount in the range of 20~140.

Also, as the epoxy (meth)acrylate resin having a carboxyl group, the naphthalene-containing resin described in JP-A-6-49174 can also be exemplified; , Japanese Patent Application Publication No. 2005-325331, Japanese Patent Application Publication No. 2001-354735, Japanese Patent Application Publication No. 2005-126674, Japanese Patent Application Publication No. 2005-55814, Japanese Patent Application Publication No. 2004-295084 Resins described in et al. Moreover, as a commercial item, "ACA-200M" by Daicel Chemical Industry Co., Ltd. etc. can also be illustrated.

The aforementioned cardo resin (5) has a carboxyl group and a polymerizable unsaturated group. Generally speaking, cardo-type resins are polymer materials with various properties such as high heat resistance, solvent solubility, high transparency, high refractive index, low birefringence, and high air permeability, and can be used as a color filter in the formation of color filters. The binder resin for each pixel or the black matrix can be used particularly preferably as the binder resin for forming the black matrix.

The aforementioned so-called cardo-type resins are a general term for resins with a structure in which a cyclic group is directly bonded to the polymer main chain, but due to the presence of bulky substituents on the main chain, it shows: (1) polymer main chain Chain rotation constraints, (2) configuration constraints of the main chain and side chains, (3) obstruction of intermolecular stacking, (4) increase in aromaticity due to the introduction of aromatic substituents in side chains, etc., and As physical characteristics, in addition to high heat resistance, solvent solubility, high transparency, high refractive index, low birefringence, etc., it also shows high air permeability.

As said cardo-type resin (5), resin represented by the following general formula is mentioned preferably, for example.

In the formula, X is the group shown in the following chemical formula, Y is the residue after removing the carboxylic anhydride group (-CO-O-CO-) from the dicarboxylic anhydride, and Z is the residue after removing two carboxyl groups from the tetracarboxylic dianhydride. The residue after the acid anhydride group; n is an integer from 0 to 20);

Specific examples of the dicarboxylic anhydride (dicarboxylic anhydride before removal of the carboxylic anhydride group) from which Y is derived include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, Formic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorobridge anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, etc.

In addition, specific examples of tetracarboxylic dianhydride (tetracarboxylic dianhydride before removal of two carboxylic anhydride groups) from which Z is derived include, for example, pyromellitic anhydride, diphenyl ketone tetracarboxylic acid di Anhydride, tetracarboxylic dianhydride such as biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, etc.

The polystyrene-equivalent weight average molecular weight (Mw) of the aforementioned cardo resin measured by gravimetric gel permeation chromatography (GPC) is preferably 1,000-1,000,000, more preferably 3,000-50,000, most preferably 5,000-15,000 .

As the alkali-soluble resin, one of the above-mentioned alkali-soluble resins (1) to (5) may be used alone, or two or more of them may be used in combination. In addition, the alkali-soluble resin is preferably used in combination with a pigment dispersant described later, so that undissolved matter does not remain in the non-pixel portion of the substrate, and the adhesion to the substrate is excellent, and high-density color pixels can be formed. Specifically, it is preferable to use a part of the alkali-soluble resin together with a pigment dispersant described later in the dispersion treatment step. At this time, it is preferable to use the alkali-soluble resin in the range of 5-200 mass % with respect to a pigment, and it is more preferable to use it in the range of 10-100 mass %.

In addition, as the alkali-soluble resin, alkali-soluble resins other than the above-mentioned alkali-soluble resins (1) to (5) can also be used. Such resins include, for example, alkali-soluble resins obtained by using a polymerizable monomer having a phenolic hydroxyl group as an acidic group as an essential component, or polymerizable monomers having a sulfonic acid group as an acidic group. Alkali-soluble resins obtained by using them as essential components. Here, as a polymeric monomer which has the said phenolic hydroxyl group, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene etc. are mentioned, for example. In addition, one or more hydrogen atoms other than the phenolic hydroxyl group bonded to the aromatic ring of these monomers and the vinyl group are substituted with an alkyl group, an alkoxy group, a halogen atom, a nitro group, a cyano group, etc. base, amido-based compounds, etc. Moreover, examples of polymerizable monomers having a sulfonic acid group as an acidic group include vinylsulfonic acid, styrenesulfonic acid, (meth)allylsulfonic acid, 2-hydroxy-3-(methyl) Allyloxypropanesulfonic acid, 2-sulfoethyl (meth)acrylate, or their salts.

When the composition of the present invention is used as a resist composition, the content ratio of the alkali-soluble resin in the composition is preferably 0.1 in the total solid content in terms of the appearance of the cured film and good adhesion to the substrate. The range of ~80% by mass, more preferably the range of 1-60% by mass.

As the radiation-sensitive substance (photosensitive substance) used in the resist composition, as long as it is mixed with the above-mentioned alkali-soluble resin, it can be irradiated with ultraviolet rays, far ultraviolet rays, excimer laser light, X-rays, electron beams, ion rays, molecular Substances that can change the solubility of the alkali-soluble resin to the developer, such as radiation and gamma rays, can be used.

Examples of the aforementioned radiation-sensitive substances include quinonediazide compounds, diazo compounds, diazide compounds, onium salt compounds, halogenated organic compounds, mixtures of halogenated organic compounds and organometallic compounds, and organic acids. Ester compounds, organic acid amide compounds, organic acid amide compounds, and poly(olefin) compounds described in JP-A-59-152, etc.

Examples of the aforementioned quinonediazide-based compounds include: 1,2-benzoquinoneazido-4-sulfonate, 1,2-naphthoquinonediazido-4-sulfonate, 1,2 -Naphthoquinonediazido-5-sulfonate, 2,1-naphthoquinonediazido-4-sulfonate, 2,1-naphthoquinonediazido-5-sulfonate, and 1 ,2-Benzoquinoneazido-4-sulfonyl chloride, 1,2-naphthoquinonediazido-4-sulfonyl chloride, 1,2-naphthoquinonediazido-5-sulfonyl chloride, 2 , sulfonyl chloride of quinonediazide derivatives such as 1-naphthoquinonediazido-4-sulfonyl chloride, 2,1-naphthoquinonediazido-5-sulfonyl chloride, etc.

Examples of the aforementioned diazo compound include: salts of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde, such as hexafluorophosphate, tetrafluoroborate, perchlorate, or periodate Inorganic salts of diazo resins which are the reaction products of the above-mentioned condensates; organic salts of diazo resins which are the products of the reactions of the above-mentioned condensates and sulfonic acids as described in USP 3,300,309.

Examples of the aforementioned azide compound and diazide compound include: azidochalconic acid and diazidebenzylidenemethylcyclohexanone as described in JP-A-58-203438 And azidocinnacinylacetophenones, aromatic azides or aromatic diazides described in Journal of the Chemical Society of Japan No. 12, p1708-1714 (1983), etc.

二唑系化合物、含鹵素的三

系化合物、含鹵素的苯乙酮系化合物、含鹵素的二苯基酮系化合物、含鹵素的亞碸系化合物、含鹵素的碸系化合物、含鹵素的噻唑系化合物、含鹵素的

唑系化合物、含鹵素的三唑系化合物、含鹵素的2-哌哢系化合物、含鹵素的脂肪族烴系化合物、含鹵素的芳香族烴系化合物、其它之含鹵素的雜環狀化合物、次磺醯基鹵化物系化合物等之各 種化合物，再者例如參(2,3-二溴丙基)磷酸酯、參(2,3-二溴-3-氯丙基)磷酸酯、氯四溴甲烷、六氯苯、六溴苯、六溴環十二烷、六溴聯苯、三溴苯基烯丙基醚、四氯雙酚A、四溴雙酚A、雙(溴乙基醚)四溴雙酚A、雙(氯乙基醚)四氯雙酚A、參(2,3-二溴丙基)異三聚氰酸酯、2,2-雙(4-羥基-3,5-二溴苯基)丙烷、2,2-雙(4-羥基乙氧基-3,5-二溴苯基)丙烷等之作為鹵素系阻燃劑使用的化合物、二氯苯基三氯乙烷等之作為有機氯系農藥使用的化合物等。 As the above-mentioned halogenated organic compound, for example, as long as it is a halide of an organic compound, it can be used. As specific examples, halogen-containing

Oxadiazole compounds, halogen-containing three

Halogen-containing acetophenone-based compounds, halogen-containing diphenyl ketone-based compounds, halogen-containing phenylene-based compounds, halogen-containing thiazole-based compounds, halogen-containing thiazole-based compounds, halogen-containing

Azole compounds, halogen-containing triazole compounds, halogen-containing 2-piperone compounds, halogen-containing aliphatic hydrocarbon compounds, halogen-containing aromatic hydrocarbon compounds, other halogen-containing heterocyclic compounds, Various compounds such as sulfenyl halide compounds, furthermore, for example, ginseng (2,3-dibromopropyl) phosphate, ginseng (2,3-dibromo-3-chloropropyl) phosphate, chlorotetra Methyl bromide, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenyl allyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, bis(bromoethyl ether) Tetrabromobisphenol A, bis(chloroethyl ether) tetrachlorobisphenol A, ginseng (2,3-dibromopropyl) isocyanurate, 2,2-bis(4-hydroxy-3,5 Compounds such as -dibromophenyl)propane and 2,2-bis(4-hydroxyethoxy-3,5-dibromophenyl)propane used as halogen-based flame retardants, dichlorophenyltrichloroethane Alkanes and other compounds used as organochlorine pesticides.

As said organic acid ester, a carboxylate, a sulfonate, etc. are mentioned, for example. Moreover, examples of the organic acid amide include carboxylic acid amide, sulfonamide, and the like. In addition, examples of organic acid imides include carboxylic acid imides, sulfonic acid imides, and the like. These radiation-sensitive substances may be used alone or in combination of two or more.

In the resist composition, the blending ratio of the radiation-sensitive substance 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.

烷等之醚類；乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二 醇單丙基醚等之醇醚類；甲酸乙酯、甲酸丙酯、甲酸丁酯、乙酸甲酯、乙酸乙酯、乙酸丁酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸丁酯、丁酸甲酯、丁酸乙酯、丁酸丁酯、丁酸丙酯、乳酸乙酯、乳酸丁酯等之酯類、2-氧基丙酸甲酯、2-氧基丙酸乙酯、2-氧基丙酸丙酯、2-氧基丙酸丁酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-甲氧基丙酸丁酯等之單羧酸酯類；溶纖劑乙酸酯、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、丙基溶纖劑乙酸酯、丁基溶纖劑乙酸酯等之溶纖劑酯類；丙二醇、丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丁基醚乙酸酯等之丙二醇類；二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇甲基乙基醚等之二乙二醇類；三氯乙烯、氟氯烷溶劑、HCFC、HFC等之鹵化烴類；如全氟辛烷之完全氟化溶劑類、甲苯、二甲苯等之芳香族類；二甲基乙醯胺、二甲基甲醯胺、N-甲基乙醯胺、N-甲基吡咯啶酮等之極性溶劑等之記載於出版書「溶劑袖珍手冊」(有機合成化學協會編，OHMSHA公司)中的溶劑。此等之溶劑係可以單獨使用，也可以併用2種以上。 Examples of the solvent used in the resist composition include: acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, butyrolactone Ketones such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tertiary butanol, pentanol, heptanol, octanol, nonanol, decanol and other alcohols; Glycol dimethyl ether, ethylene glycol diethyl ether, two

Alkanes and other ethers; alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, etc. Ethers; 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, butyl lactate, etc. esters, methyl 2-oxypropionate, ethyl 2-oxypropionate , Propyl 2-oxypropionate, Butyl 2-oxypropionate, Methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, 2 - monocarboxylic acid esters such as butyl methoxy propionate; cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, Cellosolve esters such as butyl cellosolve acetate; propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, etc. Propylene glycol; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, etc. Diethylene glycol; halogenated hydrocarbons such as trichlorethylene, fluorochloroalkane solvent, HCFC, HFC, etc.; fully fluorinated solvents such as perfluorooctane, aromatics such as toluene, xylene, etc.; dimethyl ethyl alcohol Polar solvents such as amide, dimethylformamide, N-methylacetamide, and N-methylpyrrolidone are described in the published book "Solvent Pocket Handbook" (edited by the Organic Synthetic Chemistry Association, OHMSHA Corporation) solvent in. These solvents may be used alone or in combination of two or more.

The color resist composition of another specific form of the resist composition is, for example, composed of the fluorine-containing active energy ray curable resin (I) of the present invention and a color resist. The color resist includes, for example, an alkali-soluble resin, a polymerizable compounds, colorants.

As the alkali-soluble resin used in the color resist composition, for example, the alkali-soluble resin used in the above-mentioned photoresist composition, etc. can be used.

The aforementioned polymerizable compound can be used without particular limitation as long as it has a photopolymerizable functional group capable of polymerizing 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, aromatic Esters of polyols and unsaturated carboxylic acids, esters obtained by esterification of unsaturated carboxylic acids with polycarboxylic acids and polyvalent hydroxy compounds such as the aforementioned aliphatic polyols, aromatic polyols, etc., A polymerizable compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acryl-containing hydroxyl compound, etc.

Examples of esters of the aforementioned aliphatic polyhydroxy compound and unsaturated carboxylic acid include 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 tetra (Meth)acrylates such as (meth)acrylates, dipentaerythritol penta(meth)acrylates, dipentaerythritol hexa(meth)acrylates, and glycerin (meth)acrylates. Also, itaconate esters in which the (meth)acrylic acid part of these acrylates are replaced with itaconic acid, crotonic acid esters in which crotonic acid is replaced, or maleate esters in which maleic acid is replaced wait.

Examples of esters of the aforementioned aromatic polyhydroxy compound and unsaturated carboxylic acid include: hydroquinone di(meth)acrylate, resorcinol di(meth)acrylate, gallicol tri(meth)acrylate Esters etc. Moreover, the ester obtained by the esterification reaction of an unsaturated carboxylic acid, a polycarboxylic acid, and a polyvalent hydroxyl compound may be a single thing, and may be a mixture. Such esters include, for example, esters obtained from (meth)acrylic acid, phthalic acid, and ethylene glycol, esters obtained from (meth)acrylic acid, maleic acid, and diethylene glycol, esters obtained from (meth)acrylic acid, maleic acid, and diethylene glycol, Esters derived from methacrylic acid, terephthalic acid and pentaerythritol, esters derived from (meth)acrylic acid, adipic acid, butanediol and glycerin, etc.

Examples of polymerizable compounds having a urethane skeleton obtained by reacting the aforementioned polyisocyanate compound with a (meth)acryl group-containing hydroxy compound include hexamethylene diisocyanate, trimethylhexamethylene Aliphatic diisocyanates such as methyl diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate, and ( Reactant of hydroxyl compounds having (meth)acryloyl groups such as 2-hydroxyethyl meth)acrylate and 3-hydroxy[1,1,1-tri(meth)acryloxymethyl]propane.

Examples of polymerizable compounds other than those mentioned above include: (meth)acrylamides such as ethylidenebis(meth)acrylamide; allyl esters such as diallyl phthalate; divinyl Compounds with vinyl groups such as phthalates, etc.

Moreover, as said polymeric compound, the polymeric compound which has an acidic group can also be used. Such a polymerizable compound having an acidic group is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. It is preferable to react a non-aromatic carboxylic acid anhydride with respect to an unreacted hydroxyl group of the aliphatic polyhydroxy compound. Multifunctional monomer with acid groups. Moreover, among the above-mentioned aliphatic polyhydroxy compounds, those using pentaerythritol and dipentaerythritol are particularly preferable. These single systems may use only 1 type, and may use 2 or more types together. Moreover, you may use together the monomer which has an acidic group, and the monomer which does not have an acidic group.

Furthermore, as a preferred specific example of a polyfunctional polymerizable compound having an acid group, for example, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate commercially available as "Aronix TO-1382" from Toagosei Co., Ltd. A mixture of acrylate and succinate of dipentaerythritol pentaacrylate as main components. This polyfunctional polymeric compound can also be used together with another polyfunctional polymeric compound.

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, in terms of good developability and curability. Also, when using two or more polyfunctional polymerizable compounds with different acid values or a polyfunctional polymerizable compound not having an acid group in combination, the acid value of the mixture after mixing all the polyfunctional polymerizable compounds is preferably one of the above within range.

In the aforementioned color resist composition, the content ratio of the aforementioned polymerizable compound is preferably in the range of 5 to 80% by mass of the total solid content, more preferably in the range of 10 to 70% by mass, and most preferably in the range of 20 to 50% by mass range. Moreover, the ratio of the aforementioned polymerizable compound is preferably in the range of 5 to 200% by mass, more preferably in the range of 10 to 100% by mass, and particularly preferably in the range of 20 to 80% by mass, relative to the colorant described later.

系、陰丹士林系、苝系等。再者，下述之「C.I.」意指色指數。 As the said coloring agent, if it can color, it may be a pigment or a dye, and can be used without particular limitation. In addition, both pigment-based organic pigments and inorganic pigments can be used. As said organic pigment, the pigment of each hue, such as a red pigment, a green pigment, a blue pigment, a yellow pigment, a purple pigment, an orange pigment, and a brown pigment, can be used. In addition, examples of the chemical structure of organic pigments include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, bismuth-based

Department, Indanthrene Department, Perylene Department, etc. In addition, the following "CI" means color index.

Examples of the aforementioned red pigments 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, 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, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 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 et al. Among them, C.I. Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242 or 254 is preferable, and C.I. Pigment Red 177, 209, 224 or 254 is more preferable.

Examples of the aforementioned green pigments 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. Among these, C.I. Pigment Green 7, 36 or 58 is preferable.

Examples of the aforementioned blue pigments include C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19 , 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76 , 78, 79, etc. Among them, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6 is preferable, and C.I. Pigment Blue 15:6 is more preferable.

Examples of the aforementioned yellow pigments 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, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 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, 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, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, etc. Among them, 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 aforementioned purple pigments 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 aforementioned orange pigments include C.I. 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, etc. Among these, C.I. Pigment Orange 38 or 71 is preferred.

Since the pixels of the three primary colors of the color filters used in liquid crystal display devices and organic EL display devices are red (R), green (G), and blue (B), the aforementioned red pigments, green pigments, and blue Pigment is used as the main component to improve color reproducibility, and organic pigments of yellow, purple, orange and other colors can also be used for hue adjustment.

Moreover, as said inorganic pigment, barium sulfate, lead sulfate, titanium oxide, lead yellow, iron oxide red, chromium oxide etc. are mentioned, for example.

Furthermore, in order to improve the brightness of the color liquid crystal display device and the organic EL display device, the average particle size of the aforementioned organic pigment is preferably 1 μm or less, more preferably 0.5 μm or less, especially preferably 0.3 μm or less. It is preferable to divide the organic pigment into such an average particle diameter. Used for bulk processing. In addition, the average primary particle size of the above-mentioned organic pigment is preferably 100 nm or less, more preferably 50 nm or less, especially preferably 40 nm or less, particularly preferably in the range of 10 to 30 nm. In addition, the average particle size of the organic pigment is measured by a dynamic light scattering particle size distribution meter, for example, the Nanotrac particle size distribution measuring device "UPA-EX150" and "UPA-EX150" manufactured by Nikkiso Co., Ltd. can be used. UPA-EX250" and so on.

When the aforementioned color resist composition is used to form a black matrix (BM), the coloring agent used is not particularly limited as long as it is black, and examples thereof include carbon black, lamp black, acetylene black, bone black, thermal black, Channel black, furnace black, graphite, iron black, titanium black, etc. Moreover, the combination which mixed 2 or more types of organic pigments and became black by color mixing may be sufficient. Among them, carbon black and titanium black are preferable from the viewpoint of light-shielding ratio and image characteristics.

Examples of commercially available carbon blacks include MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, and #30 manufactured by Mitsubishi Chemical Corporation. , #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, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B, etc., Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex G L, Printex A, Printex G L, etc. manufactured by Evonik Degussa Japan Co., Ltd. P, Printex U, Printex V, SpecialBlack550, SpecialBlack 350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170, etc. CABOT JAPAN stock can be cited有限公司製的Monarch120、Monarch280、Monarch460、Monarch800、Monarch880、Monarch900、Monarch1000、、Monarch1100、Monarch1300、Monarch1400、Monarch4630、REGAL99、REGAL99R、REGAL415、REGAL415R、REGAL250、REGAL250R、REGAL330、REGAL400R、REGAL55R0、REGAL660R、BLACK PEARLS480、 PEARLS130, VULCAN XC72R, ELFTEX-8, etc., RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN8V5 manufactured by COLUMBIAN CARBON CO., LTD. RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000, etc.

Among the above-mentioned carbon blacks, it is preferable to use resin-coated carbon blacks that have high optical density and high surface resistivity required for a black matrix having a color filter. Also, resin-coated carbon Black can be obtained, for example, from JP-9-26571, JP-9-71733, JP-9-95625, JP-9-238863 or JP-11-60989. The method described is obtained by processing well-known carbon black.

And, as the preparation method of aforementioned titanium black, can enumerate: the method that the mixture of titanium dioxide and metal titanium is heated and reduced under reducing gas environment described in Japanese Patent Application Publication No. 49-5432; No. 57-205322 communique records the method of reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride in a reducing gas environment containing hydrogen; The method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia described in the gazette; the method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it in the presence of ammonia described in Japanese Patent Application Laid-Open No. 61-201610. As a commercial item of titanium black, titanium black 10S, 12S, 13R, 13M, 13M-C etc. by Mitsubishi Materials Co., Ltd. are mentioned, for example.

When two or more organic pigments are mixed to form a black combination by color mixing, black pigments in which red, green, and blue three-color pigments are mixed are mentioned. In order to prepare black pigments, the color materials that can be mixed and used include: Victoria Pure Blue (C.I.42595), Auramine O (C.I.41000), Cathilon Brilliant Flavin (Basic 13), Rose Red 6GCP (C.I.45160), Rose Red B (C.I.45170), Saffron OK70: 100 (C.I.50240), Erioglaucine X (C.I.42080), No.120/Lino Yellow (Lionol Yellow)(C.I.21090), Lionol Yellow GRO(C.I.21090), Shimura Fast Yellow 8GF(C.I.21105), Benzidine Yellow 4T-564D(C.I.21095), Shimura Fast Red (Shimura Fast Red) 4015 (C.I.12355), Lion Red 7B4401 (C.I.15850), Fastogen Blue TGR-L (C.I.74160), Lion Blue SM (C.I.26150), Lion Blue ES (C.I. Pigment Blue 15:6), Laino Red GD (C.I. Pigment Red 168), Laino Green 2YS (C.I. Pigment Green 36), etc.

In order to prepare black pigments, other color materials that can be mixed and used include, for example: C.I. 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. Purple 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 pigments 23, 25, 26, etc.

When carbon black is used as the black pigment, the average primary particle size is preferably in the range of 0.01-0.08 μm, and more preferably in the range of 0.02-0.05 μm in terms of good developability. In addition, the absorption of dibutyl phthalate (hereinafter referred to as "DBP") of the carbon black used is preferably in the range of 40 to 100cm ³ /100g, and from the perspective of good dispersibility and developability, it is more preferably The range of 50~80cm ³ /100g. Furthermore, the specific surface area of the carbon black used is preferably in the range of 50 to 120 m ² /g as measured by the BET method, and is more preferably in the range of 60 to 95 m ² /g in view of good dispersion stability.

In addition, the shape of carbon black particles is different from that of organic pigments, and there is a state called a structure in which the primary particles are fused, or fine pores may be formed on the surface of the particles due to post-processing. Therefore, in order to express the particle shape of carbon black, it is generally preferable to measure the DBP absorption (JIS K6221) and the BET method in addition to the average particle diameter of the primary particle obtained by the same method as the above-mentioned organic pigment. Specific surface area (JIS K6217), used as an indicator of organizational structure or pore volume.

In addition, dyes can also be used as colorants. As such dyes, for example, azo-based dyes, anthraquinone-based dyes, phthalocyanine-based dyes, quinoneimine-based dyes, quinoline-based dyes, nitro-based dyes, carbonyl-based dyes, methine-based dyes, Xanthene-based dyes, triarylmethane-based dyes, coumarin-based dyes, trimethyl-based dyes, anthraquinone-based dyes, and other dyes.

Examples of the aforementioned other dyes include dyes such as oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes. of Dyers and Colourists), compounds classified as dyes, or various dyes described in Dyeing Notes (Yorsensha).

Examples of other dyes mentioned above include: C.I. Solvent Yellow 4 (hereinafter, C.I. 98, 99; C.I. solvent red 45, 49, 125, 130; C.I. solvent orange 2, 7, 11, 15, 26, 56; etc. 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; etc. 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 Orange 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 Orange 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; etc. C.I. Mordant dyes, etc.

Among the coloring agents listed above, it is preferable to use pigments in terms of the light resistance, weather resistance, and compactness of the finally obtained cured film. However, in order to adjust the hue, it can also be used in combination with pigments if necessary. dye.

The content ratio of the aforementioned pigments and dyes is the mass ratio [pigment:dye], preferably 1:99~99:1, more preferably 99:1~40:60, especially preferably 95:5~60:40. By containing the pigment and the dye in such a ratio, it is easy to obtain a cured film that is easy to optimize the transmission spectrum. Furthermore, it is easy to form a cured film having good heat resistance and chemical resistance.

The content ratio of the coloring agent in the color resist composition is preferably at least 1% by mass in the total solid content, more preferably in the range of 5-80% by mass, and most preferably in the range of 5-70% by mass.

Also, when the aforementioned color resist composition is used to form each pixel of red (R), green (G), and blue (B) of the color filter, the content ratio of the aforementioned colorant in the color resist composition is preferable It is the range of 5-60 mass % in the whole solid content, More preferably, it is the range of 10-50 mass %.

Furthermore, when the aforementioned color-resist composition is used to form a black matrix of a color filter, the content ratio of the coloring agent in the color-resist composition is preferably in the range of 20 to 80% by mass of the total solid content, more preferably It is in the range of 30~70% by mass.

In addition, the aforementioned organic pigments may also be subjected to rosin treatment, surface treatment using pigment derivatives introducing acidic groups or basic groups, etc., grafting treatment on the surface of pigments by polymer compounds, etc., by Micronization treatment such as sulfuric acid micronization method, cleaning treatment by organic solvent or water for removing impurities, removal treatment of ionic impurities by ion exchange method, etc. Furthermore, the particle size is preferably uniform, and an organic pigment with a uniform particle size can be obtained, for example, by adding a pigment dispersant and performing a dispersion treatment.

When using the said pigment dispersant, the usage-amount is preferably 1 mass part or less with respect to 1 mass part of pigments, More preferably, it is 0.05 mass part or more and 0.5 mass part or less. If the amount of the pigment dispersant used is within this range, it tends to obtain a uniformly dispersed pigment dispersion (dispersed in an organic solvent), which is preferable.

Examples of the pigment dispersant include surfactants; intermediates or derivatives of pigments; intermediates or derivatives of dyes; polyamide resins, polyurethane resins, polyester resins, Resin-type dispersants such as acrylic resins, etc. Among these, graft copolymers having nitrogen atoms, acrylic block copolymers having nitrogen atoms, urethane resin dispersants, and the like are preferred. Since these dispersants have nitrogen atoms, nitrogen atoms have affinity to the surface of the pigment, and by increasing the affinity of parts other than nitrogen atoms to the medium, the dispersion stability is improved. In addition, these dispersants may be used individually, and may use 2 or more types together.

Examples of commercially available pigment dispersants include "Efka" series manufactured by Efka Chemicals ("Efka 46", etc.); "Disperbyk" series manufactured by BYK Japan Co., Ltd., "BYK" series ("BYK -160", "BYK-161", "BYK-2001", etc.); "Solsperse" series manufactured by Lubrizol Co., Ltd. of Japan; "KP" series manufactured by Shin-Etsu Chemical Industry Co., Ltd., Kyoeisha Chemical Co., Ltd. "Polyflow" series manufactured by Kusumoto Chemical Co., Ltd.; "Disparlon" series manufactured by Kusumoto Chemical Co., Ltd.; "Ajisper" series manufactured by Ajinomoto Precision Technology Co., Ltd. ("Ajisper PB-814", etc.).

In addition, examples of organic solvents used in the preparation of the pigment dispersion include: acetate-based solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethoxypropionic acid Propionate-based solvents such as esters; aromatic solvents such as toluene, xylene, and methoxybenzene; butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl Ether-based solvents such as ether; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic hydrocarbon-based solvents such as hexane; N,N-dimethylformamide, Nitrogen compound-based solvents such as γ-butyrolactam and N-methyl-2-pyrrolidone; lactone-based solvents such as γ-butyrolactone; carbamates, etc. These solvents may be used alone or in combination of two or more.

Examples of the preparation method of the above-mentioned pigment dispersion liquid include a method of passing through a colorant kneading and dispersing step and a microdispersing step, a method of performing only a microdispersing step, and the like. In the above-mentioned kneading and dispersing step, the coloring agent, part of the alkali-soluble resin, and if necessary, the above-mentioned dispersant are mixed and kneaded. The mechanical system used for mixing can include double-rollers, three-rollers, ball mills, drum mills, dispersers, kneaders, co-kneaders, homogenizers, blenders, single-shaft or twin-shaft extruders, etc. By using such a kneader, the colorant can be dispersed while applying a strong shearing force. In addition, it is preferable that the particle size of the coloring agent be reduced in advance by a salt mill method or the like before the above-mentioned kneading.

On the other hand, in the above-mentioned microdispersion step, by adding a solvent to the colorant-containing composition obtained in the above-mentioned kneading and dispersing step, or by mixing a colorant, an alkali-soluble resin, a solvent, and the above-mentioned dispersion if necessary For the colorant, mix and disperse it with the dispersing medium of glass, zirconia or ceramic particles by using a disperser, so that the particles of the colorant can be dispersed to a microscopic state close to the primary particle.

Also, from the viewpoint of improving the transmittance and contrast of the color filter, the average particle diameter of the primary particles of the coloring agent is preferably 10 to 100 nm, more preferably 10 to 60 nm. Furthermore, the average particle size of the coloring agent is measured by a dynamic light scattering particle size distribution meter, for example, a Nanotrac particle size distribution measuring device "UPA-EX150" manufactured by Nikkiso Co., Ltd. , "UPA-EX250" and so on.

In the resist composition, a photopolymerization initiator may also be included.

化合物、醯基膦氧化物化合物、肟化合物。又，亦可使用日本特開2008-181087號公報中記載之光陽離子聚合起始劑(例如，由鎓陽離子與來自路易斯酸的陰離子所構成者)。其中，於感度之點，較佳為肟化合物。 As the aforementioned photopolymerization initiator, for example, biimidazole compounds, alkyl phenone compounds, three

compounds, acylphosphine oxide compounds, oxime compounds. Moreover, the photocationic polymerization initiator (for example, what consists of an onium cation and an anion derived from a Lewis acid) described in Unexamined-Japanese-Patent No. 2008-181087 can also be used. Among these, oxime compounds are preferred in terms of sensitivity.

Examples of the aforementioned biimidazole compound include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2 ,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to JP-A-6-75372, JP-A-6-75373, etc.), 2, 2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5 '-Tetrakis(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2 , 2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Laid-Open Sho 62-174204, etc.), imidazole compounds in which the phenyl at the 4,4'5,5'-position is substituted by a carboalkoxy group (for example, refer to JP-A-7-10913, etc.), etc. Preferable examples include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl )-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole .

啉基-1-(4-甲基氫硫基苯基)丙-1-酮、2-二甲基胺基-1-(4-

啉基苯基)-2-苄基丁-1-酮、2-二甲基胺基-1-(4-

啉基苯基)-2-(4-甲基苯基甲基)丁-1-酮、2-羥基-2-甲基-1-苯基丙-1-酮、苄基二甲基縮酮、2-羥基-2-甲基-1-[4-(2-羥基乙氧基)苯基]丙-1-酮、1-羥基環己基苯基酮、2-羥基-2-甲基-1-(4-異丙烯基苯基)丙-1-酮之寡聚物等，較佳可舉出2-甲基-2-

啉基-1-(4-甲基氫硫基苯基)丙-1-酮、2-二甲基胺基-1-(4-

啉基苯基)-2-苄基丁-1-酮等。亦可以使用Irgacure 369、907(以上，BASF Japan公司製)等之市售品。 Examples of the aforementioned alkylphenone compounds include diethoxyacetophenone, 2-methyl-2-

Linyl-1-(4-methylhydrogensulfurylphenyl)propan-1-one, 2-dimethylamino-1-(4-

Linylphenyl)-2-benzylbutan-1-one, 2-dimethylamino-1-(4-

Linylphenyl)-2-(4-methylphenylmethyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal , 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl- Oligomers of 1-(4-isopropenylphenyl)propan-1-one, etc., preferably 2-methyl-2-

Linyl-1-(4-methylhydrogensulfurylphenyl)propan-1-one, 2-dimethylamino-1-(4-

Linylphenyl)-2-benzylbutan-1-one, etc. Commercially available products such as Irgacure 369 and 907 (above, manufactured by BASF Japan Co., Ltd.) can also be used.

化合物，例如可舉出：2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三

、2,4-雙(三氯甲基)-6-胡椒基-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三

等。 as the aforementioned three

Compounds, for example: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-tri

wait.

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) can also 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-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl) )-9H-carbazol-3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-{2-methyl-4-(3,3-di Methyl-2,4-dioxolylmethoxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, etc. Commercially available products such as Irgacure OXE-01 and OXE-02 (the above, manufactured by BASF Japan Co., Ltd.), N-1919 (manufactured by ADEKA Corporation) can also be used.

In addition, as a polymerization initiator having a group capable of causing chain transfer, a photopolymerization initiator described in JP 2002-544205 A can also be used. Examples of the above-mentioned polymerization initiator having a group capable of causing chain transfer include compounds of the following formula and the like.

Furthermore, examples of the polymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and other benzoin compounds. Indium compounds; diphenyl ketone, methyl o-benzoyl benzoate, 4-phenyl diphenyl ketone, 4-benzoyl-4'-methyl diphenyl sulfide, 3,3', 4,4'-tetrakis(tert-butylperoxycarbonyl)diphenylketone, 2,4,6-trimethyldiphenylketone and other diphenylketone compounds; 9,10-phenanthrenequinone, 2- Quinone compounds such as ethyl anthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzophenone, methyl phenylglyoxylate, titanocene compounds, etc. These are preferably used in combination with a polymerization initiation aid (especially amines) described later.

In the resist composition, a polymerization initiation aid may be further included. The polymerization initiation aid is used in combination with a photopolymerization initiator, and is a compound or a sensitizer for promoting the polymerization of a polymerizable compound whose polymerization is initiated by the polymerization initiator.

As a polymerization start aid, an amine compound, a thiazoline compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned, for example. Examples of the aforementioned amine compound include: triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate, Isoamyl methylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4 ,4'-bis(dimethylamino)diphenyl ketone (commonly known as Michelle's ketone), 4,4'-bis(diethylamino)diphenyl ketone, 4,4'-bis(ethyl (methylamino) diphenyl ketone and the like, among which 4,4'-bis(diethylamino) diphenyl ketone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) can also be used.

As said thiazoline compound, the compound etc. which are shown below are mentioned, for example.

Examples of the aforementioned alkoxyanthracene compounds 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, etc.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone , 1-chloro-4-propoxythioxanthone, etc.

Examples of the carboxylic acid compound include: phenylthioglycolic acid, methylphenylthioglycolic acid, ethylphenylthioglycolic acid, methylethylphenylthioglycolic acid, dimethyl Phenyl mercaptoacetic acid, methoxyphenyl mercaptoacetic acid, dimethoxyphenyl mercaptoacetic acid, chlorophenyl mercaptoacetic acid, dichlorophenyl mercaptoacetic acid, N-phenylglycerin Amino acid, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, etc.

In addition, the resist composition may further contain a polyfunctional thiol compound. This polyfunctional thiol compound is a compound having two or more thiol groups in the molecule. Among these, it is preferable to use a compound having two or more mercapto groups adjacent to an aliphatic hydrocarbon group, since it can form a pattern with high sensitivity.

The solvent system contained in the resist composition is not particularly limited, and solvents generally used in this field can be used. For example, ester solvents (solvents containing -COO-), ether solvents other than ester solvents (solvents containing -O-), ether ester solvents (solvents containing -COO- and -O-), ester solvents other than Selectively use among ketone solvents (solvents containing -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl oxide, and the like. These solvents may be used alone or in combination of two or more.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, acetic acid Isoamyl Ester, Butyl Propionate, Isopropyl Butyrate, Ethyl Butyrate, Butyl Butyrate, Methyl Pyruvate, Ethyl Pyruvate, Propyl Pyruvate, Methyl Acetoacetate, Ethyl Acetoacetate Esters, cyclohexanol acetate, γ-butyrolactone, etc.

烷、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇甲基乙基醚、二乙二醇二丙基醚、二乙二醇二丁基醚、苯甲醚、苯乙醚、甲基苯甲醚等。 Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and 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-di

Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, Benzene ether, phenetole, methyl anisole, etc.

Examples of the aforementioned ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxy ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate , 2-ethoxy-2-methylpropionate ethyl ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate Esters, Propylene Glycol Monoethyl Ether Acetate, Propylene Glycol Monopropyl Ether Acetate, Ethylene Glycol Monomethyl Ether Acetate, Ethylene Glycol Monoethyl Ether Acetate, Diethylene Glycol Monoethyl Ether Acetate, diethylene glycol monobutyl ether acetate, etc.

Examples of the aforementioned ketone solvent include: 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl -2-pentanone, cyclopentanone, cyclohexanone, isophorone, etc.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.

As said aromatic hydrocarbon solvent, benzene, toluene, xylene, mesitylene etc. are mentioned, for example.

Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

Among the above-mentioned solvents, organic solvents having a boiling point at 1 atm of 120° C. to 180° C. are preferred from the viewpoint of coating properties and drying properties. Among them, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like are preferable.

With respect to the resist composition, the content of the solvent is preferably 60-95% by mass, more preferably 70-90% by mass. In other words, the solid content of the resist composition is preferably 5-40% by mass, more preferably 10-30% by mass. When content of a solvent exists in the said range, there exists a tendency for the flatness at the time of coating to become favorable.

Moreover, in the range which does not impair the effect of this invention, you may contain the surfactant other than a fluorine-containing active energy ray curable resin (I). Examples of the aforementioned surfactant include silicone-based surfactants, fluorine-based surfactants, silicone-based surfactants having fluorine atoms, surfactants having fluorine atoms and ethylenically unsaturated bonds, etc. .

Furthermore, the resist composition may contain various additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-coagulation agents, organic amine compounds, and hardeners as needed.

Examples of the aforementioned filler include fine particles of glass, alumina, and the like.

Examples of the aforementioned adhesion promoter include: vinyltrimethoxysilane, vinyltriethoxysilane, vinylparaffin (2-methoxyethoxy)silane, N-(2-aminoethyl) base)-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, etc.

Examples of the aforementioned antioxidant include: 4,4'-thio-bis(6-tert-butyl-3-methylphenol), triethylene glycol-bis[3-(3-tert-butyl base-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid ester], pentaerythritol-tetra[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-paraffin (3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,6-di tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,2'-methylene bis(4-methyl-6-tert-butylphenol) , 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-butylene-bis(3-methyl-6-tert-butylphenol), 1 ,1,3-paraffin(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-paraffin(4-hydroxybenzyl)benzene and tetra[methylene- 3-(3,5'-di-tert-butyl-4'-hydroxyphenylpropionate)]methane, etc.

-2-基)-5-己氧基苯酚等之三

系等。 As the aforementioned ultraviolet absorber, for example, benzotriazole series such as 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole; Diphenyl ketone series such as -hydroxy-4-octyloxydiphenyl ketone; 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, etc. Benzoate esters; 2-(4,6-diphenyl-1,3,5-tri

-2-yl)-5-hexyloxyphenol etc.

department etc.

Sodium polyacrylate etc. are mentioned as said antiagglomeration agent, for example.

By adding the organic amine compound, no residue is generated on the unexposed portion of the substrate during development, and a pixel with excellent adhesion to the substrate can be provided. Examples of the organic amine compound include n-propylamine, isopropylamine, n-butylamine, isobutylamine, second-butylamine, third-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, Monoalkylamines such as n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, etc.; cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine Monocycloalkylamines such as hexylamine; methylethylamine, diethylamine, methyl-n-propylamine, ethyl-n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisopropylamine Dialkylamines such as butylamine, di-2-butylamine, di-3-butylamine, di-n-pentylamine, di-n-hexylamine, etc.; monoalkyl monocycloalkanes such as methylcyclohexylamine, ethylcyclohexylamine, etc. Dicycloalkylamines such as dicyclohexylamine; 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-second butylamine, tri-tertiary butylamine, tri-n-pentylamine Trialkylamines such as amine and tri-n-hexylamine; dialkyl monocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine; methyldicyclohexylamine and ethyldicyclohexylamine Monoalkyldicycloalkylamines such as amines and tricyclohexylamine; 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1 - monoalkanolamines such as butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, etc.; monocycloalkanolamines such as 4-amino-1-cyclohexanol; Diakanolamines such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine, etc.; bis(4-cyclo Dicycloalkanolamines such as hexanol) amines; triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine Trialkanolamines such as Tris(4-cyclohexanol)amines; Tricycloalkanolamines such as Tris(4-cyclohexanol)amines; 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- Amino alkanediols such as propylene glycol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol; 4-amino-1,2-cyclohexanediol Alcohol, 4-amino-1,3-cyclohexanediol and other aminocycloalkanediols; 1-aminocyclopentanonemethanol, 4-aminocyclopentanonemethanol and other amino cycloalkanes Ketone methanol; 1-aminocyclohexanonemethanol, 4-aminocyclohexanonemethanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethyl Aminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol and other cycloalkanemethanols containing amino groups; β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4 -aminobutyric acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclopropanecarboxylic acid, Amino carboxylic acids such as 1-aminocyclohexane carboxylic acid and 4-amino cyclohexane carboxylic acid; aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, p-n-methylaniline Propylaniline, p-isopropylaniline, p-n-butylaniline, p-tert-butylaniline, 1-naphthylamine, 2-naphthylamine, N,N-dimethylaniline, N,N-diethylaniline Aromatic amines such as aniline, p-methyl-N,N-dimethylaniline, etc.; o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-aminobenzyl alcohol Aminobenzyl alcohols such as diethylaminobenzyl alcohol; aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol, etc. Amino benzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid, etc.

As said hardening|curing agent, when using the resin which has a carboxyl group as an alkali-soluble resin, the compound etc. which can react with this carboxyl group by heating, and crosslink an alkali-soluble resin etc. are mentioned, for example. Moreover, the compound which can produce a cured film by independent polymerization is also mentioned. As said compound, an epoxy compound, an oxetane compound, etc. are mentioned, for example.

Examples of the epoxy compound include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, and novolak epoxy resins. resin, other aromatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidylamine resins, epoxy resins such as epoxidized oils, or the Brominated derivatives of epoxy resins, aliphatic, cycloaliphatic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, epoxides of (co)polymers of butadiene, Epoxide of (co)polymer of isoprene, (co)polymer of glycidyl (meth)acrylate, triglycidyl isocyanurate, etc.

Examples of the aforementioned oxetane compound include: bisoxetane carbonate, dioxetane xylylene, bisoxetane adipate, terephthalamide Ester bisoxetane, cyclohexanedicarboxylic acid bisoxetane, etc.

When an epoxy compound, an oxetane compound, etc. are contained as a curing agent, a compound capable of ring-opening polymerization of the epoxy group of the epoxy compound or the oxetane skeleton of the oxetane compound may be included. As this compound, polyhydric carboxylic acid, polyhydric carboxylic acid anhydride, an acid generator etc. are mentioned, for example.

Examples of the aforementioned polyvalent carboxylic acids include: phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1 ,Aromatic polycarboxylic acids such as 4,5,8-naphthalene tetracarboxylic acid, 3,3',4,4'-diphenyl ketone tetracarboxylic acid, etc.; succinic acid, glutaric acid, adipic acid, 1, 2,3,4-butane tetracarboxylic acid, maleic acid, fumaric acid, itaconic acid and other aliphatic polycarboxylic acids; hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid Formic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, 1 , 2,4,5-cyclohexanetetracarboxylic acid and other alicyclic polycarboxylic acids, etc.

Examples of the polyvalent carboxylic acid anhydrides include phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, and the like. Aromatic polycarboxylic acid anhydrides; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarboxylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, etc. Aliphatic polycarboxylic acid anhydrides; hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4- Alicyclic polycarboxylic acid anhydrides such as cyclohexane tricarboxylic anhydride, cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, humic anhydride, nazine anhydride, etc.; Ester group-containing carboxylic acid anhydrides such as diol bis-trimellitic acid and glycerin tritrimellitic anhydride.

As the aforementioned carboxylic acid anhydrides, those commercially available as epoxy resin curing agents can also be used. Examples of the aforementioned epoxy resin curing agent include Adeka Hardener EH-700 (manufactured by Asahi Denka Co., Ltd.), Rikacid HH, and MH-700 (both manufactured by Shin Nippon Chemical Co., Ltd.).

The aforementioned curing agents may be used alone or in combination of two or more.

In addition, the resist composition may contain an organic acid having a molecular weight of 1,000 or less. Examples of the aforementioned organic acid include organic acids disclosed in JP-A-5-343631. Specifically, 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, acrylic acid, and methacrylic acid, preferably malonic acid, oxalic acid, fumaric acid, and phthalic acid.

The content of the fluorine-containing active energy ray-curable resin (I) in the resist composition varies depending on the type of resist composition, coating method, target film thickness, etc., but it is possible to express the present invention with a small amount of addition. In view of the above effects, with respect to the solid content of 100 mass in the resist composition Parts, preferably 0.0001~10 parts by mass, more preferably 0.00001~5 parts by mass, especially preferably 0.01~2 parts by mass.

The coating method of the resist composition is different depending on the application, for example, the use of a gravure coater, a roll coater, a chip coater, a knife coater, an air knife coater, a curtain coater, a kiss coater, etc. Coating methods such as coater, spray coater, wheel coater, spin coater, dipping, screen printing, spray, coater, rod coater, electrostatic coating, or forming methods using various molds, etc.

The above-mentioned resist composition changes the physical properties of the resin such as solubility, viscosity, transparency, refractive index, conductivity, and ion permeability by irradiating with light such as visible light and ultraviolet light. Among active energy ray curable compositions, resist compositions (photoresist compositions, color resist compositions for color filters, etc.) require high leveling properties. Generally, in lithography related to semiconductors or liquid crystals, the resist composition is generally coated on a silicon wafer or deposited with various metals in a thickness of about 0.01 to 5 μm by spin coating or slit coating. on the glass substrate. At this time, fluctuations in the thickness of the coating film may cause quality degradation or defects in semiconductors or liquid crystal elements, but the fluorine-containing active energy ray-curable resin (I) of the present invention is used as an additive for this composition. A uniform coating film is formed due to its high leveling property, so it is possible to improve the productivity of semiconductors and liquid crystal elements, and to achieve higher functions.

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 agent. When used as a liquid-repelling agent, it is preferably used for a negative resist composition (photosensitive resin composition) mainly composed of the aforementioned alkali-soluble resin. Relative to the total solid content of the composition, preferably The fluorine-containing active energy ray-curable resin (I) of the present invention is used in an amount of 0.01 to 5.0% by mass.

A cured film with a pattern can be obtained by applying the negative resist composition using the fluorine-containing active energy ray-curable resin (I) as a liquid-repelling agent on the surface of a substrate, and exposing and developing. This pattern is also called a partition wall. The fluorine-containing active energy ray curable resin (I) of the present invention is segregated and hardened on its upper part to exert ink repellency. The ink can be uniformly applied in the area, and the injection of the ink in the undesired area other than the partition wall can be suppressed, and the ink can be printed in a desired pattern well.

Optical elements printed by the IJ method using partition walls in this way can be applied to organic EL elements, color filters of liquid crystal elements, organic TFT array elements, and the like.

[Example]

Hereinafter, several examples related to the present invention will be described, but the present invention is not intended to be limited to those shown in the examples. In addition, "parts" and "%" in the following explanations or tables represent solid content or active ingredients on a mass basis unless otherwise specified.

Example 1: Production of fluorine-containing active energy ray-curable resin (I-i)

In a glass flask equipped with a stirring device, a thermometer, a cooling pipe and a dripping device, add 50 parts of perfluoropolyether compounds having hydroxyl groups at both ends represented by the following formula (hereinafter referred to as "compound (1)"; The hydroxyl equivalent is 740g/eq; a representing the number of repetitions is 5, b is 7), 62.5 parts of epichlorohydrin and 20 parts of ethanol. Next, stirring was started under a nitrogen stream, and 8.3 parts of 49% sodium hydroxide aqueous solution was dripped over 2 hours while maintaining the temperature in the flask at 50°C. After completion of the dropping, the temperature was raised to 60° C., stirred for 3 hours, and then returned to room temperature.

Then, the reaction solution returned to room temperature was washed with ion-exchanged water. Washing was carried out by adding 50 parts of ion-exchanged water to the reaction solution and stirring, then allowing the water layer to separate and separate by standing still, and repeating this operation twice. From the reaction solution after washing, the unreacted epichlorohydrin was distilled off by vacuum distillation, and filtered to obtain 52.2 parts of poly(perfluoroalkane) represented by the following formula (a1-1). Ether) chain and a compound having epoxy groups at both ends thereof (hereinafter referred to as "compound (a1-1)"). This compound (a1-1) was a transparent liquid with an epoxy equivalent of 1,112 g/eq., and the average value of the number n of repeating units in the following compound (a1-1) was 0.4.

Next, in a glass flask equipped with a stirring device, a thermometer, a cooling pipe, and a dropping device, 47.4 parts of compound (a1-1), 17.2 parts of bisphenol A diglycidyl ether, and 16.0 parts of bisphenol A Heating at 150°C for 40 hours with 1000ppm tetrabutylphosphonium hydroxide (TBPH) gave compound (2) with Mw 28,000. Next, in 161 parts of the solution of NV=50% diluted by propylene glycol monomethyl ether acetate (PGMEA), 0.03 part of dibutyl dilaurate was added as a urethanization catalyst. Tin, 0.1 part of p-methoxyphenol as a polymerization inhibitor, start stirring under air flow, after heating up to 75°C, drop 19.4 parts of 2-acryloxyethyl isocyanate in 1 hour, stir at 75°C for 30 Minutes, the temperature was raised to 80°C, and the reaction was carried out by further stirring for 2 hours. As a result, it was confirmed by IR spectrum measurement that the absorption peak around 2360 cm ^-1 derived from the isocyanate group disappeared. Next, PGMEA was added to obtain a PGMEA solution containing 10% of a fluorine-containing active energy ray-curable resin (1-i).

Example 2: Production of fluorine-containing active energy ray-curable resin (2-i)

In a glass flask equipped with a stirring device, a thermometer, a cooling pipe, and a dropping device, add 50 parts of a compound having a hydroxyl equivalent of 754 g/eq represented by the same formula as the aforementioned compound (1) in which a is 5 and b is 7. (3), 6.5 parts of maleic anhydride. Next, stirring was started under a nitrogen stream, the temperature in the flask was raised to 160° C., and stirring was carried out for 1 hour. Then, 0.01 part of dibutyltin dilaurate was added as an esterification catalyst, the temperature in the flask was raised to 170 degreeC, and it stirred for 5 hours. Then, return to room temperature, obtain 56.5 parts of compounds represented by the following formula (a5-1) having poly(perfluoroalkylene ether) chains and carboxyl groups at its two ends (hereinafter referred to as "compound (a5) -1)"). This compound (a5-1) was a transparent liquid with an acid value of 64.0 mgKOH/g.

Then, in a glass flask equipped with a stirring device, a thermometer, a cooling pipe and a dripping device, add 50 parts of compound (a5-1), 23 parts of bisphenol A type epoxy resin (epoxy equivalent 485g/eq) and 1000ppm tetrabutylphosphonium hydroxide (TBPH) was heated at 150°C for 30 hours to obtain compound (4) with Mw53,000. Next, in 146 parts of the solution of NV=60% diluted by propylene glycol monomethyl ether acetate (PGMEA), 0.02 part of dibutyl dilaurate was added as a urethanization catalyst. Tin, 0.03 parts of p-methoxyphenol as a polymerization inhibitor, and 0.20 parts of 2,6-di-tert-butyl-p-cresol were stirred under air flow, and the temperature was raised to 75°C. Then, 6.7 parts of 2-acryloxyethyl isocyanate was dropped over 1 hour, stirred at 75°C for 1 hour, then heated up to 80°C, and stirred for 4 hours, and it was confirmed by IR spectroscopy that the isocyanate group was derived from around 2270 cm ^-1 The absorption peak disappears. Finally, PGMEA was added to obtain a PGMEA solution containing 10% of a fluorine-containing active energy ray-curable resin (2-i).

Example 3: Production of fluorine-containing active energy ray-curable resin (1-ii)

Add 49.0 parts of compound (a1-1), 16.3 parts of bisphenol F diglycidyl ether, 14.6 parts of bisphenol F and 1000 ppm Tetrabutylphosphonium hydroxide (TBPH) was heated at 150°C for 40 hours to obtain compound (5) with Mw 26,000. Next, in 160 parts of the solution of NV=50% diluted by propylene glycol monomethyl ether acetate (PGMEA), 0.03 part of dibutyl dilaurate was added as a urethanization catalyst. Tin, 0.1 part of p-methoxyphenol as a polymerization inhibitor, start stirring under air flow, after heating up to 75°C, drop 20.1 parts of 2-acryloxyethyl isocyanate in 1 hour, and stir at 75°C for 30 Minutes, the temperature was raised to 80°C, and the reaction was carried out by further stirring for 2 hours. As a result, it was confirmed by IR spectrum measurement that the absorption peak around 2360 cm ^-1 derived from the isocyanate group disappeared. Next, 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)

Add 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 1000 ppm tetrabutylphosphonium hydroxide (TBPH) were heated at 150° C. for 40 hours to obtain compound (6) with Mw 27,000. Next, in 158 parts of the solution of NV=50% diluted by propylene glycol monomethyl ether acetate (PGMEA), 0.03 part of dibutyl dilaurate was added as a urethanization catalyst. Tin, 0.1 part of p-methoxyphenol as a polymerization inhibitor, start stirring under air flow, after heating up to 75°C, drop 21.1 parts of 2-acryloxyethyl isocyanate in 1 hour, and stir at 75°C for 30 Minutes, the temperature was raised to 80°C, and the reaction was carried out by further stirring for 2 hours. As a result, it was confirmed by IR spectrum measurement that the absorption peak around 2360 cm ^-1 derived from the isocyanate group disappeared. Next, 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)

Add 48.4 parts of compound (a1-1), 17.6 parts of bisphenol A diglycidyl ether, 16.4 parts of bisphenol A and 1000 ppm Tetrabutylphosphonium hydroxide (TBPH) was heated at 150°C for 40 hours to obtain compound (7) with Mw 28,000. Next, add 5.7 parts of succinic anhydride and 3000 ppm of triphenylphosphine to 165 parts of the NV=50% solution of compound (7) diluted with propylene glycol monomethyl ether acetate (PGMEA), and heat up to 110°C , keep for 4 hours. After confirming the end point of the reaction by the acid value, cool to 75°C, add 0.03 parts of dibutyltin dilaurate as a urethane catalyst, and 0.1 part of p-methoxyphenol as a polymerization inhibitor, in the air flow 19.4 parts of 2-acryloxyethyl isocyanate was dripped for 1 hour, stirred at 75°C for 30 minutes, heated to 80°C, and stirred for 2 hours to carry out the reaction. As a result, it was confirmed by IR spectroscopy that the 2360 cm ^- The absorption peak near ¹ disappears. Next, PGMEA was added to obtain a PGMEA solution containing 10% of a fluorine-containing active energy ray-curable resin (1-iv).

Comparative Synthesis Example 1

In a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dripping device, add 20 parts of the aforementioned compound (a1-1), 20 parts of diisopropyl ether as a solvent, and 0.02 parts of p-formaldehyde as a polymerization inhibitor. Stirring of oxyphenol and 3.1 parts by mass of triethylamine as a neutralizing agent was started under air flow, and 2.7 parts by mass of acryloyl chloride was dropped over 1 hour while keeping the inside of the flask at 10°C. After dropping, stir at 10°C for 1 After 1 hour, the temperature was raised, and after stirring at 30°C for 1 hour, the temperature was raised to 50°C and stirred for 10 hours to react, and the disappearance of acryloyl chloride was confirmed by gas chromatography. Next, after adding 40 parts of diisopropyl ether as a solvent, 80 parts of ion-exchanged water was mixed, stirred, left to stand, and the water layer was separated and removed. This washing was repeated 3 times. Next, 0.02 parts of p-methoxyphenol as a polymerization inhibitor and 8 parts of magnesium sulfate as a dehydrating agent were added, and after standing for one day to completely dehydrate, the dehydrating agent was separated by filtration. Next, by distilling off the solvent under reduced pressure, 21.5 parts of a compound (8) having an acryl group at both ends of the perfluoropolyether chain represented by the following formula was obtained.

(In the formula, a is an average of 5, and b is an average of 8; in addition, the oxyperfluoromethylene unit and the oxyperfluoroethylene unit are randomly bonded).

Next, 63 parts by mass of methyl isobutyl ketone as a solvent was added to a glass flask equipped with a stirring device, a thermometer, a cooling pipe, and a dropping device, and the temperature was raised to 105° C. while stirring under a nitrogen stream. Then, 21.5 parts of the compound (8) obtained above, 41.3 parts of 2-hydroxyethyl methacrylate, and 135.4 parts of 9.4 parts dissolved in 126 parts of methyl isobutyl ketone were used as radical polymerization. Three kinds of dripping liquids of the polymerization initiator solution of tertiary butyl peroxy-2-ethylhexanoate as the initiator were respectively installed in separate dripping devices, and while the inside of the flask was kept at 105°C, they were simultaneously It takes 2 hours to drip. After completion|finish of dripping, after stirring at 105 degreeC for 10 hours, the solvent was distilled off under reduced pressure, and the polymer of 67.5 parts was obtained. Next, 74.7 parts of methyl ethyl ketone as a solvent, 0.1 part of p-methoxyphenol as a polymerization inhibitor, and 0.06 parts of dilauric acid dilaurate as a urethanization catalyst were added to the polymer obtained above. Butyl tin was started stirring under an air flow, and 44.8 parts of 2-acryloyloxyethyl isocyanate was dripped over 1 hour while maintaining 60 degreeC. After completion of the dropping, the mixture was stirred at 60°C for 1 hour, then heated to 80°C and stirred for 10 hours to react. As a result, the absorption peak around 2360 cm ^-1 originating from the isocyanate group was confirmed to disappear by IR spectrum measurement. Next, 37.4 parts of methyl ethyl ketones were added as a solvent, and 224.6 parts of methyl ethyl ketone solutions containing 50% of polymerizable fluorine compounds were obtained. When the molecular weight of this polymerizable fluorine compound was measured by GPC (polystyrene conversion molecular weight), the number average molecular weight was 2,200, and the weight average molecular weight was 6,500. Also, the fluorine content was 11%.

<Formation method of coating film>

Examples and Comparative Production of 3.0 parts of Unidic RS20-160 manufactured by DIC Co., Ltd., 1.2 parts of Aronix M-402 manufactured by Toa Gosei Chemical Co., Ltd., and solid content ratios of 0.1%, 0.5%, 1.0%, and 2.0% For example, the obtained resin was diluted with PGMEA, and a solution was prepared so that NV19.5%. 1 mL of the prepared solution was dropped onto the central portion of a 7 cm x 7 cm glass substrate, spin-coated at a rotation speed of 1000 rpm, and a rotation time of 10 seconds, and then heated and dried at 80° C. for 3 minutes to evaporate the solvent. Next, the dried coating film was cured by irradiating ultraviolet rays (UV) with an ultraviolet curing device (high-pressure mercury lamp in air atmosphere, ultraviolet irradiation dose: 0.5 kJ/m ² ). Furthermore, it heat-processed at 230 degreeC for 20 minutes, and produced the coating film as Examples 6-10 and the comparative example 1. Except not using a fluorine-type surfactant, the coating film of the comparative example 2 was produced similarly to the comparative example 1.

<Measurement of contact angle of PGMEA>

On the surface of the coating film, the contact angle of PGMEA was measured using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd. "MODEL CA-W701"). The results are shown in Table 1. The contact angle of Comparative Example 2 (blank) was 15°.

Claims (19)

A fluorine-containing active energy ray-curable resin characterized by having, in one molecule: at least one: an alkylene chain whose both ends are hydroxyl groups and at least one of the hydrogen atoms is substituted with a fluorine atom (provided that the alkylene chain A residue of (A) whose chain contains an etheric oxygen atom, and at least one: a residue of a divalent phenolic hydroxyl-containing compound (B) other than (A) and/or a divalent carboxylic acid (C) Residues; have their structural units through the linking group shown in the following structural formula (1),

[In the formula (1), X is a hydrogen atom or an organic group having a polymerizable group and/or an acid group], and at least one of the linking groups represented by the structural formula (1) contained in 1 molecule is : a linking group represented by the following structural formula (2), or a linking group represented by the aforementioned structural formula (1) in which X is a (meth)acryloyl group,

[In the formula (2), Y is a divalent linking group, and R is a hydrogen atom or a methyl group]. A fluorine-containing active energy ray-curable resin characterized by having in one molecule: at least one: an alkylene chain whose both ends are carboxyl groups and at least one of the hydrogen atoms is substituted with a fluorine atom (provided that the alkylene chain chain containing an etheric oxygen atom) (D), or an alkylene chain whose two ends are hydroxyl groups and at least one of the hydrogen atoms is substituted with a fluorine atom (provided that the alkylene chain contains ether Oxygen atoms) (A) and the residue of the reactant of dicarboxylic acid anhydride (E), and at least one: the residue of the divalent hydroxyl-containing compound (F) other than (A); The structural unit formed by the linking group shown in the structural formula (1),

[In formula (1), X is a hydrogen atom or an organic group having a polymerizable group and/or an acid group], and at least one of the linking groups represented by the structural formula (1) contained in one molecule X in is a monovalent organic group having a vinyl group or a (meth)acryl group. The fluorine-containing active energy ray curable resin according to claim 1 or 2, wherein the terminal is a hydrogen atom, carboxyl group or glycidyl group. The fluorine-containing active energy ray-curable resin according to claim 1 or 2, wherein the fluorine atom content of the fluorine-containing active energy ray-curable resin is in the range of 3 to 40% by mass. The fluorine-containing active energy ray-curable resin according to claim 1 or 2, wherein the weight average molecular weight of the fluorine-containing active energy ray-curable resin is The range of 5,000~200,000. The fluorine-containing active energy ray-curable resin according to claim 1 or 2, wherein the active energy ray-curable functional group concentration of the fluorine-containing active energy ray-curable resin is in the range of 0.5 to 3.0 mmol/g. The fluorine-containing active energy ray-curable resin according to claim 1 or 2, wherein the two terminals are hydroxyl groups and at least one of the hydrogen atoms is substituted with a fluorine atom in the alkylene chain (provided that the alkylene chain contains ether (A) an alkylene chain whose both ends are carboxyl groups and at least one of the hydrogen atoms is substituted with a fluorine atom (provided that the alkylene chain contains an etheric oxygen atom) ( D) are those with perfluoroalkylene ether chains. The fluorine-containing active energy ray-curable resin according to claim 1 or 2, wherein the divalent phenolic hydroxyl-containing compound (B) and the divalent hydroxyl-containing compound (F) are biphenols that may have substituents on the aromatic ring , bisphenol, binaphthol or naphthalenediol. The fluorine-containing active energy ray curable resin according to claim 1 or 2, wherein the structural formula (1) is a structure represented by the following structural formula (2),

[In the formula (2), Y is a divalent linking group, and R is a hydrogen atom or a methyl group]. A method for producing a fluorine-containing active energy ray-curable resin, characterized in that: For an alkylene chain having at least one hydrogen atom substituted with a fluorine atom (provided that the alkylene chain contains etheric oxygen atom) and epoxy group compound (a1), and divalent phenolic hydroxyl compound (a2) And/or divalent carboxylic acid (a3) as the secondary hydroxyl group in the reactant obtained by reacting as the essential raw material, the compound having (meth)acryl group and isocyanate group which is active energy ray hardening functional group ( a4) Reaction. A method for producing a fluorine-containing active energy ray-curable resin, characterized in that: For an alkylene chain having at least one hydrogen atom substituted with a fluorine atom (provided that the alkylene chain contains etheric oxygen atom) and carboxyl or hydroxyl compound (a5), and divalent epoxy compound (a6) as the necessary raw material in the reaction product of the secondary hydroxyl group, so that the (a group) acryl group, react with the compound (a4) of isocyanate group. The method for producing a fluorine-containing active energy ray-curable resin according to claim 10 or 11, which further reacts an acid anhydride group-containing compound (a7) with respect to a secondary hydroxyl group. A liquid repellent, characterized by comprising the fluorine-containing active energy ray-curable resin according to any one of claims 1 to 9. 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 other than the fluorine-containing active energy ray-curable resin (II) or an active energy ray-curing monomer (III). 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. The active energy ray-curable resin composition according to claim 14 or 15, further comprising a polymerization initiator. The active energy ray curable resin composition as claimed in item 14 or 15, It is a resist composition. A cured film obtained from the active energy ray curable resin composition according to any one of claims 14 to 17. The hardened film as claimed in item 18 is a partition wall.

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