TW201930385A - Fluorine-containing active energy ray-curable resin, liquid repellent agent, resin composition containing same, and cured film - Google Patents

Abstract

Provided are: a fluorine-containing active energy ray-curable resin which has a resin structure that enables easy adjustment of the fluorine atom content, and which has excellent surface segregation properties, while exhibiting sufficient leveling properties, water repellent oil repellent properties, liquid repellent properties and the like even if the amount of use thereof is small; a liquid repellent agent; a resin composition which contains this fluorine-containing active energy ray-curable resin; and a cured film. Specifically used is a fluorine-containing active energy ray-curable resin which comprises, in each molecule, a residue of an alkylene chain (A), wherein hydroxyl groups are at both ends and at least one hydrogen atom is substituted by a fluorine atom, and a residue of a divalent phenolic hydroxyl group-containing compound (B) other than the component (A) and/or a residue of a divalent carboxylic acid (C), and which has a structural unit wherein the above-described components are bonded by means of a linking group represented by formula (1) (wherein X represents a hydrogen atom, an organic group (x1) having a polymerizable group or an organic group (x2) having an acid group). This fluorine-containing active energy ray-curable resin is also configured such that at least one linking group contained in each molecule, said linking group being represented by the above-described structural formula (1), is a monovalent organic group (x1) having a polymerizable group.

Description

Fluorinated active energy ray curable resin, liquid repellent, resin composition containing the same, and cured film

The present invention relates to a fluorine-containing active energy ray-curable resin, a resin composition containing the same, and a cured film thereof, which can be applied as a surface modifier such as surface smoothness or water and oil repellency of a cured film, or as a liquid repellent.

In the past, fluorine-based surfactants or fluorine-based surface modifiers have been recognized for their excellent leveling properties, wettability, permeability, anti-blocking properties, sliding properties, water and oil repellency, and antifouling properties. Widely used in various coating materials, surface modifiers, etc.

Apply 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 only called "fluorine-based surfactants"), The cured film obtained by curing it exhibits excellent surface characteristics. On the other hand, fluorine-based surfactants are exposed to heat, humidification, exposure to chemicals such as acids and alkalis, and cleaning for dirt removal. One part is easily detached or volatilized from the surface of the hardened film. 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 for solving such a problem, there is a method of including an active energy ray-curable functional group in the structure of a fluorine-based surfactant and firmly bonding it to the surface of a cured film (for example, refer to Patent Document 1) . The fluorine-containing polymerizable resin provided in this Patent Document 1 becomes a component of the active energy ray-curable resin composition, thereby reducing problems such as detachment from the surface of the cured film, and can maintain functions such as the antifouling property of the surface for a long period of time. However, in order to create various fluorine-based surfactants with excellent performance balance, in the acrylic copolymer as in the aforementioned Patent Document 1, the content rate of fluorine atoms that can be contained in one molecule has an upper limit, and it is necessary to increase the Add amount.

In recent years, as one use of fluorine-based surfactants, liquid repellents have been known. Liquid repellents are used in the production of optical elements such as organic EL (Electro-Luminescence) devices, quantum dot displays, TFT (Thin Film Transistor) arrays, thin-film solar cells, etc. When the organic layer is used as a dot and pattern printing is performed by the inkjet (IJ) method, a photosensitive resin composition is used in order to prevent the ink mixture between adjacent dots from being uniformly coated with the ink during dot formation When the partition wall is formed by the lithography method, the additives included in the photosensitive resin composition are also called ink repellents (for example, refer to Patent Document 2).

The partition wall system 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 by a point surrounded by the partition wall including the side wall of the partition wall The opening used must have ink affinity. Although the film obtained from the resist composition containing the liquid repellent provided in the aforementioned Patent Document 2 can form such a partition wall, when the finer pattern printing is to be performed, the liquid repellency of the upper surface is insufficient In the case of the side wall of the partition wall, due to the transfer of the component from the fluorine-based surfactant, the ink affinity of the opening becomes insufficient, and higher performance is required (higher liquid-repellent performance, less addition The following effects show) liquid repellent.

Prior technical literature Patent Literature

Patent Literature 1 Japanese Unexamined Patent Publication No. 2012-092308

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

In view of the above-mentioned actual circumstances, the problem to be solved by the present invention is to provide a resin structure having an easy adjustment of the content of fluorine atoms, excellent surface segregation when used as one component of an active energy ray-curable composition, and even a small amount of use The amount of fluorine-containing active energy ray-curable resin, liquid-repellent agent, resin composition containing the same, and cured film can also exhibit sufficient leveling properties, water and oil repellency, and liquid repellency.

The present inventors have made intensive efforts to solve the above-mentioned problems, and found that by using a fluorine-containing active energy ray-curable resin, which has a linear structure linking the structural unit having a fluorine-containing alkylene chain and other A structural unit composed of a divalent hydrocarbon group and a structure containing an active energy ray-curable functional group in the connecting portion 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 method for producing the same, 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 one molecule : At least one: the residue of (A) an alkylene chain in which both ends are hydroxyl groups and at least one hydrogen atom is replaced with a fluorine atom (however, the aforementioned alkylene chain contains an oxygen atom having ethericity) (A), and At least one: the residues of the divalent phenolic hydroxyl group-containing compound (B) other than the aforementioned (A) and/or the residues of the divalent carboxylic acid (C); having those represented by the following structural formula (1) The structural unit bonded 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 acid group], and the aforementioned structural formula (1) contained in 1 molecule At least one of the connecting 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 method for producing the same, 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 being in one molecule Having: at least one: the residue of (D) an alkylene chain having at least one carboxyl group at both ends and at least one hydrogen atom substituted with a fluorine atom (however, the aforementioned alkylene chain contains an oxygen atom having ethericity) (D), Or an alkylene chain with hydroxyl groups at both ends and at least one hydrogen atom substituted with a fluorine atom (however, the alkylene chain contains an oxygen atom with etheric properties) (A) and dicarboxylic anhydride (E) The residue of the reactant, and at least one: the residue of the divalent hydroxyl group-containing compound (F) other than the aforementioned (A); having their structure bonded by the 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 acid group], and the aforementioned structural formula (1) contained in 1 molecule At least one of the connecting 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 can be applied when a cured film having a surface with excellent leveling properties, water and oil repellency, and liquid repellency is obtained. In addition, the fluorine-containing active energy ray-curable resin of the present invention can be used as a liquid repellent, and is suitable for the manufacture of optical elements such as organic EL elements, quantum dot displays, TFT arrays, thin-film solar cells, etc. that have become increasingly sophisticated in recent years. It is used as the material of the active energy ray-curable resin composition for pattern formation.

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

Forms 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 in which both ends are hydroxyl groups and at least one hydrogen atom is replaced with a fluorine atom (however, the aforementioned alkylene The base chain contains an etheric oxygen atom) (A) residues, and at least one: the residue of a divalent phenolic hydroxyl compound (B) other than (A) and/or a divalent carboxylic acid (C ); having their structural units bonded by a linking group represented by 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 acid group], and the aforementioned structural formula (1) contained in 1 molecule At least one of the connecting groups shown is a monovalent organic group (x1) having a polymerizable group. Hereinafter, this is also referred to as 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 by having in one molecule: at least one: an alkylene chain in which both ends are carboxyl groups and at least one hydrogen atom is substituted with a fluorine atom (however, The aforementioned alkylene chain contains an oxygen atom having etheric properties) (D), or an alkylene chain having hydroxyl groups at both ends and at least one hydrogen atom substituted with a fluorine atom (however, the aforementioned alkylene chain contains (Ether oxygen atom) (A) and the residue of the reactant of dicarboxylic anhydride (E), and at least one: the residue of a divalent hydroxyl group-containing compound (F) other than the aforementioned (A); A structural unit bonded by a linking group represented by 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 acid group], and the aforementioned structural formula (1) contained in 1 molecule At least one of the connecting groups shown is a monovalent organic group (x1) having a polymerizable group. Hereinafter, this is also referred to as a fluorine-containing active energy ray-curable resin (I-2).

Conventionally, as a fluorine-containing compound such as a fluorine-based surfactant, a perfluoroalkyl chain (however, the aforementioned alkyl chain includes those having etheric oxygen atoms) or a perfluoroalkylene chain (but, the aforementioned alkylene Acrylic monomers whose chains contain etheric oxygen atoms) are copolymerized with monomers copolymerizable therewith, and those obtained are mostly provided. In addition, there are also provided difunctional monomers having (meth)acryloyl groups at both ends of the perfluoroalkylene chain (but the aforementioned alkylene chain contains an oxygen atom having ethericity) and other polymerizability Copolymer of monomers. Among these, 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 these acrylic copolymerization methods has (meth)acrylic acid at both ends of the perfluorinated alkylene chain (but the aforesaid alkylene chain contains etheric oxygen atoms) Acyl-based bifunctional monomers, so if you want to increase the content of fluorine atoms contained in one molecule, gelation will occur. Therefore, the amount of fluorine atoms that can be introduced in one molecule has an upper limit, and the degree of freedom in design is low. In addition, regarding the water and oil repellency and leveling properties originally possessed by fluorine atoms, in order to exhibit a certain effect, it is necessary to increase the blending amount of the fluorine-containing compound (fluorine-based surfactant) in the composition. In addition, since a bifunctional monomer is used and a copolymerization method of acrylic monomers is used, a manufacturing method capable of suppressing gelation must be used, and as a result, a problem of easily containing a copolymer having a lower molecular weight occurs.

In the present invention, in order to solve these problems, raw materials easily obtained in industry are used to design a fluorine-containing active energy ray-curable resin having a new structure. Furthermore, the "(meth)acryloyl group" in the present invention refers to one or both of methacryloyl group and acryloyl group, and the so-called "(meth)acrylate" refers to nails One or both of acrylate and acrylate, the so-called "(meth)acrylic acid" refers to one or both of methacrylic acid and acrylic acid.

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

An alkylene chain in which the two terminals are hydroxyl groups and at least one hydrogen atom is substituted with a fluorine atom (however, the alkylene chain contains an oxygen atom having an etheric nature) (A), the two terminals are carboxyl groups and hydrogen The alkylene chain of which at least one of the atoms is substituted with a fluorine atom (however, the aforementioned alkylene chain contains an oxygen atom having an etheric nature) (D) The alkylene chain in the chain is a sub-structure having a fluorine atom, which At least one of the hydrogen atoms in the alkylene chain is replaced by a fluorine atom, which may be a fluoroalkylene chain, or a fluoroalkylene ether chain formed by connecting oxygen atoms, and another as an alkylene The base chain may include a straight-chain, branched or part of a ring-extended alkyl structure formed by forming a ring.

Among these, from the viewpoint of ease of handling, it is preferably a perfluoroalkylene chain having 1 to 6 carbon atoms or a perfluoroalkylene chain having 1 to 6 carbon atoms. The perfluorinated alkyl ether chain formed by connecting plural oxygen atoms is preferably a perfluorinated alkyl ether chain because it is easy to adjust the content of fluorine atoms. In addition, it may be a structure in which a hydroxyl group is directly bonded to both ends of the perfluoroalkylene ether chain, or a structure in which a hydroxyl group is bonded through an alkylene chain having no fluorine atom.

Furthermore, the number of carbon atoms directly bonded to the fluorine atoms 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 perfluoroalkyl ether chains, it is preferred that the number of carbon atoms to which the fluorine atoms are directly bonded is 1 to 6, and the number of repetitions is in the range of 1 to 50. Particularly preferred are those having 1 to 3 carbon atoms. The alkylene chain is a repeating unit, and the perfluoroalkylene ether chain has a repeating number in the range of 1 to 50.

The aforesaid alkylene chain in which both terminals are hydroxyl groups and at least one hydrogen atom is substituted with a fluorine atom (however, the alkylene chain contains etheric oxygen atoms) (A), the residues are as described above, both When the terminal becomes "O-", for example, when at least one hydrogen atom is substituted with a fluorine atom to extend the alkyl chain as "Rf", this residue is a structural unit represented by "-O-Rf-O-" .

Similarly, the residue of the alkylene chain in which the two terminal ends are carboxyl groups and at least one hydrogen atom is replaced by a fluorine atom (however, the alkylene chain contains an oxygen atom having ethericity) (D) is as follows As mentioned above, if both ends become "C(=O)O-", if the same Rf as above is used, the structure is represented by "-OC(=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 above (A) The residue of (B) and/or the residue of divalent carboxylic acid (C).

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

This aromatic ring part is composed of a single benzene ring or condensed rings such as naphthalene, anthracene, phenanthrene, acenaphthene naphthalene, stilbene, 1,2 benzoacenaphthene, pyrene, etc. It can also be two or more benzene rings, condensed Bonding, or a branched or linear alkylene chain (some or all of hydrogen atoms can be replaced by fluorine atoms), oxygen atoms, sulfur atoms, -NR- (however, R is a hydrogen atom or The structure formed by the bonding of a divalent linking group such as alkyl) may have a monovalent substituent other than the hydroxyl group on the benzene ring or the condensed ring. In addition, the residues of the divalent phenolic hydroxyl group-containing compound (B) present in one molecule may all be the same or may be different.

The aforementioned substituents may be monovalent, and examples thereof include bromine atom, chlorine atom, iodine atom, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, and alkyl disulfide. Group, aryldisulfide group, amine group, N-alkylamine group, N,N-dialkylamine group, N-arylamine group, N,N-diarylamine group, N-alkyl- N-arylamino, acetyloxy, carbamoyloxy, N-alkylaminemethyloxy, N-arylaminemethyloxy, N,N-dialkylaminemethyloxy, N,N-diarylamine methyoxy, N-alkyl-N-arylamine methyoxy, alkyl arylene, aryl arylene, thiothio, amide amine, N -Alkyl amide amino group, N-aryl amide amino group, urea group, N'-alkyl ureido group, N', N'-dialkyl ureido group, N'-aryl ureido group, N' , N'-diarylureido, N'-alkyl-N'-arylureido, N-alkylureido, N-arylureido, N'-alkyl-N-alkylureido , N'-alkyl-N-arylureido, N',N'-dialkyl-N-alkylureido, N',N'-dialkyl-N-arylureido, N' -Aryl-N-alkylureido, N'-aryl-N-arylureido, N',N'-diaryl-N-alkylureido, N',N'-diaryl -N-arylureido, N'-alkyl-N'-aryl-N-alkylureido, N'-alkyl-N'-aryl-N-arylureido, alkoxycarbonyl Amino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamine Group, N-aryl-N-aryloxycarbonylamino group, methyl amide group, acetyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, amine methyl group, N-alkyl amine methyl group, N ,N-dialkylamine carboxamide, N-arylamine carboxamide, N,N-diarylamine carboxamide, N-alkyl-N-arylamine carboxamide, alkylsulfinyl Acyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfonate (-SO ₃ H) and its conjugate base (called sulfonate), alkoxysulfonyl Group, aryloxysulfonyl group, sulfinamide group, N-alkylamine sulfinyl group, N,N-dialkylamine sulfinyl group, N-arylamine sulfinyl group, N, N-diarylamine sulfenyl, N-alkyl-N-arylamine sulfenyl, sulfamoyl, N-alkyl sulfamoyl, N,N-dialkyl sulfamoyl Group, N-aryl sulfonamide, N,N-diaryl sulfonamide, N-alkyl-N-aryl sulfonamide, phosphonamide (-PO ₃ H ₂ ) and their common Conjugated base (called phosphonate group), dialkyl phosphinyl group (-PO ₃ (alkyl) ₂ ) "alkyl=alkyl, the same below", diaryl phosphinyl group (-PO ₃ (aryl) ₂ ) "Aryl=aryl, the same below", alkyl aryl phosphinyl (-PO ₃ (alkyl) (aryl)), monoalkyl phosphinyl (-PO ₃ (alkyl)) and their conjugated bases (Called alkylphosphonate), monoarylphosphonoyl (-PO ₃ H (aryl)) and its conjugated base (called arylphosphonate), phosphinyloxy (-OPO ₃ H ₂ ) and its conjugated base (called phosphinoxy), dialkylphosphine Acyloxy (-OPO ₃ H(alkyl) ₂ ), diarylphosphine acetyloxy (-OPO ₃ (aryl) ₂ ), alkylarylphosphine acetyloxy (-OPO ₃ (alkyl)(aryl)) , Monoalkylphosphonooxy (-OPO ₃ H (alkyl)) and its conjugate base (called alkylphosphonooxy), monoarylphosphonooxy (-OPO ₃ H (aryl)) And its conjugated base (called arylphosphonooxy), cyano, nitro, aryl, heterocyclic, silyl, vinyl, 1-propenyl, 1-butenyl, cinnamyl, Alkenyl such as 2-chloro-1-vinyl such as alkenyl, ethynyl, 1-propynyl, 1-butynyl, trimethylsilylethynyl, etc.

Among these, from the viewpoint that the manufacturing method described later can be industrially easily manufactured, it is preferable that the structural unit derived from biphenol, bisphenol, binaphthol or naphthol may have a substituent on the ring In particular, structural units derived from biphenol and bisphenol are preferred, and structural units derived from bisphenol A or bisphenol F are most preferred.

In addition, 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. For example, when the skeleton portion is regarded as R ¹ , it is represented by "-OC( =O)-R ¹ -C(=O)-O-" represents the structural unit.

The partial system of R ¹ is not particularly limited, and may be derived from an aliphatic compound or an aromatic ring. For example, from malic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, Aliphatic divalent carboxylic acid such as cyclohexane dicarboxylic acid, dimer acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, and The structural units of the compounds having the aforementioned monovalent substituents on these aromatic rings, the residues of the divalent carboxylic acid (C) present in one molecule may be composed of the same, or may have a plurality of different residues. Among these, from the viewpoint of the ease of obtaining industrial raw materials in the manufacturing method described later, the obtained fluorine-containing active energy ray-curable resin has excellent performance balance such as heat resistance and surface segregation properties, it is preferably Structural units [residues] from succinic acid and maleic acid.

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

The alkylene chain in which both terminals are hydroxyl groups and at least one hydrogen atom is replaced by a fluorine atom (however, the alkylene chain contains an oxygen atom having ethericity) (A) and the dicarboxylic anhydride (E) When the residue of the reactant is the R ² of the skeleton of the dicarboxylic anhydride (E), it is regarded as "-OC(=O)-R ² -C(=O)-O-Rf-O-" The structural unit represented or the structural unit represented by "-OC(=O)-R ² -C(=O)-O-Rf-OC(=O)-R ² -C(=O)-O-".

The portion of R ² in the foregoing is not particularly limited, and may be derived from an aliphatic compound or an aromatic ring. For example, from phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride , Hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride and other structures, one molecule has a plurality of R'may have the same structure, or may include a plurality of different structures. Among these, from the viewpoint of the ease of obtaining industrial raw materials in the manufacturing method described later, the obtained fluorine-containing active energy ray-curable resin has excellent performance balance such as heat resistance and surface segregation properties, it is preferably Structural units derived from succinic anhydride and maleic anhydride.

The residue of the divalent hydroxyl group-containing compound (F) other than the aforementioned (A) includes the residue of the aforementioned divalent hydroxyl group-containing compound (B) and the residue of an 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 R ³ in the foregoing is the same as Φ listed in the residue of the aforementioned divalent phenolic hydroxyl-containing compound (B), or an alkylene chain, oxyalkylene chain, cyclopentane, Cyclic rings such as cyclohexane may have a plurality of R ³ in one molecule and may have the same structure or may include a plurality of different structures. Among these, from the viewpoint of the ease of obtaining industrial raw materials in the manufacturing method described later, the obtained fluorine-containing active energy ray-curable resin has excellent performance balance such as heat resistance and surface segregation properties, it is preferably The alkylene chain with 1 to 6 carbon atoms.

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

[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 acid group], and the aforementioned structural formula (1) included in 1 molecule At least one of the connecting groups shown is a monovalent organic group (x1) having a polymerizable group.

Examples of the polymerizable group included in the organic group (x1) include a vinyl group and a (meth)acryloyl group. From the viewpoint of the polymerizability when the active energy ray-curable resin composition described below is used, It is preferably an organic group containing (meth)acryloyl group.

In the aforementioned structural formula (1), examples of the method for making X a monovalent organic group (x1) having a polymerizable group include, for example, a secondary hydroxyl group in which X is a hydrogen atom, and an isocyanate group, a carboxyl group, or a carboxyl group. Acid halide group, a method of reacting with vinyl or (meth) acryl compound.

Among these, from the viewpoint of easy reaction, it is preferable that the secondary hydroxyl group is a group obtained by reacting a (meth)acrylate having an isocyanate group, and particularly preferably contains the following structural formula (2) The linking base of the structure shown,

[In 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. Examples include a monomer having one isocyanate group and one (meth)acryloyl group, and one isocyanate. Monomer with 2 (meth)acryloyl groups, monomer with 1 isocyanate group and 3 (meth)acryloyl groups, monomer with 1 isocyanate group and 4 (meth)acryloyl groups Monomers, monomers having one isocyanate group and 5 (meth)acryloyl groups, etc.

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

Examples of specific products of these (meth)acrylates having isocyanate groups include 2-acryloxyethyl isocyanate (trade name: "Karenz AOI" manufactured by Showa Denko Co., Ltd.), 2 -Methacryloyloxyethyl isocyanate (trade name: "Karenz MOI" manufactured by Showa Denko Co., Ltd.), 1,1-bis(acryloyloxymethyl) ethyl isocyanate (trade name: Showa Denko Limited company "Karenz BEI", etc.).

Furthermore, a compound obtained by adding a hydroxyl group-containing (meth)acrylate compound to one isocyanate group of the diisocyanate compound can be mentioned. Examples of the diisocyanate compound used in this reaction include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4- Aliphatic diisocyanates such as trimethylhexamethylene diisocyanate, xylylene diisocyanate, m-tetramethyl xylylene diisocyanate; cyclohexane-1,4-diisocyanate, isophorone di Alicyclic diisocyanates such as isocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanate methyl)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 can be used alone or in combination of two or more.

At least one of the X series in the aforementioned general formula (1) is a monovalent organic group (x1) having a polymerizable group as described above, but in the plural linking groups present in one molecule, a monovalent organic group having an acid group is further used in combination The group (x2) is preferably used as a curable composition described below, especially when used as a resist composition.

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

The method of introducing the acid group is not particularly limited, and examples thereof include a method of reacting a compound having an acid anhydride group with respect to a secondary hydroxyl group where 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 system of acid groups becomes more excellent in alkali developability and is more suitable for high-definition pattern formation. From such a point of view, although the introduction amount of the acid group is appropriately set according to the application or performance level used, the acid value is preferably in the range of 5 to 120 mgKOH/g, more preferably in the range of 7 to 100 mgKOH/g Range, the best range is 10~80mgKOH/g.

The fluorine-containing active energy ray-curable resin of the present invention has chain-like structural units as described above, but its end is derived from a compound used as a raw material, and is not particularly limited, but the manufacturing method described later During synthesis, the terminal is a hydrogen atom, an epoxy group or a carboxyl group. These terminal structures are naturally determined according to the feed ratio of the raw materials or the reaction sequence. The plural compounds contained in the resin may be composed of only those with the same terminal structure, or may have different terminals. A mixture of structural compounds.

Examples of the fluorine-containing active energy ray-curable resin of the present invention include those represented by the following formulas. In the following formulas, m and n each represent the number of repetitions, which is an integer of 1 or more. In addition, PFPE represents a perfluoroalkylene ether chain.

The fluorine atom content rate of the fluorine-containing active energy ray-curable resin of the present invention can be easily set according to the use or desired water- and oil-repellent properties, liquid-repellent properties, leveling properties, etc., but it is cured as an active energy ray In the case of a reactive 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, and particularly preferably in the range of 3 to 40% by mass.

The fluorine atom content rate is calculated from the raw material type and the ratio when the resin is designed, but it may also be measured by combustion ion chromatography. In the present invention, among the actual measured values of the latter, the aforementioned range is preferred.

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 is good in compatibility with other blending components when it becomes a curable resin composition, and it is easy to realize a high degree In terms of leveling properties, 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, and more preferably in the range of 10,000 to 100,000. In addition, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are based on the measurement of gel permeation chromatography (hereinafter, abbreviated as "GPC"), and are polystyrene conversion values. In addition, the measurement conditions of GPC are as follows.

[GPC measurement conditions]

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation,

Pipe Column: Tosoh Co., Ltd.-made protective pipe "HHR-H" (6.0mmI.D.×4cm)

+ "TSK-GEL GMHHR-N" manufactured by Tosoh Corporation (7.8mmI.D.×30cm)

+ "TSK-GEL GMHHR-N" manufactured by Tosoh Corporation (7.8mmI.D.×30cm)

+ "TSK-GEL GMHHR-N" manufactured by Tosoh Corporation (7.8mmI.D.×30cm)

+ "TSK-GEL GMHHR-N" manufactured by Tosoh Corporation (7.8mmI.D.×30cm)

Detector: ELSD ("ELSD2000" manufactured by ALLTECH)

Data processing: "GPC-8020 type II data analysis version 4.30" manufactured by Tosoh Corporation

Sample: A microfilter is used to filter a tetrahydrofuran solution (5 μl) converted into 1.0% by mass in terms of resin solid content.

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

(Monodisperse polystyrene)

"A-500" manufactured by Tosoh Corporation

"A-1000" manufactured by Tosoh Corporation

"A-2500" manufactured by Tosoh Corporation

"A-5000" manufactured by Tosoh Corporation

"F-1" by Tosoh Corporation

"F-2" manufactured by Tosoh Corporation

"F-4" manufactured by Tosoh Corporation

"F-10" manufactured by Tosoh Corporation

"F-20" manufactured by Tosoh Corporation

"F-40" manufactured by Tosoh Corporation

"F-80" manufactured by Tosoh Corporation

"F-128" manufactured by Tosoh Corporation

"F-288" manufactured by Tosoh Corporation

"F-550" manufactured by Tosoh Corporation

In addition, the fluorine-containing active energy ray-curable resin of the present invention is excellent in curability when used as a curable resin composition described later, and is excellent in long-term water and oil repellency and liquid repellency of the cured film surface. The concentration of the active energy ray-curable functional group 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 viewpoints of industrial availability of raw materials and excellent production efficiency in production, it is preferably produced by the following method .

Preparation method 1: For the compound (a1) with an alkylene chain in which at least one hydrogen atom is substituted with a fluorine atom (but the aforesaid alkylene chain contains an oxygen atom having ethericity) and an epoxy group, and A compound having a divalent phenolic hydroxyl group-containing compound (a2) and/or a divalent carboxylic acid (a3) as a secondary raw material in the reactant obtained by reacting as a necessary raw material, a compound having an active energy ray-curable functional group and an isocyanate group ( a4) The method of reaction.

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

First, the preparation method 1 will be described in detail.

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

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

Since the terminal epoxy group in the aforementioned compound (a1) is excellent in reactivity, a linear form can be obtained by the ring-opening reaction with the epoxy group of the divalent phenolic hydroxyl group-containing compound (a2) or the divalent carboxylic acid (a3). At the same time, a secondary hydroxyl group derived from an epoxy group is generated at the linking moiety.

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

In this reaction, a divalent epoxy compound (a6) other than the aforementioned 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 in the resin obtained in this way, that is, the terminal of the fluorine-containing active energy ray-curable resin, can be any one of a hydrogen atom, an epoxy group, and a carboxyl group in accordance with the ratio of raw materials used.

The use ratio of the aforementioned compound (a1) and the aforementioned divalent phenolic hydroxyl group-containing compound (a2) or divalent carboxylic acid (a3), or the combined use of the divalent epoxy compound (a6), although not particularly limited, However, for example, the total number of moles of the phenolic hydroxyl group or carboxyl group is smaller than the total number of moles of the epoxy group in the aforementioned compound (a1) and the epoxy group of the divalent epoxy compound (a6) optionally used together. Jiawei is used in the range of 0.9~1.1. This reaction is a general ring-opening reaction of epoxy groups. It can be used in a solvent-free or organic solvent, using quaternary onium salts, imidazoles, TPP and other catalysts, stirring at 150 ~ 180 ℃ to easily get the reaction Thing.

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, second butanol, and third butanol, glycol ethers such as methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether acetate, tetrahydrofuran, 1,4 -two Alkane, 1,3-di Ether compounds such as alkane and diethoxyethane, aprotic polar solvents such as acetonitrile, dimethylsulfoxide, dimethylformamide, etc. These organic solvents may be used alone, and in order to adjust the polarity, two or more kinds may be suitably used in combination.

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

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

(Wherein R ^{1 is} independently any one of hydrogen atom, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, aryl group, aralkyl group, p is 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 these, from the standpoints of easy availability of industrial raw materials, excellent performance balance of the obtained fluorine-containing active energy ray-curable resin, such as heat resistance and surface segregation, it is preferable to use biphenol and bisphenol , Binaphthol or naphthol, bisphenol A and bisphenol F are particularly preferred.

The divalent carboxylic acid (a3) may be any of an aliphatic system and an aromatic system, and examples thereof include malic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and pimelic acid. , Dimer carboxylic acid such as pimelic acid, suberic acid, azelaic acid, sebacic acid, decane dicarboxylic acid, cyclohexane dicarboxylic acid, dimer acid, fumaric acid, maleic acid, etc. Acids, phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acids, and compounds having the aforementioned monovalent substituents on these aromatic rings. These systems may be used alone or in combination of two or more. Among these, from the standpoints of easy availability of industrial raw materials, excellent balance of properties such as heat resistance and surface segregation of the fluorine-containing active energy ray-curable resin obtained, it is preferable to use succinic acid or male acid.

As the compound (a4) having the active energy ray-curable functional group and the isocyanate group, a compound having an isocyanate group and a (meth)acryloyl group is preferable from the viewpoint of good reactivity, and the aforementioned ones can be mentioned. In either case, it is preferable to use 2-ethyl isocyanate acrylate and 2-ethyl isocyanate methacrylate. In addition, these systems may be used alone or in combination of two or more. Since this reaction is a reaction between a normal 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. ; Organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate, tin octoate, etc.; carbamate catalysts such as organic metal compounds such as zinc octoate, The product having the secondary hydroxyl group obtained above is added while dropping the compound (a4) while heating to 50 to 120°C.

The use ratio of the aforementioned compound (a4) having an active energy ray-curable functional group and an isocyanate group can be appropriately set according to the target functional group concentration, for example, the mole number of the isocyanate group is better than the secondary hydroxyl group For use in the range of 0.3~1.0.

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

In addition, when it becomes the curable composition for resists mentioned later, it is preferable to further introduce an acid group. This acid group can be easily obtained by reacting the acid anhydride group-containing compound (a7) with a secondary hydroxyl group that 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, and 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 easy reaction, it is preferable to use succinic anhydride or maleic anhydride.

Next, the manufacturing method 2 will be described in detail.

In the production method 2, for the compound (a5) having at least one hydrogen atom substituted with a fluorine atom to an alkylene chain (but the aforementioned alkylene chain contains an etheric oxygen atom) and a carboxyl group or a hydroxyl group , React with the secondary hydroxyl group of the reactant obtained by reacting the divalent epoxy compound (a6) as an essential raw material, react the compound (a4) having an active energy ray-curable functional group with an isocyanate group, and introduce active energy ray to harden Functional group, but the divalent epoxy compound used at this time, the compound (a4) having an active energy ray-curable functional group and an isocyanate group are the same compounds as those used in the production method 1, and preferably the same.

The alkylene chain system of the compound (a5) in which at least one alkylene chain having a hydrogen atom is replaced by a fluorine atom (however, the aforementioned alkylene chain contains an oxygen atom having an etheric nature) and a carboxyl group or a hydroxyl group Synonymous with the foregoing, that is, preferably a perfluoroalkylene chain having 1 to 6 carbon atoms or a perfluoroalkylene chain having a repeating structure in which a perfluoroalkylene chain having 1 to 6 carbon atoms is connected by an oxygen atom Alkyl ether chain.

Examples of the aforementioned compound (a5) include those represented by the following structural formulas. The PFPE system in the following formula is the same as described above. As a method of introducing a carboxyl group at the terminal, the compound having a hydroxyl group at the terminal can be easily obtained by reacting a dicarboxylic anhydride.

The reaction of the carboxyl group or the hydroxyl group in the compound (a5) with the divalent epoxy compound (a6) is a normal ring-opening reaction of an epoxy group, and by this reaction, the compound (a5) linked with a linking group having a secondary hydroxyl group is obtained Reactant with the structure of compound (a6). To 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 Production Method 1.

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

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

This reaction is a general ring-opening reaction of epoxy groups. It can be used in a solvent-free or organic solvent, using quaternary onium salts, imidazoles, TPP and other catalysts, stirring at 150 ~ 180 ℃ to easily get the reaction Thing.

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, second butanol, and third butanol, glycol ethers such as methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether acetate, tetrahydrofuran, 1,4 -two Alkane, 1,3-di Ether compounds such as alkane and diethoxyethane, aprotic polar solvents such as acetonitrile, dimethylsulfoxide, dimethylformamide, etc. These organic solvents may be used alone, and in order to adjust the polarity, two or more kinds may be suitably used in combination.

The reaction system thereafter is the same as in Production Method 1. The above-mentioned reactions are carried out stoichiometrically, and the compounds used as raw materials hardly remain in the system in an unreacted state, so they have the characteristic that it is difficult for the resulting resin to contain low molecular weight compounds. Therefore, when the obtained resin is used in the same manner as the conventional fluorine-based surfactant, it is possible to effectively suppress volatilization during curing and detachment from the surface of the cured film.

Although the fluorine-containing active energy ray-curable resin of the present invention can be used as a main agent of an active energy ray-curable composition, it can be used as an active energy ray-curable composition in order to have extremely excellent surface modification properties. The fluorine-based surfactants (fluorine-based surface modifiers) added to it are used to give the cured film excellent antifouling properties such as water repellency, oil repellency, liquid repellency (ink repellency), and 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 as its main component, it contains active energy ray curable properties other than the aforementioned fluorine-containing active energy ray curable resin 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. In addition, the fluorine-containing active energy ray-curable resin [hereinafter, also referred to as fluorine-containing active energy ray-curable resin (I)] of the present invention is included in the active energy ray-curable composition as a surface modifier Have an effect.

Examples of the active energy ray-curable resin (II) include urethane (meth)acrylate resins, unsaturated polyester resins, epoxy (meth)acrylate resins, and acrylic acrylates. Resin, resin containing maleimide group, cardo type resin, etc.

Examples of the aforementioned urethane (meth)acrylate resin include an aminomethacrylate obtained by reacting an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound with a hydroxyl-containing (meth)acrylate compound Resin with ester bond and (meth)acryloyl group.

Examples of the aforementioned aliphatic polyisocyanate compounds include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, and decapylene. 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, Alkyl diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate, cyclohexyl diisocyanate, etc. In addition, as an aromatic polyisocyanate compound, Examples include toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, toluene diisocyanate, and p-phenylene diisocyanate.

Examples of the aforementioned aromatic polyisocyanate compounds 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 aforementioned hydroxyl-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) ) Acrylic ester, hydroxy trimethyl acetate neopentyl glycol mono (meth) acrylate and other mono alcohol (meth) acrylate; trimethylol propane di (meth) acrylate, ethoxy Trimethylolpropane (meth)acrylate, propoxylated trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, bis(2-(meth)acryloyloxy) Mono- or di(meth)acrylates of trihydric alcohols such as ethyl ethyl) hydroxyethyl isocyanurate, or hydroxyl-containing ones whose part of these alcoholic hydroxyl groups have been modified by ε-caprolactone Mono- and di-(meth)acrylates; pentaerythritol tri(meth)acrylates, ditrimethylolpropane tri(meth)acrylates, dipentaerythritol penta(meth)acrylates, etc. have monofunctional hydroxyl groups and (Meth)acryloyl compound with more than 3 functions, or a polyfunctional (meth)acrylate containing hydroxyl group modified by ε-caprolactone; dipropylene glycol mono(meth)acrylate, (Meth)acrylate compounds having an oxyalkylene chain such as diethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate; Poly(ethylene glycol-polypropylene glycol mono(meth)acrylate, polyoxybutylene-polyoxypropylene mono(meth)acrylate, etc. (meth)acrylate compound having a block structure of oxyalkylene chain ; Poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate, etc. having an internal amide structure of the oxy stretch (Meth)acrylate compound of alkyl chain, etc.

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

Among these urethane (meth)acrylate resins, especially those obtained by reacting aliphatic polyisocyanate compounds with hydroxyl-containing (meth)acrylate compounds, the cured film has excellent transparency, In addition, the sensitivity to the active energy ray is good and the curability is excellent because it is preferable.

Examples of the aforementioned unsaturated polyester resins 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 glycols 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 the dibasic acids or anhydrides other than the aforementioned α,β-unsaturated dibasic acids or anhydrides include aromatic saturated dibasic acids, aliphatic dibasic acids, alicyclic saturated dibasic acids, and the like The anhydride, etc. Examples of the aromatic saturated dibasic acid or its anhydride include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, and tetrahydrophthalic acid. Anhydride, internal methylenetetrahydrophthalic anhydride, halogenated phthalic anhydride and these esters, etc. Examples of the aliphatic dibasic acid, alicyclic saturated dibasic acid and these anhydrides include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, Hexahydrophthalic anhydride and these esters. Examples of glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, and 2-methylpropane-1,3-diene. Alcohol, neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2, 2-Di-(4-hydroxypropoxydiphenyl) propane and the like, and oxides such as ethylene oxide and propylene oxide can also be used in the same manner.

Examples of the epoxy (meth)acrylate resin include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, and cresol novolac epoxy resin. The epoxy group of epoxy resin is obtained by reacting (meth)acrylic acid.

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

Examples of the aforementioned maleimide group-containing resin include, for example, a bifunctional maleimide obtained by carbamate-producing N-hydroxyethyl maleimide and isophorone diisocyanate. Aminocarbamate compounds, bifunctional maleimide ester compounds obtained by esterifying maleimide acetic acid and polytetramethylene glycol, of maleimide caproic acid and pentaerythritol 4-functional maleimide ester compound obtained by esterifying tetraethylene oxide adduct, and multi-functional maleimide ester compound obtained by esterifying maleimide acetic acid and a polyol compound Wait. These active energy linear curable resin systems may be used alone or in combination of two or more.

The aforementioned so-called cardot resin is generally a general term for a resin having a structure in which a cyclic group is directly bonded to a polymer chain, and for example, a resin having the following structure 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 of 0-20).

As the active energy ray-curable monomer (III), for example, a compound having one or more ethylenically unsaturated bonds can be exemplified.

Examples of the compound having one ethylenically unsaturated bond include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth) Group) butyl acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxy ethyl (meth) acrylate , Phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isocyanate (meth)acrylate (Meth)acrylates such as esters, 2-hydroxyethyl (meth)acrylate, glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate; 2-hydroxyethyl (meth)acrylate , Hydroxyalkyl (meth)acrylate such as hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxyalkyl (meth)acrylate 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; (meth)acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, cinnamic acid, 2-(meth)acrylamide Oxyethyl succinic acid, 2-(meth)acryloyloxyethyl adipate, 2-(meth)acryloyloxyethylmaleic acid, 2-(meth)acryloyloxyethyl Hexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxypropyl succinic acid, 2-(meth)acryloyloxy Propyl adipate, 2-(meth)acryloxypropylmaleic acid, 2-(meth)acryloxypropylhydrophthalic acid, 2-(meth)acryloxy Propyl phthalic acid, 2-(meth)acryloyloxybutyl succinic acid, 2-(meth)acryloyloxybutyl adipic acid, 2-(meth)acryloyl oxybutyl Polymerizable monomers such as maleic acid, 2-(meth)acryloxybutylhydrophthalic acid, 2-(meth)acryloxybutylphthalic acid; addition on acrylic acid Polymerizable monomers with lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone; succinic acid added to hydroxyalkyl (meth)acrylate, Polymerizable monomers of maleic acid, phthalic acid, or these anhydrides; 2-sulfoethyl (meth)acrylate, 2-sulfopropyl (meth)acrylate, 2-hydroxy-3 -(Meth)acryloxypropanesulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid or salts thereof; poly(meth)acrylate macromonomer, poly Macromonomers such as styrene macromonomers, poly(meth)acrylic acid 2-hydroxyethyl macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, polycaprolactone macromonomers, etc.

Examples of active energy ray-curable monomers having two ethylenically unsaturated bonds include 1,3-butanediol di(meth)acrylate and 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 Oxygenated 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-hydroxyl) Ethyl)isocyanurate tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate 、Pentaerythritol tri(meth)acrylate and acid anhydride reactant, caprolactone modified pentaerythritol tri(meth)acrylate, caprolactone modified ginseng (2-hydroxyethyl) isocyanurate tri( Methacrylic acid ester, caprolactone modified pentaerythritol tri(meth)acrylate and acid anhydride reactant, caprolactone modified dipentaerythritol penta(meth)acrylate and acid anhydride reactant, etc.

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

Examples of active energy ray-curable monomers having five or more ethylenic unsaturated bonds include dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tripentaerythritol penta(meth) Base) acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, dipentaerythritol penta(meth)acrylate and acid 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(methyl) Acrylic ester, caprolactone modified tripentaerythritol hepta(meth)acrylate, caprolactone modified three pentaerythritol octa(meth)acrylate, caprolactone modified three pentaerythritol hepta(meth)acrylate and anhydride, etc. .

Among these, especially from the viewpoint of excellent hardness of the cured coating film, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(methyl ) Multifunctional (meth)acrylates with more than 3 functions such as acrylate, pentaerythritol tetra(meth)acrylate, etc. These active energy ray-curable 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, the resulting cured film can be easily leveled and water-repellent. From the viewpoint that the oiliness and antifouling property are sufficient, and the hardness or transparency of the composition after curing becomes sufficient, the active energy ray-curable resin (II) and the active energy ray are hardened relative to the foregoing The total amount of the reactive monomer (III) is 100 parts by mass, and the usage amount thereof is preferably in the range of 0.01 to 10 parts by mass, and more preferably in the range of 0.1 to 5 parts by mass.

The fluorine-containing active energy ray-curable resin (I) of the present invention alone or the aforementioned active energy ray-curable composition can be a cured film by applying active energy ray after coating on a substrate. Examples of this active energy ray include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. As an active energy ray, when ultraviolet rays are irradiated to form a cured film, it is preferable to add a photopolymerization initiator to increase the curability. Furthermore, if necessary, a light sensitizer may be further added to improve the hardenability. On the other hand, when ionizing radiation such as electron beam, α-ray, β-ray, and γ-ray is used, since it can be hardened quickly even without using a photopolymerization initiator or photosensitizer, especially no photopolymerization is added. It is necessary to start agent or light sensitizer, but even if added, there is no problem.

Examples of the aforementioned photopolymerization initiator include intramolecular cleavage-type photopolymerization initiators and hydrogenation-type photopolymerization initiators. Examples of the intramolecular cleavage-type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and benzyl dimethyl ketal , 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)one , 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- Porphyrinyl (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenyl phenyl) butanone and other acetophenone compounds; benzoin, benzoin methyl ether, benzoin isopropyl ether and other benzoins; 2,4,6-trimethylbenzene Acetylphosphine oxide compounds such as diphenylphosphine oxide and bis(2,4,6-trimethylbenzyl)phenylphosphine oxide; diphenylethanedione, methylphenyl Glyoxylate etc.

Examples of the hydrogenation type photopolymerization initiator include diphenyl ketone, o-benzoyl benzoic acid methyl-4-phenyl diphenyl ketone, 4,4'-dichlorodiphenyl ketone , Hydroxydiphenyl ketone, 4-benzyl-4'-methyl-diphenyl sulfide, acryloyl diphenyl ketone, 3,3',4,4'-tetra (third butyl (Peroxycarbonyl) diphenyl ketone, 3,3'-dimethyl-4-methoxydiphenyl ketone and other diphenyl ketone compounds; 2-isopropyl thioxanthone, 2,4-di Thioxanthone-based compounds such as methylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; Michelinone, 4,4'-diethylaminodi Amino diphenyl ketone compounds such as phenyl ketone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, etc.

Among the above-mentioned photopolymerization initiators, from the viewpoint of excellent compatibility with the active energy ray-curable resin (II) and the active energy ray-curable monomer (III) in the active energy ray-curable composition In view, 1-hydroxycyclohexyl phenyl ketone and diphenyl ketone are preferred, and 1-hydroxycyclohexyl 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, and s-benzyl isosulfide. Sulfur compounds such as ureonium p-toluenesulfonate.

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

In addition, the active energy ray-curable composition of the present invention is adjusted for viscosity or refractive index, or for adjusting the color tone of the coating film or other types within the range that does not impair the effects of the present invention according to the purpose of use and characteristics. For the purpose of adjusting the properties and shape of the coating or the properties of the coating film, various blending materials can be used in combination, such as various organic solvents, acrylic resins, phenol resins, polyester resins, polystyrene resins, urethane resins, urea resins , Melamine resin, alkyd resin, epoxy resin, polyamide resin, polycarbonate resin, petroleum resin, fluorine resin and other resins, PTFE (polytetrafluoroethylene), polyethylene, polypropylene, carbon, titanium oxide , Various organic or inorganic particles such as alumina, copper, silica fine particles, other polymerization initiators, polymerization inhibitors, antistatic agents, defoamers, viscosity regulators, light stabilizers, weather stabilizers, heat stabilizers Agents, antioxidants, rust inhibitors, slip aids, waxes, gloss modifiers, mold release agents, miscible agents, conductivity modifiers, pigments, dyes, dispersants, dispersion stabilizers, polysiloxane-based, hydrocarbon-based interfaces Active agent, etc.

In each of 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 in particular, it is easy to adjust the film thickness for film coating. Examples of organic solvents that can be used here include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, and third butanol; ethyl acetate and propylene glycol monomethyl ether Esters such as acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. These solvent systems may be used alone or in combination of two or more.

As the active energy ray for curing the active energy ray-curable composition of the present invention, as described above, there are ionizing radiations such as ultraviolet rays, electron beams, α rays, β rays, and γ rays, but as a specific energy source or curing device, Examples include: germicidal lamps, fluorescent lamps for ultraviolet rays, carbon arc, 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 light using natural light as a light source , Or scanning type, curtain type electron beam accelerator electron beam, etc.

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

The coating method of the active energy ray-curable composition of the present invention differs depending on the application, and examples thereof include the use of a gravure coater, roll coater, corner wheel coater, knife coater, air knife coater, and curtain Application methods such as curtain coater, kiss coater, spray coater, wheel coater, spin coater, dipping, screen printing, spray, applicator, bar coater, etc., or forming methods using various molds, etc.

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

Examples of the antifouling properties that 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 polarizing plates for liquid crystal displays (LCD) such as TAC films Thin films; various display screens such as plasma displays (PDP) and organic EL displays; touch panels; housings 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 such as CD, DVD, Blu-ray disc, etc.; transfer film for insert molding (IMD, IMF); rubber roller for OA equipment such as photocopiers, printers, etc. ; The glass surface of the reading part of OA equipment such as photocopiers, scanners; optical lenses of cameras, cameras, glasses, etc.; the windshield, glass surface of watches such as watches; windows of various vehicles such as automobiles and railway vehicles; Cover glass or film for solar cells; various building materials such as cosmetic boards; window glass for houses; woodworking materials for furniture; various plastic molded products such as artificial and synthetic leather; housings for 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 active energy rays such as ultraviolet rays to form a cured film, the stain resistance 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, coating and drying, the stain resistance can also be imparted to the surface of the article.

In addition, as the coating material to which the fluorine-containing active energy ray-curable resin (I) of the present invention is added to improve the leveling property, and at the same time, antifouling properties or chemical resistance can be imparted to the coating film, examples include TAC film and the like Hard coating material for LCD polarizer film, anti-glare (AG: anti-glare) coating material or anti-reflection (LR) coating material; plasma display (PDP), organic EL display and other display screen hard coating Materials; hard coating materials for touch panels; printing inks, inkjet inks or coatings; coatings or hard coating materials for electronic terminal housings such as mobile phones; hard coating materials for mobile phone screens; protecting the transparency of the CF surface Coatings for protective films; coatings for organic insulating films of liquid crystal TFT arrays; hard coating materials for optical recording media such as CDs, DVDs, and Blu-ray discs; hard coating materials for transfer films for insert molding (IMD, IMF); photocopiers, Coating materials for rubber rollers for OA equipment such as printers; coating materials for glass for reading parts of OA equipment such as photocopiers and scanners; coating materials for optical lenses such as cameras, cameras, and glasses; 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 anti-reflective films of cover glasses or thin films for solar cells; printing for various building materials such as cosmetic boards Ink or coatings; coating materials for residential window glass; coatings for carpentry of furniture, etc.; coating materials for artificial and synthetic leather; coatings or coating materials for various plastic molded products such as housings of home appliances; coatings for FRP baths Or coating materials.

Furthermore, as the article using the fluorine-containing active energy ray-curable resin (I) or the active energy ray-curable composition of the present invention, which can impart scratch resistance (scratch resistance) and antifouling properties, there can be mentioned The LCD panel's backlight components are diffused or diffused. In addition, by adding the fluorine-containing active energy ray-curable resin (I) of the present invention to the coating material for the sheet or diffusion sheet, the leveling property of the coating material is improved, and at the same time, the scratch resistance (scratch resistance) Injurious) and antifouling properties are imparted to the coating film of the coating material.

Moreover, 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 anti-reflection layer that can prevent fluorescent lamps and the like from reflecting 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 possible to maintain the coating The low refractive index of the film imparts antifouling properties to the surface of the coating film.

Furthermore, as 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, optical fiber cladding materials, waveguides, sealing materials for liquid crystal panels, various optical 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 protective film for a polarizing plate for LCD, among the above-mentioned compositions, by The ratio of the total mass of the hardening component in the active energy ray-curable composition of the present invention is 0.1 to 0.5 times the amount of inorganic or organic fine particles such as silica fine particles, acrylic resin fine particles, polystyrene resin fine particles, etc. It is better for those with excellent anti-glare properties.

Furthermore, when the fluorine-containing active energy ray-curable resin (I) or 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 is also applicable to: Before the coating material is hardened, it is brought into contact with the mold of the uneven surface shape, and then the active energy ray is irradiated from the side opposite to the mold, hardened, and the surface of the coating is embossed, and a transfer method 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. Examples of the resist composition include a photoresist composition and a color resist composition. 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. The photoresist includes, for example, an alkali-soluble resin, a radiation-sensitive substance (photosensitive substance), and a solvent.

Here, the so-called alkali solubility refers to the property of being dissolved in an aqueous solution (developing solution) of an alkali compound. Specifically, for example, a resin solution with a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate) is used to form a resin film with a film thickness of 1 μm on the substrate and immersed in an aqueous solution of KOH with a concentration of 0.05% by mass At 1 minute, it can show the dissolving property of film thickness of 0.01μm or more.

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

As the aforementioned alkali-soluble resin, for example, an alkali-soluble resin having no photocurability (alkali-soluble resin not containing a photocurable group) or an alkali-soluble resin having photocurability (alkali-soluble resin containing a photocurable group) can be exemplified. Wait.

Examples of the alkali-soluble resin containing no photocurable group include the following resins.

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

‧A polymer which does not have an acidic group obtained by polymerizing a (meth)acrylic polymerizable monomer having a reactive group as an essential component, and a reactive group and an acid group having reactivity with the reactive group Alkali-soluble resin obtained by the reaction of the compound (2)

Examples of the alkali-soluble resin containing a photocurable group include the following resins.

‧For copolymers containing epoxy group-containing (meth)acrylates and other polymerizable monomers, unsaturated monocarboxylic acid is added to at least a part of the epoxy groups possessed by the copolymer. An alkali-soluble resin (3) obtained by performing an addition reaction of at least a part of a hydroxyl group generated by an addition reaction of a saturated monocarboxylic acid and 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.

Examples of the alkali-soluble resin (1) include an alkali-soluble resin obtained by polymerizing a (meth)acrylic polymerizable monomer having a carboxyl group as an essential component or a (meth)acrylic resin having a sulfonic acid group An alkali-soluble resin obtained by polymerizing a polymerizable monomer 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 preferred.

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, and 2-(methyl ) Acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl adipic acid, 2-(meth)acryloyloxyethylmaleic acid, 2-(meth)acryloyl Oxyethyl hexahydrophthalic acid, 2-(meth)acrylic acid oxyethyl phthalic acid, 2-(meth)acrylic acid oxypropyl succinic acid, 2-(meth)acrylic acid Acetyloxypropyladipic acid, 2-(meth)acrylic acidoxypropylmaleic acid, 2-(meth)acrylic acidoxypropylhydrophthalic acid, 2-(meth)acrylic acid Acetyloxypropyl phthalic acid, 2-(meth)acrylic acid oxybutyl succinic acid, 2-(meth)acrylic acid oxybutyl adipic acid, 2-(meth)acrylic acid oxyacetyl Polymerizable monomers such as butylbutylmaleic acid, 2-(meth)acryloyloxybutylhydrophthalic acid, 2-(meth)acryloyloxybutylphthalic acid; in acrylic acid Polymerizable monomers to which lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone are added; addition to hydroxyalkyl (meth)acrylate Polymerizable monomers such as succinic acid, maleic acid, phthalic acid, or these anhydrides. Only one type of these (meth)acrylic polymerizable monosystems having a carboxyl group may be used, or two or more types may be used in combination. Among the (meth)acrylic polymerizable monomers having a carboxyl group, (meth)acrylic acid and 2-(meth)acryloyloxyethylsuccinic acid are preferred.

Examples of the (meth)acrylic polymerizable monomer having a sulfonic acid group include: (meth)acrylic acid-2-sulfoethyl ester, (meth)acrylic acid-2-sulfopropyl ester, 2 -Hydroxy-3-(meth)acryloxypropanesulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, or salts thereof, etc.

When preparing the alkali-soluble resin (1), other polymerizable monomers may be used in combination as long as the effect of the present invention is not impaired. Examples of other monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, and butyl (meth)acrylate. Ester, isobutyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, (methyl )Phenoxymethyl acrylate, 2-ethylhexyl (meth)acrylate, isocyanate (meth)acrylate (Meth)acrylates such as esters, 2-hydroxyethyl (meth)acrylate, glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate; 2-hydroxyethyl (meth)acrylate , Hydroxyalkyl (meth)acrylate such as hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxyalkyl (meth)acrylate 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(meth)acrylate macromonomer, polystyrene macromonomer, poly(meth)acrylate 2-hydroxyethyl macromonomer Body, polyethylene glycol macromonomer, polypropylene glycol macromonomer, polycaprolactone macromonomer, etc. Only one type of other polymerizable single systems may be used, or two or more types may be used in combination.

Among the other polymerizable monomers mentioned above, styrene, methyl (meth)acrylate, cyclohexyl (meth)acrylate, and 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 use amount of these other polymerizable monomers is preferably 95% by mass or less of all the polymerizable monomer components, and more preferably 85% by mass or less.

Specific examples of the alkali-soluble resin (1) include, for example, (meth)acrylic acid, methyl (meth)acrylate, benzyl (meth)acrylate, butyl (meth)acrylate, (meth) ) Isobutyl acrylate, cyclohexyl (meth)acrylate, cyclohexylmaleimide and other non-hydroxyl polymerizable monomers, and 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid Copolymers of hydroxyl-containing polymerizable monomers such as hydroxypropyl ester, 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, 2-hydroxyethyl methacrylate; copolymers of (meth)acrylic acid and styrene; (A Base) copolymer of acrylic acid and styrene and α-methylstyrene; copolymer of (meth)acrylic acid and cyclohexylmaleimide, etc. Among the alkali-soluble resins (1), alkali-soluble resins using benzyl (meth)acrylate are preferred.

The acid value of the alkali-soluble resin (1) is preferably in the range of 10 to 300, more preferably in the range of 20 to 350, and particularly preferably in the range of 30 to 300. Moreover, the weight-average molecular weight (Mw) of the alkali-soluble resin (1) in terms of polystyrene measured by GPC is preferably in the range of 2,000 to 100,000, more preferably in the range of 3,000 to 70,000, and particularly preferably in the range of 4,000 to 50,000 Scope.

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

Examples of the epoxy group-containing unsaturated compound include, for example, glycidyl (meth)acrylate, allyl glycidyl ether, glycidyl propyl-α-ethyl acrylate, and crotonyl ring Oxypropyl ether, (iso)crotonic acid glycidyl ether, N-(3,5-dimethyl-4-epoxypropyl)benzylacrylamide, 4-hydroxybutyl (meth)acrylate Epoxypropyl ether, etc. From the viewpoint of improving heat resistance and dispersibility when using a pigment as a colorant, an unsaturated compound containing an alicyclic epoxy group is preferred.

Examples of the alicyclic epoxy group included in the alicyclic epoxy group-containing unsaturated compound include 2,3-epoxycyclopentyl, 3,4-epoxycyclohexyl, and 7 , 8-epoxy [tricyclo[5.2.1.0]dec-2-yl]yl and the like. Moreover, as an ethylenic unsaturated group, (meth)acryloyl group is preferable. As the unsaturated compound system containing an alicyclic epoxy group, only one type may be used, or two or more types may be used in combination.

In order to add the aforementioned epoxy group-containing unsaturated compound to the carboxyl group of the aforementioned carboxyl group-containing alkali-soluble resin, a well-known technique can be used. For example, by combining an alkali-soluble resin containing a carboxyl group and an unsaturated compound containing an epoxy group in a tertiary amine such as triethylamine, benzylmethylamine, etc.; dodecyltrimethylammonium chloride, tetramethyl Quaternary ammonium salts of ammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride, etc.; in the presence of catalysts such as pyridine and triphenylphosphine, in organic solvents In the reaction temperature of 50 ~ 150 ℃ for several hours to several tens of hours, and can be added to the carboxyl group of the resin containing unsaturated unsaturated compounds.

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

In addition, among the alkali-soluble resins (1), preferably, an alkali-soluble resin (1) obtained by using an ether dimer or (meth)acrylate having an alicyclic structure such as adamantyl as a polymerizable monomer. -2).

Examples of the aforementioned ether dimer include dimethyl-2,2′-[oxybis(methylene)]bis-2-propionate and diethyl-2,2′-[oxygen Bis(methylene)]bis-2-propionate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propionate, di(isopropyl Radical)-2,2'-[oxybis(methylene)]bis-2-propionate, di(n-butyl)-2,2'-[oxybis(methylene)]bis- 2-propionate, di(isobutyl)-2,2'-[oxybis(methylene)]bis-2-propionate, di(third butyl)-2,2'-[ Oxybis(methylene)]bis-2-propionate, di(third pentyl)-2,2'-[oxybis(methylene)]bis-2-propionate, di( Stearyl)-2,2'-[oxybis(methylene)]bis-2-propionate, di(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 Group)] bis-2-propionate, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-propionate, di(third butylcyclohexyl)-2, 2'-[oxybis(methylene)]bis-2-propionate, di(dicyclopentadienyl)-2,2'-[oxybis(methylene)]bis-2- Propionate, di(tricyclodecyl)-2,2'-[oxybis(methylene)]bis-2-propionate, di(iso Group)-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 and diethyl-2,2'-[oxybis( Methylene)]bis-2-propionate, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-propionate, dibenzyl-2,2'-[ Oxybis(methylene)]bis-2-propionate. Only one type of these ether dimer systems may be used, or two or more types may be used in combination.

The solvent system used in the solution polymerization method may be the user used in ordinary radical polymerization reactions. 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; ethyl acetate, 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, ethylbenzene; chloroform; dimethyl sulfoxide, etc. Only one type of these solvent systems may be used, or two or more types may be used in combination.

When polymerizing the polymerizable monomer, a polymerization initiator may be used as necessary. Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-tert-butyl peroxide, lauryl peroxide, and benzoyl peroxide. Organic peroxides such as oxides, third butyl peroxyisopropyl carbonate, third pentyl peroxy-2-ethylhexanoate, third butyl peroxy-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-methyl propionate). Only one type of these polymerization initiator systems may be used, or two or more types may be used in combination. The use amount of these polymerization initiators may be appropriately set according to the combination of monomers used, the reaction conditions, the molecular weight of the target alkali-soluble resin, etc., and is not particularly limited, but it never gels. From the viewpoint of obtaining an alkali-soluble resin having a weight-average molecular weight of thousands to tens of thousands, it is preferably in the range of 0.1 to 15% by mass, and more preferably in the range of 0.2 to 10% by mass relative to the total polymerizable monomer components.

In addition, a chain transfer agent may be added for molecular weight adjustment. Examples of the chain transfer agent include thiol-based chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid, and methyl mercaptoacetate; α-methylstyrene dimer, etc., but chain transfer is preferred The effect is high, which can reduce the residual polymerizable monomer in the reaction system, and it is easy to obtain n-dodecyl mercaptan and mercaptoacetic acid. The amount used when the chain transfer agent is used may be appropriately set according to the combination of monomers used, the reaction conditions, the molecular weight of the target monomer, etc., and is not particularly limited, but never gelatinizes to obtain a weight In view of the alkali-soluble resin having an average molecular weight of several thousands to tens of thousands, it is preferably in the range of 0.1 to 15% by mass, and more preferably in the range of 0.5 to 10% by mass relative to all monomers.

The alkali-soluble resin (2) used in the present invention is a polymer which does not have an acidic group obtained by polymerizing a (meth)acrylic polymerizable monomer having a reactive group as an essential component, and has a reactive group It is obtained by reacting reactive reactive groups with acid groups. Examples of the alkali-soluble resin (2) include the following alkali-soluble resins.

‧The polymer is obtained by using a polymerizable monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate as an essential component, and then added with an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride, etc. Alkali soluble resin.

‧After obtaining a polymer using an epoxy polymerizable monomer such as glycidyl (meth)acrylate as an essential component, add N-methylaminobenzoic acid, N-methylaminophenol, etc. Alkali-soluble resins derived from compounds with amine and acid groups.

‧After obtaining a polymer using an isocyanate group-containing polymerizable monomer such as (meth)acrylic acid 2-isocyanate ethyl ester as an essential component, a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid is added The resulting alkali-soluble resin.

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 polystyrene-converted weight-average molecular weight measured by GPC from the viewpoint of good coating film formation and excellent heat resistance. , More preferably in the range of 2,000~10,000, especially in the range of 2,000~50,000. In addition, if necessary, the polymerizable monomer used in the preparation of the alkali-soluble resin (1) may be used in combination to obtain the alkali-soluble resin (2).

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

Examples of the epoxy group-containing (meth)acrylates include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and (meth)acrylic acid ( 3,4-epoxycyclohexyl) methyl ester, 4-hydroxybutyl (meth)acrylate epoxypropyl ether, etc. Among them, glycidyl (meth)acrylate is preferred. Only one type of these epoxy group-containing (meth)acrylate systems may be used, or two or more types may be used in combination.

In addition, other polymerizable monomers other than epoxy group-containing (meth)acrylate as the raw material of the alkali-soluble resin (3), if used have Monomers with an alicyclic structure such as an ene skeleton and a dicyclopentadiene skeleton can improve the heat resistance and mechanical strength of the cured product, which is preferable.

In addition, a polymerizable monomer having no alicyclic structure may be used as the other polymerizable monomer other than the epoxy group-containing (meth)acrylate. Examples of such polymerizable monomers include styrene, vinyl aromatics such as α-, o-, m-, p-alkyl, nitro, cyano, amide, and ester derivatives of styrene. Groups; diene such as butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene, etc.; methyl (meth)acrylate, ethyl (meth)acrylate, ( N-propyl meth)acrylate, 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 Ester, (meth)acrylic acid Ester, adamantyl (meth)acrylate, propynyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, anthracene (meth)acrylate, amine (meth)acrylate Aniseyl ester, piperonyl (meth)acrylate, salicyl (meth)acrylate, furan (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofuran (meth)acrylate, (meth)acrylic acid Piperanyl ester, benzyl (meth)acrylate, phenethyl (meth)acrylate, cresyl (meth)acrylate, (meth)acrylic acid-1,1,1-trifluoroethyl, (meth) ) Perfluoroethyl acrylate, perfluoro-n-propyl (meth)acrylate, perfluoroisopropyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, (Meth)acrylic acid-3-(N,N-dimethylamino)propyl ester, (meth)acrylic acid-2-hydroxyethyl ester, (meth)acrylic acid-2-hydroxypropyl ester, etc. ) Acrylic esters; (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethyl amide, (meth)acrylic acid N,N-diethyl amide, (meth)acrylic acid N, N-dipropylamide, (meth)acrylic acid-N,N-diisopropylamide, (meth)acrylic anthracenamide, etc. (meth)acrylic acid amide; (meth)acrylic acid amide Vinyl compounds such as aniline, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, etc. Unsaturated dicarboxylic acid diesters such as diethyl citrate, diethyl maleate, diethyl fumarate, diethyl iconate, etc.; N-phenyl maleimide, Mono-maleimides such as N-cyclohexylmaleimide, N-laurylmaleimide, N-(4-hydroxyphenyl)maleimide, etc.; N-(methyl) Acryloyl phthalimide and so on.

Among the other polymerizable monomers mentioned above, it is preferable to use styrene, benzyl (meth)acrylate and monomaleimide from the viewpoint of improving the heat resistance and mechanical strength of the cured product. At least 1 kind. The use ratio of styrene, benzyl (meth)acrylate and monomaleimide is based on the total amount of other polymerizable monomers, preferably 1 to 70 mol%, more preferably 3 to 50 Moore%.

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

As the copolymer of the epoxy group-containing (meth)acrylate and the other polymerizable monomer, it is preferable that the repeating unit derived from the epoxy group-containing (meth)acrylate is 5 to 90 mol %, It is more preferably composed of 20-80 mol% of the former and 80-20 mol% of the latter, and particularly preferably composed of the repeating units from other radical polymerizable monomers of 10-95 mol% 30 to 70 mol% and the latter 70 to 30 mol%.

The alkali-soluble resin (3) can, for example, use the epoxy group of the copolymer of the epoxy group-containing (meth)acrylate and other polymerizable monomer to make the unsaturated monocarboxylic acid (polymerizable component) ) And polycarboxylic acid anhydride (alkali soluble component) reaction.

Examples of the unsaturated monocarboxylic acid include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl group, alkoxy group, halogen atom, Monocarboxylic acids such as (meth)acrylic acid substituted with nitro or cyano. Among these, (meth)acrylic acid is preferable. Only one type of these unsaturated monocarboxylic acids may be used, or two or more types may be used in combination. By using this unsaturated monocarboxylic acid, the polymerizability can be imparted to the aforementioned alkali-soluble resin (3).

The unsaturated monocarboxylic acid is usually preferably added to 10 to 100 mol% of the epoxy group of the copolymer, more preferably added to 30 to 100 mol%, and particularly preferably added to 50 ~100 mol%.

Examples of the acid anhydride of the polycarboxylic acid include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorobridge anhydride. Anhydride of dicarboxylic acid; anhydride of carboxylic acid having three or more carboxyl groups such as trimellitic anhydride, pyromellitic anhydride, diphenyl ketone tetracarboxylic anhydride, biphenyltetracarboxylic anhydride, etc. Among these, tetrahydrophthalic anhydride and succinic anhydride are preferred. Only one type of these polycarboxylic acid anhydride systems may be used, or two or more types may be used in combination. By using the anhydride of this polycarboxylic acid, alkali solubility can be imparted to the aforementioned alkali-soluble resin (3).

The acid anhydride of the polycarboxylic acid is usually preferably added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monocarboxylic acid to the epoxy group of the copolymer, more preferably an addition At 20-90 mol%, it is especially preferable to add at 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. In addition, the dispersion degree (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, by adding α,β-unsaturated monocarboxylic acid to the epoxy resin or α,β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester part , It is further obtained by reacting polybasic acid anhydride.

As the aforementioned epoxy resin, for example, bisphenol A type epoxy resin (commercially available products are "Epikote 828", "Epikote 1001", "Epikote 1002", "Epikote 1004", etc. manufactured by Mitsubishi Chemical Corporation). 、Epoxy resin obtained by the reaction of alcoholic hydroxyl group of bisphenol A epoxy resin and epichlorohydrin (commercially available product is "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 323 , Softening point 76°C)), bisphenol F type resin (commercially available products are "Epikote 807", "EP-4001", "EP-4002", "EP-4004", etc., manufactured by Mitsubishi Chemical Corporation), Epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol F type epoxy resin with epichlorohydrin (commercially available product is "NER-7406" (epoxy equivalent 350, manufactured by Nippon Kayaku Co., Ltd. (Softening point 66℃)), bisphenol S type epoxy resin, biphenyl epoxypropyl ether (commercially available product is "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin ( Commercially available products are "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152", "EP-154" manufactured by Mitsubishi Chemical Co., Ltd., and "DEN-438" manufactured by Dow Chemical Japan Co., Ltd. ), cresol novolac epoxy resin (commercially available products are "EOCN-102S", "EOCN-1020", "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), triepoxypropyl heterotrimer Cyanate ester (commercially available product is "TEPIC" manufactured by Nissan Chemical Industry Co., Ltd.), triphenol methane epoxy resin (commercially available product is "EPPN-501" and "EPN- 502'', ``EPPN-503''), Fu epoxy resin (commercially available product is Cardo epoxy resin "ESF-300" manufactured by Nippon Steel Chemical Co., Ltd.), alicyclic epoxy resin (DAICEL Chemical Industry "Celloxide 2021P", "Celloxide EHPE" manufactured by Co., Ltd., dicyclopentadiene-type epoxy resin (for example, Nippon Chemical Co., Ltd.) which is a phenol resin reacted with dicyclopentadiene and phenol by epoxypropylation "XD-1000" manufactured by Pharmaceutical Co., Ltd., "EXA-7200" manufactured by DIC Corporation, "NC-3000" and "NC-7300" manufactured by Nippon Kayaku Co., Ltd.) Oxygen resin (refer to Japanese Patent Laid-Open No. 4-355450), etc. Only one type of these epoxy resins may be used, or two or more types may be used in combination.

As another example of the epoxy resin, a copolymerized epoxy resin may be mentioned. Examples of the copolymerization type epoxy resin include glycidyl (meth)acrylate, (meth)acryloylmethylmethylcyclocyclohexane, and vinylepoxycyclohexane. Oxygen monomer, with methyl (meth)acrylate, ethyl (meth)acrylate, (butyl) butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, ( Methacrylic acid, styrene, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, α-methylstyrene, glycerol mono(meth)acrylate, with polyoxyalkylene chain (Meth)acrylic acid ester and other non-epoxy polymerizable monomers copolymerized copolymer.

Examples of the (meth)acrylate having a polyoxyalkylene chain include diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, and tetraethylene glycol. Monoethylene glycol mono(meth)acrylate such as mono(meth)acrylate; methoxy diethylene glycol mono(meth)acrylate, methoxytriethylene glycol mono(meth)acrylate , Methoxytetraethylene glycol mono(meth)acrylate, alkoxy polyethylene glycol (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 the monomer having an epoxy group used as a raw material of the copolymerization type epoxy resin is preferably in the range of 10 to 70% by mass relative to the monomer having no epoxy group, and more preferably It is in the range of 20-50% by mass.

Examples of commercially available products of the aforementioned copolymerized epoxy resins include "CP-15", "CP-30", "CP-50", "CP-20SA", and "CP" manufactured by NOF Corporation. -510SA", "CP-50S", "CP-50M", "CP-20MA", etc.

The molecular weight of the aforementioned epoxy resin is good for the formation of the coating film and can prevent the gelation of the addition reaction of α,β-unsaturated monocarboxylic acid. The weight average molecular weight in terms of polystyrene measured by GPC is The preferred range is 200~200,000, and the preferred range is 300~100,000.

Examples of α,β-unsaturated monocarboxylic acids include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, and methacrylic acid. Acrylic acid and methacrylic acid are preferred. From the viewpoint of good reactivity, more Preferably acrylic. Examples of the α,β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion include 2-succinyl acrylate ethyl acrylate, 2-maleyl acrylate ethyl acrylate, and 2-o-acrylic acid acrylate Phthaloxyethyl, 2-Hexahydrophthalic acid acrylate, 2-Succinyloxyethyl methacrylate, 2-Maleoxyethyl methacrylate Ester, methacrylic acid-2-phthalic acid ethyl ester, methacrylic acid-2-hexahydrophthalic acid ethyl ester, crotonic acid-2-succinic acid ethyl ester, etc. Preferably, it is 2-maleimoxyethyl acrylate and 2-phthalimoxyethyl acrylate, and more preferably 2-maleimoxyethyl acrylate. These α,β-unsaturated monocarboxylic acids and α,β-unsaturated monocarboxylic acid ester systems may use only one type, or may use two or more types together.

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 reaction at a temperature of 50 to 150°C in the presence of an esterification catalyst . As the esterification catalyst, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, benzyldiethylamine, etc.; tetramethylammonium chloride, tetraethylammonium chloride, twelve Quaternary ammonium salts such as trimethylammonium chloride.

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

Examples of the polyanhydride further added to the epoxy resin to which α,β-unsaturated carboxylic acid or its ester is added include, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, diphenyl ketone tetracarboxylic dianhydride, methylhexahydrophthalic anhydride, nemethylene Tetrahydrophthalic anhydride, chlorobridge anhydride, methyltetrahydrophthalic anhydride, biphenyltetracarboxylic dianhydride, etc. Among these, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, and partial benzene are preferred Tricarboxylic anhydride and biphenyltetracarboxylic dianhydride, more preferably tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride. Only one type of these polybasic anhydride systems may be used, or two or more types may be used in combination.

Regarding the addition reaction of polybasic acid anhydride, a well-known method can also be used, and it can be continuously reacted under the same conditions as the addition reaction of α,β-unsaturated carboxylic acid or its ester. The use amount of the polybasic acid anhydride is preferably an amount in which the acid value of the generated epoxy (meth)acrylate resin is in the range of 10 to 150 from the viewpoint of improving alkali developability and coating film formation, and more preferably The amount becomes the range of 20~140.

In addition, as the epoxy (meth)acrylate resin having a carboxyl group, a naphthalene-containing resin described in Japanese Patent Laid-Open No. 6-49174; Japanese Patent Laid-Open No. 2003-89716 and Japanese Patent Laid-Open No. 2003-165830 can also be exemplified. , Japanese Unexamined Patent Publication No. 2005-325331, Japanese Unexamined Patent Publication No. 2001-354735 contains stilbene resin; Japanese Unexamined Patent Publication No. 2005-126674, Japanese Unexamined Patent Publication No. 2005-55814, Japanese Unexamined Patent Publication No. 2004-295084 The resin described in etc. In addition, as a commercially available product, "ACA-200M" manufactured by DAICEL Chemical Industry Co., Ltd. may be exemplified.

The cardo resin-type resin (5) has a carboxyl group and a polymerizable unsaturated group. Generally speaking, Cardo type resins are polymer materials with various characteristics such as high heat resistance, solvent solubility, high transparency, high refractive index, low birefringence, high air permeability, etc., which can be used as a color filter The adhesive resin for each pixel or black matrix is particularly suitable as the adhesive resin for forming the black matrix.

The aforementioned so-called card multi-type resin is a general term for a resin having a structure in which a cyclic group is directly bonded to a polymer main chain, but the presence of bulky substituents on the main chain shows: (1) polymer main Rotational restraint of the chain, (2) configuration restriction of the main chain and side chains, (3) obstruction of intermolecular accumulation, (4) increase in aromaticity due to introduction of aromatic substituents on the side chain, etc. 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 the cardo type resin (5), for example, resins represented by the following general formulas are preferably mentioned.

Where X is the group represented by the following chemical formula, Y is the residue after removing the carboxylic acid anhydride group (-CO-O-CO-) from the dicarboxylic acid anhydride, and Z is the removal of two carboxyl groups from the tetracarboxylic dianhydride Residue after 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, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride. Formic anhydride, hexahydrophthalic anhydride, methyl internal methylenetetrahydrophthalic anhydride, chlorobridge anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, etc.

In addition, specific examples of the tetracarboxylic dianhydride (tetracarboxylic dianhydride before removing two carboxylic anhydride groups) from which Z is derived include, for example, pyromellitic anhydride and diphenyl ketone tetracarboxylic dianhydride. Anhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, etc., tetracarboxylic dianhydride, etc.

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

In the alkali-soluble resin system, one kind of the above-mentioned alkali-soluble resins (1) to (5) may be used alone, or two or more kinds may be used in combination. In addition, the alkali-soluble resin is preferably used in combination with a pigment dispersant to be described later, whereby undissolved matter does not remain in the non-pixel portion on the substrate, and has excellent adhesion to the substrate, and can form high-density color pixels. Specifically, it is preferable to use a part of the alkali-soluble resin together with the pigment dispersant described later in the dispersion treatment step. In this case, the alkali-soluble resin is preferably used in the range of 5 to 200% by mass relative to the pigment, more preferably in the range of 10 to 100% by mass.

As the alkali-soluble resin, alkali-soluble resins other than the above-mentioned alkali-soluble resins (1) to (5) can also be used. Examples of such a resin include an alkali-soluble resin obtained by using a polymerizable monomer having a phenolic hydroxyl group as an acid group as an essential component, or a polymerizable monomer having a sulfonic acid group as an acid group. Alkali-soluble resin used as an essential ingredient. Here, examples of the polymerizable monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene. In addition, one or more hydrogen atoms other than the phenolic hydroxyl group and vinyl group bonded to the aromatic ring of these monomers may be substituted with an alkyl group, an alkoxy group, a halogen atom, a nitro group, or a cyanide Compounds such as radicals and amides. In addition, examples of the polymerizable monomer having a sulfonic acid group as an acid group include vinylsulfonic acid, styrenesulfonic acid, (meth)allylsulfonic acid, and 2-hydroxy-3-(methyl). Allyloxypropane sulfonic acid, 2-sulfoethyl (meth)acrylate or salts thereof.

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 from the viewpoint of the appearance of the cured film or the good adhesion to the substrate. The range of ~80 mass% is more preferably the range of 1~60 mass%.

As the radioactive substance (photosensitive substance) used in the resist composition, as long as it is mixed with the above-mentioned alkali-soluble resin, by irradiating ultraviolet rays, far ultraviolet rays, excimer laser light, X-rays, electron beams, ion rays, molecules Radiation, gamma rays, etc., which can change the solubility of the alkali-soluble resin in the developer, can be used.

Examples of the radiation-sensitive substance include quinonediazide compounds, diazo compounds, diazide compounds, onium salt compounds, halogenated organic compounds, mixtures of halogenated organic compounds and organometallic compounds, and organic acids. An ester compound, an organic acid amide compound, an organic acid amide imine compound, and a poly(olefin sulfone) compound described in Japanese Patent Laid-Open No. 59-152, etc.

Examples of the quinonediazide-based compounds include 1,2-benzoquinoneazido-4-sulfonate, 1,2-naphthoquinonediazide-4-sulfonate, and 1,2. -Naphthoquinonediazide-5-sulfonate, 2,1-naphthoquinonediazide-4-sulfonate, 2,1-naphthoquinonediazide-5-sulfonate, and 1 ,2-benzoquinone azide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 2 , 1-naphthoquinonediazide-4-sulfonyl chloride, 2,1-naphthoquinonediazide-5-sulfonyl chloride and other quinonediazide derivatives such as sulfonyl chloride.

Examples of the aforementioned diazo compound include salts of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde, such as hexafluorophosphate, tetrafluoroborate, perchlorate or periodate The diazo resin inorganic salt of the reaction product with the above condensate; such as the diazo resin organic salt of the reaction product of the above condensate and sulfonic acid described in USP 3,300,309.

Examples of the azide compound and diazide compound include azido-chalcone acid and diazidebenzylidenemethylcyclohexanone as described in Japanese Patent Laid-Open No. 58-203438. And azido cinnamylidene acetophenones, the Japanese Chemical Society Journal No. 12, p1708-1714 (1983) described in aromatic azide compounds or aromatic diazide compounds, etc.

As the halogenated organic compound, for example, it can be used as long as it is a halide of an organic compound. As a specific example, a halogen-containing Diazole compounds, halogen-containing three Compounds, halogen-containing acetophenone-based compounds, halogen-containing diphenyl ketone-based compounds, halogen-containing sulfonium-based compounds, halogen-containing ash-based compounds, halogen-containing thiazoline-based compounds, halogen-containing Azole compounds, halogen-containing triazole compounds, halogen-containing 2-piperidine compounds, halogen-containing aliphatic hydrocarbon compounds, halogen-containing aromatic hydrocarbon compounds, other halogen-containing heterocyclic compounds, Various compounds such as sulfenyl halide compounds, and ginseng (2,3-dibromopropyl) phosphate, ginseng (2,3-dibromo-3-chloropropyl) phosphate, chlorotetramine 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 -Dibromophenyl)propane, 2,2-bis(4-hydroxyethoxy-3,5-dibromophenyl)propane and other compounds used as halogen flame retardants, dichlorophenyltrichloroethane Alkanes and other compounds used as organochlorine pesticides.

Examples of the organic acid esters include carboxylic acid esters and sulfonic acid esters. In addition, examples of the above-mentioned organic acid amides include carboxylic acid amides, sulfonic acid amides, and the like. In addition, examples of the organic acid amide imine include carboxylic acid imide and sulfonic acid imide. These radiation-sensitive substances may be used alone or in combination of two or more.

In the resist composition, with respect to 100 parts by mass of the alkali-soluble resin, the blending ratio of the radiation-sensitive substance is preferably in the range of 10 to 200 parts by mass, and more preferably in the range of 50 to 150 parts by mass.

Examples of the solvent used in the resist composition include acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, and butyrolactone. Ketones; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, third butanol, pentanol, heptanol, octanol, nonanol, decanol, etc.; Glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol Ethers such as alkane; 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 and other esters, 2-oxymethyl propionate, 2-oxy ethyl propionate , Propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2 -Monocarboxylic acid esters such as butyl methoxypropionate; 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 trichloroethylene, chlorofluoroalkane solvents, HCFC, HFC, etc.; fully fluorinated solvents such as perfluorooctane, aromatics such as toluene and xylene; dimethyl ethyl The polar solvents such as amide, dimethylformamide, N-methylacetamide, N-methylpyrrolidone, etc. are described in the published book "Solvent Pocket Handbook" (Organic Synthetic Chemistry Association, OHMSHA) In the solvent. These solvent systems 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, alkali-soluble resin, polymerizable Compounds, colorants.

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

The polymerizable compound can be used without particular limitation as long as it has a photopolymerizable functional group that can be polymerized or cross-linked by irradiation with active energy rays such as ultraviolet rays. Examples of such a polymerizable compound 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, and aromatic groups. Esters of polyhydroxy compounds and unsaturated carboxylic acids, esters obtained by esterification of unsaturated carboxylic acids and polycarboxylic acids, and polyvalent hydroxy compounds such as aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, etc., A polymerizable compound having a carbamate skeleton obtained by reacting a polyisocyanate compound with a hydroxy compound containing (meth)acrylonitrile and the like.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and trimethylolpropane tri( Methacrylate, 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 glycerol (meth)acrylates. In addition, the methacrylic acid portion of these acrylates can be replaced by an itaconic acid ester of itaconic acid, a crotonic acid ester of crotonic acid, or a maleic acid ester of maleic acid. Wait.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone di(meth)acrylate, resorcinol di(meth)acrylate, and gallic acid tri(meth)acrylic acid. Ester etc. In addition, the ester system obtained by the esterification reaction of an unsaturated carboxylic acid, a polycarboxylic acid, and a polyvalent hydroxyl compound may be a single substance or a mixture. Examples of such esters include esters derived from (meth)acrylic acid, phthalic acid, and ethylene glycol, esters derived from (meth)acrylic acid, maleic acid, and diethylene glycol. Esters derived from meth)acrylic acid, terephthalic acid and pentaerythritol, esters derived from (meth)acrylic acid, adipic acid, butanediol and glycerin.

Examples of the polymerizable compound having a carbamate skeleton obtained by reacting the aforementioned polyisocyanate compound with a hydroxy compound containing a (meth)acryloyl group include hexamethylene diisocyanate and 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 ( A reactant of a hydroxy compound having a (meth)acryloyl group such as 2-hydroxyethyl methacrylate, 3-hydroxy[1,1,1-tris(meth)acryloyloxymethyl]propane, etc.

Examples of the polymerizable compound other than the above include (meth)acrylamide such as ethylidene bis(meth)acrylamide; allyl esters such as diallyl phthalate; diethylene Compounds having a vinyl group such as phthalate.

As the polymerizable compound, a polymerizable compound having an acid group can also be used. As the polymerizable compound having an acid group, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, preferably an unreacted hydroxyl group of the aliphatic polyhydroxy compound, reacted with a non-aromatic carboxylic acid anhydride to make it Multifunctional monomer with acid groups. In addition, among the aforementioned aliphatic polyhydroxy compounds, it is particularly preferable to use pentaerythritol or dipentaerythritol. Only one type of these single systems may be used, or two or more types may be used in combination. In addition, a monomer having an acid group and a monomer having no acid group may be used in combination.

In addition, as a preferred specific example of the polyfunctional polymerizable compound having an acid group, for example, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate commercially available as "Aronix TO-1382" from East Asia Synthetic Co., Ltd. can be cited. A mixture of succinate esters of acrylate and dipentaerythritol pentaacrylate as main components. This polyfunctional polymerizable compound can also be used in combination with other polyfunctional polymerizable compounds.

The acid value of the polyfunctional polymerizable compound having an acid group is preferably in the range of 0.1 to 40, and more preferably in the range of 5 to 30, from the viewpoint of good developability, curability, and the like. Furthermore, when two or more polyfunctional polymerizable compounds having different acid values are used in combination or when a polyfunctional polymerizable compound having no acid group is used in combination, the acid value of the mixture after mixing all the polyfunctional polymerizable compounds is preferably the above Within range.

In the color resist composition, the content ratio of the 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 particularly preferably 20 to 50% by mass Scope. In addition, the ratio of the polymerizable compound is preferably 5 to 200% by mass, more preferably 10 to 100% by mass, and particularly preferably 20 to 80% by mass relative to the coloring agent described later.

As the coloring agent, as long as it is capable of coloring, 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 the organic pigment, pigments of various hues such as red pigment, green pigment, blue pigment, yellow pigment, purple pigment, orange pigment, and brown pigment can be used. In addition, examples of the chemical structure of the organic pigment include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, and Department, Yindanshilin Department, Perylene Department, etc. Furthermore, the following "CI" means color index.

Examples of the aforementioned red pigments include CI 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 etc. Among these, C.I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, or 254 is preferred, and C.I. Pigment Red 177, 209, 224, or 254 is more preferred.

Examples of the aforementioned green pigments include CI Pigment Green 1, 2, 4, 7, 8, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, and 54. 55, 58 etc. Among these, C.I. Pigment Green 7, 36 or 58 is preferred.

Examples of the blue pigments include CI 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 these, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4 or 15:6 is preferred, and C.I. Pigment Blue 15:6 is more preferred.

Examples of the yellow pigments include CI 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 these, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, or 185 is preferred, and C.I. Pigment Yellow 83, 138, 139, 150, or 180 is more preferred.

Examples of the aforementioned purple pigments include CI 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 preferred, and C.I. Pigment Violet 23 is more preferred.

Examples of the aforementioned orange pigments include CI pigment oranges 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 and so on. Among these, C.I. Pigment Orange 38 or 71 is preferred.

Since the pixels of the three primary colors of the color filter used in the liquid crystal display device and the organic EL display device are red (R), green (G), and blue (B), the red pigment, green pigment, and blue Pigments are used as the main component for the purpose of improving color reproducibility, and organic pigments such as yellow, purple, and orange can also be used for hue adjustment.

In addition, examples of the inorganic pigment include barium sulfate, lead sulfate, titanium oxide, lead yellow, iron oxide red, and chromium oxide.

Furthermore, in order to improve the brightness of the color liquid crystal display device and the organic EL display device, the average particle diameter of the organic pigment is preferably 1 μm or less, more preferably 0.5 μm or less, and particularly preferably 0.3 μm or less. Preferably, the organic pigment is dispersed and used so as to have such an average particle diameter. In addition, the average primary particle diameter of the organic pigment is preferably 100 nm or less, more preferably 50 nm or less, particularly preferably 40 nm or less, and particularly preferably 10 to 30 nm. In addition, the average particle size of the organic pigment is measured by a dynamic light scattering type particle size distribution meter. For example, the Nanotrac (Nanotrac) particle size distribution measuring device "UPA-EX150", "" "UPA-EX250" and other measurements.

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, and thermal black. Channel black, furnace black, graphite, iron black, titanium black, etc. In addition, it may be a combination in which two or more kinds of organic pigments are mixed and become black by color mixing. Among these, carbon black and titanium black are preferred from the viewpoint of light shielding rate and image characteristics.

Examples of the commercially available carbon black products 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. include Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex manufactured by Evonik Degussa Japan Co., Ltd. P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack 350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color B1ack FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170, etc., include Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, manufactured by CABOT JAPAN Co., Ltd. REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK P EARLS480, PEARLS130, VULCAN XC72R, ELFTEX-8, etc., include RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890 made by COLUMBIAN CARBON RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000 and so on.

Among the above carbon blacks, as the high optical density and high surface resistivity required for a black matrix having a color filter, it is preferable to use carbon black coated with resin. In addition, the carbon black coated with the resin can be obtained, for example, by JP-A 9-26571, JP-A 9-71733, JP-A 9-95625, JP-A 9-238863 or The method described in Japanese Patent Laid-Open No. 11-60989 is obtained by processing well-known carbon black.

In addition, as a method for producing the aforementioned titanium black, there may be mentioned a method described in Japanese Patent Laid-Open No. 49-5432 for heating and reducing a mixture of titanium dioxide and metallic titanium in a reducing gas environment; 57-205322 discloses a method for reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride in a reducing gas environment containing hydrogen; Japanese Patent Laid-Open No. 60-65069 and Japanese Patent Laid-Open No. 61-201610 The gazette describes a method of high-temperature reduction of titanium dioxide or titanium hydroxide in the presence of ammonia; a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide described in Japanese Patent Laid-Open No. 61-201610, and a method of high-temperature reduction in the presence of ammonia, etc. As a commercially available product of titanium black, for example, titanium black 10S, 12S, 13R, 13M, 13M-C, etc. manufactured by Mitsubishi Materials Co., Ltd. may be mentioned.

When two or more types of organic pigments are mixed, and a combination of blacks is obtained by mixing colors, a black pigment in which three color pigments of red, green, and blue are mixed can be mentioned. In order to prepare black pigments, as color materials that can be used in combination, Victoria Pure Blue (CI42595), Auramine O (CI41000), Cathilon Bri1liant Flavin (Basic 13), Rose Red 6GCP (CI45160), Rose Red B (CI45170), Safranine OK70: 100 (CI50240), Erioglaucine X (CI42080), No. 120/Leno Yellow (Lionol Yellow) (CI21090), Leno Yellow GRO (CI21090), Shimura Fast Yellow (Shimura Fast Yellow) 8GF (CI21105), benzidine yellow 4T-564D (CI21095), Shimla Fast Red (Shimura Fast Red) 4015 (CI12355), Leno Red 7B4401 (CI15850), Fastogen blue (Fastogen blue) TGR-L (CI74160), Leno blue SM (CI26150), Leno blue ES (CI Pigment Blue 15:6), Leno Red GD (CI Pigment Red 168), Leno Green 2YS (CI Pigment Green 36), etc.

In order to prepare black pigments, examples of other color materials that can be mixed include CI yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, CI orange pigment 36, 43, 51, 55, 59, 61, CI red pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, CI purple pigment 19, 23, 29, 30, 37, 40, 50, CI blue pigment 15, 15: 1, 15: 4, 22, 60, 64, CI green pigment 7, CI 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 to 0.08 μm, and from the viewpoint of good developability, more preferably in the range of 0.02 to 0.05 μm. In addition, the absorption amount of the carbon black dibutyl phthalate (hereinafter, abbreviated as "DBP") is preferably in the range of 40 to 100 cm ³ /100g. From the viewpoint 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 measured by the BET method is preferably in the range of 50 to 120 m ² /g, and from the viewpoint of good dispersion stability, it is more preferably in the range of 60 to 95 m ² /g.

In addition, the shape of the carbon black-based particles is different from that of organic pigments, and there is a state called a structure in which the primary particles have been fused, or fine pores may be formed on the surface of the particles due to post-treatment. Therefore, in order to express the particle shape of carbon black, in addition to the average particle size of the primary particles obtained by the same method as the aforementioned organic pigment, it is preferable to measure the DBP absorption (JIS K6221) and the method using the BET method. The specific surface area (JIS K6217) is used as an indicator of the structure or pore volume.

In addition, dyes can also be used as colorants. Examples of such dyes include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes. Xanthene-based dyes, triarylmethane-based dyes, coumarin-based dyes, tertiary methyl-based dyes, anthraquinone-based dyes, and other dyes.

Examples of the aforementioned other dyes include oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes. Specifically, for example, the material index (The Society of Dyers and Colourists), compounds classified as dyes, or various dyes described in Dyeing Notes (Dyeing Society).

Examples of the aforementioned other dyes include CI Solvent Yellow 4 (hereinafter, CI solvent yellow is omitted, only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99; CI Solvent Red 45, 49, 125, 130; CI Solvent Orange 2, 7, 11, 15, 26, 56; etc. CI Solvent Dye,

CI 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; CI 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; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94 , 95, 107, 108, 169, 173; CI Acid Violet 6B, 7, 9, 17, 19; CI Acid Dyes, CI 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; CI 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; CI direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct violet 47, 52, 54, 59, 60, 65 , 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI direct dyes, CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI 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; CI Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI Mordant Violet 1 , 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; CI mordant dyes, etc.

Among the coloring agents listed above, it is preferable to use a pigment in that the cured film finally obtained has excellent light resistance, weather resistance, and compactness, but it can also be used in combination with the pigment as needed in order to adjust the hue. dye.

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

The content ratio of the colorant in the color resist composition is preferably 1% by mass or more of the total solid content, more preferably in the range of 5 to 80% by mass, and particularly preferably in the range of 5 to 70% by mass.

Furthermore, when the color resist composition is used to form the red (R), green (G), and blue (B) pixels of the color filter, the content ratio of the colorant in the color resist composition is preferably It is in the range of 5 to 60% by mass of all solid components, more preferably in the range of 10 to 50% by 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 in the entire solid content, more preferably 30 to 70% by mass.

In addition, the aforementioned organic pigment may be subjected to rosin treatment, surface treatment using a pigment derivative introduced with an acidic group or a basic group, and grafting treatment with a polymer compound to the surface of the pigment as necessary. Micronization treatment such as sulfuric acid micronization method, cleaning treatment with organic solvent or water for removing impurities, removal treatment of ionic impurities by ion exchange method, etc. In addition, the particle diameter is preferably uniform, and the organic pigment with a uniform particle diameter can be obtained by, for example, containing a pigment dispersant and performing a dispersion treatment.

When the aforementioned pigment dispersant is used, the usage amount thereof is preferably 1 part by mass or less per 1 part by mass of the pigment, and more preferably 0.05 parts by mass or more and 0.5 parts by mass or less. If the amount of the pigment dispersant used is within this range, there is a tendency to obtain a pigment dispersion liquid in a uniformly dispersed state (those dispersed in an organic solvent), which is preferable.

Examples of the aforementioned 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. Among these, a graft copolymer having a nitrogen atom, an acrylic block copolymer having a nitrogen atom, a urethane resin dispersant, and the like are preferred. Since these dispersants have nitrogen atoms, the nitrogen atoms have an affinity for the pigment surface, and by increasing the affinity of the parts other than the nitrogen atoms to the medium, the dispersion stability is increased. In addition, these dispersing agents may be used alone or in combination of two or more.

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

In addition, examples of the organic solvent 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 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 solvents such as ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic hydrocarbon solvents such as hexane; N,N-dimethylformamide, Nitrogen-based solvents such as γ-butyrolactam and N-methyl-2-pyrrolidone; lactone-based solvents such as γ-butyrolactone; carbamate and the like. These solvent systems may be used alone or in combination of two or more.

Examples of the method for preparing the pigment dispersion liquid include a method of passing through the kneading and dispersing step of the colorant and a micro-dispersing step, and a method of performing only the micro-dispersing step. In the aforementioned kneading and dispersing step, a part of the colorant, the alkali-soluble resin, and the aforementioned dispersing agent as necessary are mixed and kneaded. Examples of mechanical systems used for kneading include twin rolls, triple rolls, ball mills, rotary drum mills, dispersers, kneaders, co-kneaders, homogenizers, blenders, uniaxial or biaxial extruders, etc. By using these kneaders, while applying a strong shearing force, the dispersion can be performed to disperse the colorant. In addition, it is preferable that the colorant be fine-grained in advance by the salt mill method or the like before performing the above kneading.

On the other hand, in the microdispersion step, a solvent is added to the colorant-containing composition obtained in the kneading and dispersing step, or a colorant, an alkali-soluble resin, a solvent, and the foregoing dispersion as needed are mixed If the agent is used, the dispersion medium of glass, zirconia or ceramic fine particles is mixed and dispersed using a disperser to disperse the colorant particles to a tiny state close to the primary particles.

In addition, from the viewpoint of improving the transmittance and contrast of the color filter, the average particle diameter of the primary particles of the colorant is preferably 10 to 100 nm, and more preferably 10 to 60 nm. Furthermore, the average particle size of this colorant is measured by a dynamic light scattering type particle size distribution meter, for example, a Nanotrac (Nanotrac) particle size distribution measuring device "UPA-EX150" manufactured by Nikkiso Co., Ltd. , "UPA-EX250" and other measurements.

The photoresist initiator may be included in the resist composition.

As the photopolymerization initiator, for example, a biimidazole compound, an alkyl ketone compound, a Compounds, acetylphosphine oxide compounds, oxime compounds. In addition, the photo-cationic polymerization initiator described in Japanese Patent Laid-Open No. 2008-181087 (for example, an onium cation and an anion derived from Lewis acid) may be used. Among them, oxime compounds are preferred in terms of sensitivity.

Examples of the aforementioned biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole and 2,2'-bis(2 ,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2, 2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5 '-Tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2 ,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (for example, see Japanese Patent Publication No. 48-38403, Japanese Patent Laid-Open JP 62-174204, etc.), an imidazole compound in which a phenyl group in 4,4'5,5'-position is substituted with a carbonylalkoxy group (for example, refer to Japanese Patent Laid-Open No. 7-10913, etc.). Preferably, 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 .

Examples of the alkyl benzophenone compounds include diethoxyacetophenone and 2-methyl-2- Linolin-1-(4-methylhydrothiophenyl)propan-1-one, 2-dimethylamino-1-(4- Phenylphenyl)-2-benzylbutan-1-one, 2-dimethylamino-1-(4- Phenylphenyl)-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-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl- Oligomers of 1-(4-isopropenylphenyl)propan-1-one and the like, preferably 2-methyl-2- Linolin-1-(4-methylhydrothiophenyl)propan-1-one, 2-dimethylamino-1-(4- Phenylphenyl)-2-benzylbutan-1-one and the like. Commercial products such as Irgacure 369 and 907 (above, manufactured by BASF Japan) can also be used.

As the preceding three Compounds include, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tris , 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-tris , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-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)vinyl]-1,3,5-tri , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tri Wait.

Examples of the above-mentioned acylphosphine oxide starter include 2,4,6-trimethylbenzyldiphenylphosphine oxide and the like. Commercial products such as Irgacure 819 (manufactured by CIBA Japan) can also be used.

Examples of the oxime compound include N-benzyloxy-1-(4-phenylhydrothiophenyl)butan-1-one-2-imine and N-benzyloxy- 1-(4-phenylhydrothiophenyl)octan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl amide )-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-di Methyl-2,4-dioxolylmethoxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine and the like. Commercial products such as Irgacure OXE-01, OXE-02 (above, manufactured by BASF Japan), and N-1919 (manufactured by ADEKA) can also be used.

In addition, as a polymerization initiator having a group capable of causing chain transfer, a photopolymerization initiator described in Japanese Patent Publication No. 2002-544205 can also be used. Examples of the polymerization initiator having a group capable of causing chain transfer include compounds of the following formula.

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

The resist composition may further contain a polymerization initiation aid. The polymerization initiator is used in combination with a photopolymerization initiator, and is a compound or a sensitizer, which is used to promote the polymerization of the polymerizable compound started to be polymerized by the polymerization initiator.

Examples of the polymerization start adjuvant include amine compounds, thiazoline compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds. Examples of the aforementioned amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-diethylaminobenzoate. Isoamyl methylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl p-toluidine, 4 ,4'-bis(dimethylamino)diphenyl ketone (commonly known as Michler's ketone), 4,4'-bis(diethylamino) diphenyl ketone, 4,4'-bis(ethyl Methylamino group) diphenyl ketone and the like, among which 4,4'-bis(diethylamino) diphenyl ketone is preferred. Commercial products such as EAB-F (Hodogaya Chemical Industry Co., Ltd.) can also be used.

Examples of the thiazoline compounds include the compounds shown below.

Examples of the aforementioned alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2- Ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, 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 phenylhydrothioacetic acid, methylphenylhydrothioacetic acid, ethylphenylhydrothioacetic acid, methylethylphenylhydrothioacetic acid, and dimethyl Phenylhydrothioacetic acid, methoxyphenylhydrothioacetic acid, dimethoxyphenylhydrothioacetic acid, chlorophenylhydrothioacetic acid, dichlorophenylhydrothioacetic acid, N-phenylglycine Amino acid, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

In addition, the resist composition may further contain a multifunctional thiol compound. This multifunctional thiol compound is a compound having two or more hydrogen sulfide groups in the molecule. Among them, if a compound having two or more hydrogen sulfide groups adjacent to the aliphatic hydrocarbon group is used, a pattern can be formed with high sensitivity, which is preferable.

The solvent system included in the resist composition is not particularly limited, and a solvent generally used in this field can be used. For example, it can be selected from ester solvents (solvents containing -COO-), ether solvents (solvents containing -O-) other than ester solvents, ether ester solvents (solvents containing -COO- and -O-), and ester solvents. The ketone solvent (solvent containing -CO-), alcohol solvent, aromatic hydrocarbon solvent, amide solvent, dimethyl sulfoxide, etc. are selected and used. These solvent systems 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, pentyl formate, and acetic acid. Isoamyl ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate Ester, cyclohexanol acetate, γ-butyrolactone, etc.

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, tetrahydropiperan, 1,4-di Alkanes, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, benzoic acid Ether, phenethyl ether, methyl anisole, etc.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate and 3-methoxyethyl acetate Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionate Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate , Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate Ester, 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 ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl -2-pentanone, cyclopentanone, cyclohexanone, isophorone, etc.

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

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.

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

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

The content of the solvent is preferably 60 to 95% by mass relative to the resist composition, and more preferably 70 to 90% by mass. In other words, the solid content of the resist composition is preferably 5 to 40% by mass, more preferably 10 to 30% by mass. If the content of the solvent is in the aforementioned range, the flatness during coating tends to be good.

In addition, as long as the effect of the present invention is not impaired, a surfactant other than the fluorine-containing active energy ray curable resin (I) may be contained. Examples of the surfactant include polysiloxane-based surfactants, fluorine-based surfactants, polysiloxane-based surfactants having fluorine atoms, and surfactants having fluorine atoms and ethylenically unsaturated bonds. .

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

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

Examples of the adhesion promoter include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl ginseng (2-methoxyethoxy) silane, and N-(2-aminoethyl Group)-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 antioxidants include 4,4'-thio-bis(6-tert-butyl-3-methylphenol) and triethylene glycol-bis[3-(3-tert-butyl 5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid Ester], pentaerythritol-butan[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-ginseng (3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,6-di Tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,2'-methylenebis(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-ginseng (2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-ginseng (4-hydroxybenzyl)benzene, and [methylene- 3-(3,5'-di-tert-butyl-4'-hydroxyphenyl propionate)] methane, etc.

Examples of the aforementioned ultraviolet absorber include benzotriazoles such as 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole; 2 -Hydroxy-4-octyloxy diphenyl ketone and other diphenyl ketones; 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, etc. Benzoate series; 2-(4,6-diphenyl-1,3,5-tri -2-yl)-5-hexyloxyphenol and so on Department etc.

Examples of the aforementioned anti-agglomerating agent include sodium polyacrylate.

By adding the organic amine compound, no residue is generated on the substrate in the unexposed area during development, and a pixel with excellent adhesion to the substrate can be given. Examples of the aforementioned organic amine compounds 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, and n-dodecylamine; cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclo Monocyclic alkylamines such as hexylamine; methylethylamine, diethylamine, methyl-n-propylamine, ethyl-n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisopropylamine Dialkylamines such as butylamine, di-second butylamine, di-third butylamine, di-n-pentylamine, and di-n-hexylamine; monoalkyl monocycloalkanes such as methylcyclohexylamine, ethylcyclohexylamine, etc. Amines; dicyclohexylamines such as dicyclohexylamine; dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine , Methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-second butylamine, tri-third-butylamine, tri-n-pentylamine Trialkylamines such as amines and tri-n-hexylamine; dialkyl monocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine; methyldicyclohexylamine and ethyldicyclohexylamine Monoalkyl dicycloalkylamines such as amines, tricyclohexylamine, etc.; 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; monocycloalkanolamines such as 4-amino-1-cyclohexanol; Dialkanolamines such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine, etc.; di(4-cyclo Hexanol)amines and other dicycloalkanolamines; triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine Tricycloalkanolamines such as tris(4-cyclohexanol)amine; 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- Aminoalkanediols such as propylene glycol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol, etc.; 4-amino-1,2-cyclohexanedione Aminocycloalkanediols such as alcohol, 4-amino-1,3-cyclohexanediol, etc.; amine-containing naphthenes such as 1-aminocyclopentanone methanol, 4-aminocyclopentanone methanol, etc. Ketone methanol; 1-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentane methanol, 4-diethylaminocyclopentane methanol, 4-dimethyl Amino-containing cycloalkane methanols such as aminoaminocyclohexane methanol, 4-diethylaminocyclohexane methanol, etc.; β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4 -Aminobutyric acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminohexanoic acid, 1-aminocyclopropanecarboxylic acid, Aminocarboxylic acids such as 1-aminocyclohexanecarboxylic acid and 4-aminocyclohexanecarboxylic acid; aniline, o-methylaniline, m-methyl Aniline, p-toluidine, p-ethylaniline, p-n-propylaniline, p-isopropylaniline, p-n-butylaniline, p-third butylaniline, 1-naphthylamine, 2-naphthylamine, N , N-dimethylaniline, N,N-diethylaniline, p-methyl-N,N-dimethylaniline and other aromatic amines; o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-amine Aminobenzyl alcohols such as benzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol, etc.; o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylamino Aminophenols such as phenol and p-diethylaminophenol; m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid and other aminophenols Formic acid, etc.

As the curing agent, for example, when a resin having a carboxyl group is used as the alkali-soluble resin, a compound that can react with the carboxyl group by heating to crosslink the alkali-soluble resin can be exemplified. Moreover, the compound which can produce a cured film by individual polymerization can also be mentioned. Examples of the aforementioned compounds include epoxy compounds and oxetane compounds.

Examples of the epoxy compound include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, and novolac epoxy resin. Epoxy resins such as resins, other aromatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidylamine resins, epoxidized oils, etc. 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, triglycidoxy isocyanurate, etc.

Examples of the aforementioned oxetane compounds include carbonate dioxetane, xylylene dioxetane, adipic acid dioxetane, and paraxylylene Acetate dioxetane, cyclohexane dicarboxylic acid dioxetane, etc.

When an epoxy compound, an oxetane compound, or the like is contained as a hardener, a compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound may also be included. Examples of the compound include polycarboxylic acids, polycarboxylic acid anhydrides, and acid generators.

Examples of the aforementioned polycarboxylic acids include phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, and 1 ,4,5,8-naphthalene tetracarboxylic acid, 3,3',4,4'-diphenyl ketone tetracarboxylic acid and other aromatic polycarboxylic acids; succinic acid, glutaric acid, adipic acid, 1, Aliphatic polycarboxylic acids such as 2,3,4-butane tetracarboxylic acid, maleic acid, fumaric acid, and itaconic acid; hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid Formic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentane tricarboxylic acid, 1,2,4-cyclohexane tricarboxylic acid, cyclopentane tetracarboxylic acid, 1 , 2,4,5-cyclohexane tetracarboxylic acid and other alicyclic polycarboxylic acids.

Examples of the aforementioned polycarboxylic acid anhydrides include phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, etc. Aromatic polycarboxylic anhydrides; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, glycerin anhydride, maleic anhydride, 1,2,3,4-butane tetracarboxylic dianhydride, etc. Of aliphatic polycarboxylic anhydrides; hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentane tricarboxylic anhydride, 1,2,4- Alicyclic polycarboxylic anhydrides such as cyclohexane tricarboxylic anhydride, cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, humic anhydride, and nalazine anhydride; Ester group-containing carboxylic acid anhydrides such as diol bistrimellitic acid and glycerol trimellitic anhydride.

As the aforementioned carboxylic acid anhydrides, those sold as epoxy resin hardeners can also be used. Examples of the aforementioned epoxy resin hardeners include trade names Adeka Hardener EH-700 (manufactured by Asahi Denki Kagaku Kogyo Co., Ltd.), Rikacid HH, and MH-700 (all manufactured by New Japan Chemical Co., Ltd.).

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

In addition, the resist composition may contain an organic acid with a molecular weight of 1,000 or less. Examples of the aforementioned organic acids include those disclosed in Japanese Patent Laid-Open No. 5-343631. Specific examples include malonic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, citraconic acid, and itaconic acid. , Mesaconic acid, fumaric acid, phthalic acid, acrylic acid, methacrylic acid, preferably malonic acid, oxalic acid, fumaric acid, phthalic acid.

The content of the fluorine-containing active energy ray-curable resin (I) of the resist composition varies depending on the type of resist composition, the coating method, the target film thickness, etc. In view of the above effect, it is preferably 0.0001 to 10 parts by mass, more preferably 0.00001 to 5 parts by mass, and particularly preferably 0.01 to 2 parts by mass relative to 100 parts by mass of the solid content in the resist composition.

The coating method of the resist composition differs depending on the application, and examples include: using a gravure coater, roll coater, corner-cutter coater, knife coater, air knife coater, curtain coater, kiss Coating methods such as coater, spray coater, wheel coater, spin coater, dipping, screen printing, spray, applicator, bar coater, electrostatic coating, etc., 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 light such as visible light and ultraviolet light. Among the active energy ray-curable compositions, the resist composition (photoresist composition, color resist composition for color filters, etc.) requires a high level of leveling. Generally, in lithography related to semiconductors or liquid crystals, the resist composition is generally applied by spin coating or slit coating to a silicon wafer or a variety of metals deposited in a thickness of about 0.01 to 5 μm. On the glass substrate. At this time, the variation of the coating film thickness may cause the deterioration of the quality of the semiconductor or liquid crystal element or defects. However, the fluorine-containing active energy ray-curable resin (I) of the present invention is used as an additive for this composition. By forming a uniform coating film due to its high leveling properties, it is possible to improve the productivity of semiconductors and liquid crystal elements and increase the functionality.

From such a viewpoint, the fluorine-containing active energy ray-curable resin (I) of the present invention can be suitably used as a liquid repellent. When used as a liquid repellent, it is preferably a negative resist composition (photosensitive resin composition) containing the aforementioned alkali-soluble resin as a main component, and is preferably relative to the total solid content in the composition The fluorine-containing active energy ray-curable resin (I) of the present invention is used at 0.01 to 5.0% by mass.

The negative resist composition using the fluorine-containing active energy ray-curable resin (I) as a liquid repellent is applied to the surface of the substrate, and by exposure and development, a patterned cured film can be obtained. 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. When the pattern is printed by the IJ method, the partition wall is surrounded by The ink can be evenly applied in the area, and it is possible to suppress those who inject ink into undesired areas other than the partition wall, and the ink can be printed well in a desired pattern.

The optical element printed by the IJ method using the partition wall in this way can be applied as an organic EL element, a color filter of a liquid crystal element, an organic TFT array element, or the like.

[Example]

Hereinafter, several embodiments related to the present invention will be described, but it is not intended to limit the present invention to those shown in the embodiments. In addition, unless otherwise specified, "parts" and "%" in the following descriptions or tables indicate solid components or effective components on a mass basis.

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 tube, and a dripping device, add 50 parts of a perfluoropolyether compound having hydroxyl groups at both ends represented by the following formula (hereinafter, referred to as "compound (1)"; The hydroxyl equivalent weight is 740g/eq; a represents 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 flow, and while maintaining the temperature in the flask at 50°C, 8.3 parts of 49% sodium hydroxide aqueous solution was dropped over 2 hours. After the dropping, the temperature was raised to 60°C, and after stirring for 3 hours, the temperature was returned to room temperature.

Subsequently, the ion-exchanged water was used to wash the reaction liquid that had returned to room temperature. In the washing system, 50 parts of ion-exchanged water was added to the reaction solution and stirred, and the aqueous layer was separated by standing and separated, and this operation was repeated twice. From the washed reaction liquid, unreacted epichlorohydrin was distilled off by distillation under reduced pressure, and it was taken out by filtration to obtain 52.2 parts of the poly(perfluoroalkylene) represented by the following formula (a1-1) Compound) and a compound having an epoxy group at both ends (hereinafter, abbreviated as "compound (a1-1)"). This compound (a1-1) is 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) is 0.4.

Next, 47.4 parts of compound (a1-1), 17.2 parts of bisphenol A diglycidyl ether, and 16.0 parts of bisphenol A were added to a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device With 1000 ppm of tetrabutylphosphonium hydroxide (TBPH), heating at 150°C for 40 hours to obtain compound (2) with Mw 28,000. Next, in 161 parts of a solution of compound (2) diluted with propylene glycol monomethyl ether acetate (PGMEA) in NV = 50%, 0.03 part of dibutyl dilaurate as a carbamate catalyst was added Tin and 0.1 parts of p-methoxyphenol as a polymerization inhibitor were stirred under an air flow. After the temperature was raised to 75°C, 19.4 parts of 2-propenyl acrylate was dropped in 1 hour and stirred for 30 minutes at 75 minutes. The temperature was raised to 80°C in 1 minute, and the reaction was further stirred for 2 hours. As a result, it was confirmed by IR spectroscopy that the absorption peak near 2360 cm ^-1 derived from the isocyanate group disappeared. Next, PGMEA was added to obtain a PGMEA solution containing 10% of 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 tube, and a dripping device, add 50 parts of a compound with a hydroxyl equivalent of 754g/eq of a=5 and b=7, which are represented by the same formula as the aforementioned compound (1) (3), 6.5 parts of maleic anhydride. Next, stirring was started under a nitrogen flow, the temperature in the flask was raised to 160°C, and stirring was performed for 1 hour. Then, 0.01 parts of dibutyltin dilaurate as an esterification catalyst was added, and the temperature in the flask was raised to 170°C and stirred for 5 hours. Then, it returned to room temperature, and obtained 56.5 parts of the compound which has a poly (perfluoro alkyl ether) chain represented by the following formula (a5-1) and a carboxyl group at both ends (hereinafter, abbreviated as "compound (a5 -1)"). This compound (a5-1) is a transparent liquid with an acid value of 64.0 mgKOH/g.

Next, in a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dripping device, 50 parts of compound (a5-1), 23 parts of bisphenol A epoxy resin (epoxy equivalent 485g/eq) and 1000 ppm of tetrabutylphosphonium hydroxide (TBPH) was heated at 150° C. for 30 hours to obtain compound (4) with Mw 53,000. Next, to compound 146 parts of a solution of compound = (4) diluted with propylene glycol monomethyl ether acetate (PGMEA) in NV = 60%, add 0.02 parts of dibutyl dilaurate as a carbamate 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 started to stir under an air flow, and the temperature was raised to 75°C. Then, 6.7 parts of 2-acryloyloxyethyl acrylate was dropped over 1 hour, and after stirring at 75°C for 1 hour, the temperature was raised to 80°C, and the mixture was further stirred for 4 hours. It was confirmed by IR spectroscopy that the isocyanate group originated near 2270 cm ^-1 The absorption peak disappears. Finally, PGMEA was added to obtain a PGMEA solution containing 10% of fluorine-containing active energy ray-curable resin (2-i).

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

In a glass flask equipped with a stirring device, a thermometer, a cooling tube and a dripping device, 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 The tetrabutylphosphonium hydroxide (TBPH) was heated at 150°C for 40 hours to obtain compound (5) with a Mw of 26,000. Next, in 160 parts of a solution of compound (5) diluted with propylene glycol monomethyl ether acetate (PGMEA) in NV=50%, 0.03 parts of dibutyl dilaurate as a carbamate catalyst was added Tin and 0.1 parts of p-methoxyphenol as a polymerization inhibitor were stirred under an air flow. After the temperature was raised to 75°C, 20.1 parts of 2-propenyl acrylate was dropped in 1 hour and stirred at 75 minutes for 30 minutes The temperature was raised to 80°C in 1 minute, and the reaction was further stirred for 2 hours. As a result, it was confirmed by IR spectroscopy that the absorption peak near 2360 cm ^-1 derived from the isocyanate group disappeared. Next, PGMEA was added to obtain a PGMEA solution containing 10% of fluorine-containing active energy ray-curable resin (1-ii).

Example 4: Production of fluorine-containing active energy ray-curable resin (1-iii)

In a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dripping device, add 51.4 parts of compound (a1-1), 15.2 parts of 1,6-naphthalene diglycidyl ether, and 12.2 parts of 1,6 -Naphthalenediol and 1000 ppm of tetrabutylphosphonium hydroxide (TBPH) are heated at 150° C. for 40 hours to obtain a compound (6) of Mw 27,000. Next, in 158 parts of a solution of compound (6) diluted with propylene glycol monomethyl ether acetate (PGMEA) in NV = 50%, 0.03 part of dibutyl dilaurate was added as a carbamate catalyst Tin and 0.1 parts of p-methoxyphenol as a polymerization inhibitor were stirred under an air flow. After the temperature was raised to 75°C, 21.1 parts of 2-propenyl acrylate was dropped in 1 hour and stirred for 30 minutes at 75 minutes. The temperature was raised to 80°C in 1 minute, and the reaction was further stirred for 2 hours. As a result, it was confirmed by IR spectroscopy that the absorption peak near 2360 cm ^-1 derived from the isocyanate group disappeared. Next, PGMEA was added to obtain a PGMEA solution containing 10% of fluorine-containing active energy ray-curable resin (1-iii).

Example 5: Production of fluorine-containing active energy ray curable resin (1-iv)

In a glass flask equipped with a stirring device, a thermometer, a cooling tube and a dripping device, 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 The tetrabutylphosphonium hydroxide (TBPH) was heated at 150°C for 40 hours to obtain compound (7) with Mw 28,000. Next, in 165 parts of a solution of compound (7) diluted with propylene glycol monomethyl ether acetate (PGMEA) in NV = 50%, 5.7 parts of succinic anhydride and 3000 ppm of triphenylphosphine were added, and the temperature was raised to 110°C For 4 hours. After confirming the end of the reaction by acid value, cool to 75°C, add 0.03 parts of dibutyltin dilaurate as the urethane-forming catalyst, and 0.1 part of p-methoxyphenol as the polymerization inhibitor. dropwise over 1 hour under charge of 19.4 parts of ethyl acrylate, 2-yloxy Bingxi Xi, stirred at 75 minutes and 30 minutes, and warmed to 80 ℃, stirred for a further 2 hours the reaction was confirmed by IR spectroscopy from 2360cm isocyanate group ^- The absorption peak near ¹ disappears. Next, PGMEA was added to obtain a PGMEA solution containing 10% of 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 dropping device, add 20 parts of the aforementioned compound (a1-1-1), 20 parts of diisopropyl ether as a solvent, and 0.02 parts as a polymerization inhibitor P-methoxyphenol and 3.1 parts by mass of triethylamine as a neutralizing agent were stirred under an air flow, and while maintaining the flask at 10°C, 2.7 parts by mass of acrylic chloride was dropped over 1 hour. After completion of the dripping, the mixture was stirred at 10°C for 1 hour to increase the temperature. After stirring at 30°C for 1 hour, the temperature was raised to 50°C and the reaction was stirred for 10 hours. The disappearance of propylene acetyl chloride was confirmed by gas chromatography. Next, after adding 40 parts of diisopropyl ether as a solvent, it was washed by mixing 80 parts of ion-exchanged water, stirring and standing, and separating and removing the water layer, and 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 1 day to completely dehydrate, the dehydrating agent was separated by filtration. Next, the solvent was distilled off under reduced pressure to obtain 21.5 parts of a compound (8) having an acryloyl group at both ends of the perfluoropolyether chain represented by the following formula.

(In the formula, a is an average of 5, and b is an average of 8; and, 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 tube, and a dripping device, and the temperature was raised to 105°C while stirring under a nitrogen flow. 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 of 126 parts of methyl isobutyl ketone were dissolved as 9.4 parts as radical polymerization The three kinds of dripping liquids of the polymerization initiator solution of the tertiary butylperoxy-2-ethylhexanoate of the starting agent are respectively installed in separate dropping devices, while keeping the inside of the flask at 105°C, simultaneously It took 2 hours to drop. After completion of the dripping, after stirring at 105°C for 10 hours, the solvent was distilled off under reduced pressure to obtain 67.5 parts of the polymer. Next, 74.7 parts of methyl ethyl ketone as a solvent, 0.1 part of p-methoxyphenol as a polymerization inhibitor, and 0.06 part of dilauric acid as a carbamate catalyst were added to the polymer obtained above Butyl tin was stirred under an air flow, and while maintaining at 60°C, 44.8 parts of 2-acryloyloxyethyl acrylate was dropped over 1 hour. After the completion of the dropping, the mixture was stirred at 60°C for 1 hour, and then heated to 80°C and stirred for 10 hours to carry out the reaction. As a result, it was confirmed by IR spectroscopy that the absorption peak near 2360 cm ^-1 derived from the isocyanate group disappeared. Next, 37.4 parts of methyl ethyl ketone as a solvent was added to obtain 224.6 parts of a methyl ethyl ketone solution containing a 50% polymerizable fluorine-based compound. The molecular weight of this polymerizable fluorine-based compound was measured by GPC (polystyrene-equivalent molecular weight), and as a result, the number average molecular weight was 2,200 and the weight average molecular weight was 6,500. In addition, the fluorine content is 11%.

<Formation method of coating film>

Examples and comparative manufacturing of 3.0 parts of Unidic RS20-160 manufactured by DIC Corporation and 1.2 parts of Aronix M-402 manufactured by East Asia Synthetic Chemical Co., Ltd. with a solid content ratio of 0.1%, 0.5%, 1.0%, and 2.0% The resin obtained in the example was diluted with PGMEA to prepare a solution so as to become NV 19.5%. 1 mL of the prepared solution was dropped onto the central portion of a 7 cm×7 cm glass substrate, spin-coated at a rotation number of 1000 rpm and a rotation time of 10 seconds, and then heated and dried at 80° C. for 3 minutes to volatilize the solvent. Next, the dried coating film was irradiated with ultraviolet rays (UV) by an ultraviolet curing device (under an air atmosphere, a high-pressure mercury lamp, and an ultraviolet irradiation dose of 0.5 kJ/m ² ) to cure. In addition, heat treatment was performed at 230° C. for 20 minutes, and as Examples 6 to 10 and Comparative Example 1, a coating film was produced. A coating film of Comparative Example 2 was produced in the same manner as Comparative Example 1, except that the fluorine-based surfactant was not used.

<Measurement of contact angle of PGMEA>

For the surface of the coating film, the contact angle of PGMEA was measured using a contact angle measuring device ("MODEL CA-W701" manufactured by Kyowa Interface Science Co., Ltd.). Table 1 shows the results. 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 in which both ends are hydroxyl groups and at least one hydrogen atom is replaced with a fluorine atom (however, the alkylene group The chain contains an etheric oxygen atom) (A) residues, and at least one: residues of a divalent phenolic hydroxyl-containing compound (B) other than (A) and/or divalent carboxylic acid (C) Residues; having their structural units bonded by a linking group represented by 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 acid group], and the structural formula (1) included in 1 molecule At least one of the connecting groups shown is a monovalent organic group (x1) having a polymerizable group. A fluorine-containing active energy ray-curable resin characterized by having in one molecule: at least one: an alkylene chain in which a carboxyl group at both ends and at least one hydrogen atom is replaced by a fluorine atom (however, the alkylene group The chain contains an etheric oxygen atom) (D) residues, or an alkylene chain in which both ends are hydroxyl groups and at least one hydrogen atom is replaced with a fluorine atom (however, the alkylene chain contains an ether chain Oxygen atom) (A) the residue of the reactant with dicarboxylic anhydride (E), and at least one: the residue of a divalent hydroxyl group-containing compound (F) other than (A); having the following The structural unit bonded by the linking group shown in the 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 acid group], and the structural formula (1) included in 1 molecule At least one of the connecting groups shown is a monovalent organic group (x1) having a polymerizable group. The fluorine-containing active energy ray-curable resin according to claim 1 or 2, wherein the terminal is a hydrogen atom, a carboxyl group or an epoxypropyl group. The fluorine-containing active energy ray-curable resin according to any one of claims 1 to 3, wherein the fluorine atom-containing curable resin has a fluorine atom content rate in a range of 3 to 40% by mass. The fluorine-containing active energy ray-curable resin according to any one of claims 1 to 4, wherein the weight-average molecular weight of the fluorine-containing active energy ray-curable resin is in the range of 5,000 to 200,000. The fluorine-containing active energy ray-curable resin according to any one of claims 1 to 5, wherein the concentration of the active energy ray-curable functional group 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 any one of claims 1 to 6, wherein the alkylene chain in which both ends are hydroxyl groups and at least one of the hydrogen atoms is replaced with a fluorine atom (however, the alkylene group The chain contains an etheric oxygen atom) (A), an alkylene chain in which both ends are carboxyl groups and at least one hydrogen atom is replaced by a fluorine atom (however, the alkylene chain contains etheric oxygen Atom) (D) is a perfluoroalkyl ether chain. The fluorine-containing active energy ray-curable resin according to any one of claims 1 to 7, wherein the divalent phenolic hydroxyl-containing compound (B) and the divalent hydroxyl-containing compound (F) may have a substitution on the aromatic ring Based biphenol, bisphenol, binaphthol or naphthol. The fluorine-containing active energy ray-curable resin according to any one of claims 1 to 8, wherein the structural formula (1) is a structure represented by the following structural formula (2), [In formula (2), Y is a divalent linking group, and R is a hydrogen atom or a methyl group]. A method for manufacturing a fluorine-containing active energy ray-curable resin, characterized in that: for at least one alkylene chain having a hydrogen atom substituted with a fluorine atom (however, the alkylene chain contains etheric oxygen Atom) and the epoxy compound (a1), and the divalent phenolic hydroxyl group-containing compound (a2) and/or the divalent carboxylic acid (a3) as the necessary raw materials to react the secondary hydroxyl group in the reactant, so The active energy ray-curable functional group reacts with the isocyanate group compound (a4). A method for manufacturing a fluorine-containing active energy ray-curable resin, characterized in that: for at least one alkylene chain having a hydrogen atom substituted with a fluorine atom (however, the alkylene chain contains etheric oxygen Atom) the compound (a5) with a carboxyl group or a hydroxyl group, and the secondary hydroxyl group in the reactant obtained by reacting with a divalent epoxy compound (a6) as a necessary raw material, which has the active energy ray hardening functional group and the isocyanate group Compound (a4) reacts. The method for producing a fluorine-containing active energy ray-curable resin according to claim 10 or 11 further reacts the secondary hydroxyl group-containing anhydride group-containing compound (a7). A liquid repellent characterized by containing 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 active energy ray-curable 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, which further contains a polymerization initiator. The active energy ray-curable resin composition according to any one of claims 14 to 16, which 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. If the hardened film of claim 18 is a partition wall.