TW201431942A - Curable composition, cured film, display element and dry film - Google Patents

Abstract

This invention provides a curable composition. The curable composition has an excellent development property even under the high coloring agent concentration and can form a color filter with the high productivity rate. A curable composition is characterized by comprising (A) a polymer having the group represented by formula (1), substituted or non-substituted alicyclic hydrocarbyl and polymerizable unsaturated group, and (B) solvent. In formula (1), R1 represents the C2-4 linear alkylene, R2 represents the aliphatic hydrocarbyl, n represents an integer of 1 to 100, * represents the bonding site, and wherein when n is 2 or more, multiple R1's can be the same or different.

Description

Curable composition, cured film, display element, and dry film

The present invention relates to a curable composition, a cured film, and a display element, and more particularly to a transparent liquid crystal display element, a solid-state image sensor, an organic EL display element, an electronic paper, or the like used in a transmissive or reflective type. A curable composition used for forming a cured film, a cured film formed using the curable composition, and a display element including the cured film.

When a color filter is produced using a colored radiation-sensitive composition, it is known that a pigment-dispersed colored radiation-sensitive composition is applied onto a substrate and dried, and then the dried coating film is irradiated with radiation (hereinafter referred to as "exposure"). A method of developing a desired pattern shape to obtain pixels of respective colors (for example, Patent Documents 1 and 2). Further, a method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed is also known (for example, Patent Document 3). Further, a method of obtaining pixels of respective colors by an inkjet method using a pigment dispersion type colored resin composition (for example, Patent Document 4) is also known.

When the concentration of the coloring agent contained in the colored radiation-sensitive composition increases with the high color purity of the color liquid crystal display device, there is a possibility that residue or scum is likely to occur on the substrate or the light-shielding layer on the unexposed portion during development. tendency. In order to avoid the generation of such residues and scum, Increasing the development time is effective, but if the development time is increased, there is a drawback that the take-up time becomes long.

In addition, when the concentration of the coloring agent contained in the colored radiation-sensitive composition is increased, the solubility of the coating film in the alkali developing solution tends to be remarkably lowered. Therefore, when the development is carried out by the shower development method, the coating film of the unexposed portion which has been peeled off is not completely dissolved in the developing tank and floats, and foreign matter adheres to the color filter, and the product yield is lowered. The most important factor.

Therefore, there is a strong demand for a colored radiation-sensitive composition that satisfies various requirements relating to developability and product yield at the time of production of a color filter. For example, a colored photosensitive resin composition containing a monomer having a hydrophilic group has been proposed. (for example, Patent Document 5).

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open No. 2-144502

Patent Document 2 Japanese Patent Laid-Open No. 3-53201

Patent Document 3 Japanese Patent Laid-Open No. Hei 6-35188

Patent Document 4 Japanese Patent Laid-Open Publication No. 2000-310706

Patent Document 5 Japanese Patent Laid-Open Publication No. 2006-208796

However, the actual situation is that even if such a colored photosensitive resin composition is used, it cannot be said that various requirements relating to developability and product yield are sufficiently obtained.

Therefore, an object of the present invention is to provide a curable composition which is excellent in developability even when the concentration of the colorant is high, and which can form a cured film at a high product yield. Further, an object of the present invention is to provide a cured film formed using the curable composition and a display element including the cured film.

The inventors of the present invention conducted intensive studies and found that the above problems can be solved by using a polymer having a specific structure.

In other words, the present invention provides a curable composition comprising (A) a polymer having a group represented by the following formula (1), a substituted or unsubstituted alicyclic hydrocarbon group, and a polymerizable unsaturated group. And (B) a solvent.

In the formula (1), R ¹ represents an alkanediyl group having 2 to 4 carbon atoms, R ² represents an aliphatic hydrocarbon group, n represents an integer of 1 to 100, and * represents a bonding site (bonding hand); When n is 2 or more, a plurality of R ¹ may be the same or different.

Further, the present invention provides a cured film formed using the above curable composition, and a display element comprising the cured film. Further, a dry film formed using the above curable composition is provided. Here, the "cured film" means a display element, a pixel of each color used in the solid-state image sensor, a protective film, a black matrix, a spacer, an insulating film, and the like.

When the curable composition of the present invention is used, the developability is excellent even when the concentration of the colorant is high, and it is possible to form a high product yield. Into a color filter. However, it is surprisingly confirmed that the pixel pattern formed by using the curable composition of the present invention does not cause speckle-like color unevenness (hereinafter referred to as "water spot"). If water spots are generated during the manufacture of the color filter, there is a problem that the inspection process which is performed after the development process and the end of the water washing process is hindered, and the production efficiency is lowered. However, if the curable composition of the present invention is used, the pixel pattern is used. Water spots are not generated on the top, so this problem can be eliminated.

Therefore, the curable composition of the present invention can be variously represented by a color liquid crystal display element, a color separation color filter for a solid-state image sensor, a color filter for an organic EL display element, and a color filter for an electronic paper. Very useful in the manufacture of color filters. In addition, it is extremely useful as a protective film material, a spacer material, and an insulating film material.

Hereinafter, the present invention will be described in detail.

[Sclerosing composition]

Hereinafter, the constituent components of the curable composition of the present invention will be described in detail.

The curable composition of the present invention contains the component (A) and the component (B). Hereinafter, the constituent components of the curable composition of the present invention will be described in detail.

- (A) polymer -

The curable composition of the present invention contains a group having a group represented by the following formula (1), a substituted or unsubstituted alicyclic hydrocarbon group, and a polymerizable unsaturated group (hereinafter, also referred to as "specific polymer" "). The specific polymer of the present invention is a component which undergoes a crosslinking reaction during exposure and post-baking processes to harden the coating film. The curable composition of the present invention is excellent in developability by containing a specific polymer, and can form a color filter with a high product yield. Further, it is surprising that the curable composition of the present invention is also produced in a pixel. There is no effect of water spots on the pattern.

In the formula (1), R ¹ represents an alkanediyl group having 2 to 4 carbon atoms, R ² represents an aliphatic hydrocarbon group, n represents an integer of 1 to 100, and * represents a bonding site. Wherein, n-2 or more, a plurality of R ¹ may be the same or different].

As the alkanediyl group having 2 to 4 carbon atoms in R ¹ , an ethyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group can be exemplified. , propane-1,3-diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl, etc. Among them, an alkanediyl group having 2 to 3 carbon atoms is preferred, and an ethyl group, a propane-1,2-diyl group, and a propane-1,3-diyl group are more preferred.

The aliphatic hydrocarbon group in R ² is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and more specifically, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms; An alkynyl group having 2 to 20 carbon atoms. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, and a third group. Butyl, pentyl, isopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl, dodecyl and the like. Further, the alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms, and specific examples thereof include a vinyl group, a 1-propenyl group, a 1-butenyl group, a 1,3-butadienyl group, and 1 Pentenyl, 2-pentenyl, 1-hexenyl, 2-ethyl-2-butenyl, 2-octenyl, (4-vinyl)-5-hexenyl, 2-decene Base. The alkynyl group is preferably an alkynyl group having 2 to 12 carbon atoms, and specific examples thereof include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a 1-pentynyl group, and a 3-pentynyl group. 1-hexynyl, 2-ethyl-2-butynyl, 2-octynyl, (4-ethynyl)-5-hexynyl, 2-decynyl, and the like.

Among them, an alkyl group having 1 to 20 carbon atoms is preferred, and a linear or branched alkyl group having 1 to 12 carbon atoms is preferred. When the alkyl group is a linear alkyl group, a linear alkyl group having 1 to 6 carbon atoms is preferred, and a methyl group is more preferred. When the alkyl group is a branched alkyl group, it is preferably a branched alkyl group having 3 to 10 carbon atoms, more preferably 2-ethylhexyl group.

n represents an integer of 1 to 100, preferably an integer of 1 to 30, more preferably an integer of 1 to 15, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5. When n is 2 or more, a plurality of R ^{1 's} may be the same or different, and a plurality of R ¹ O groups may be bonded in an arbitrary order. As examples in which a plurality of R ^{1 are} different, for example, a combination of an alkanediyl group having 2 carbon atoms and an alkanediyl group having 3 carbon atoms, an alkanediyl group having 2 carbon atoms, and 3 carbon atoms can be exemplified. A combination of an alkanediyl group and an alkanediyl group having 4 carbon atoms. Among them, a combination of an ethyl group and a propane-1,2-diyl group, a combination of an ethyl group and a propane-1,3-diyl group, and an ethyl group, a propane-1,2-diyl group and a butane group are preferred. a combination of -1,4-diyl groups, a combination of ethyl, propane-1,3-diyl, butane-1,4-diyl.

The specific polymer of the present invention preferably has a group represented by the formula (1) in the side chain, and specifically, preferably has a repeating unit represented by the following formula (2).

[In the formula (2), Z ¹ represents -O-, -CO-, -C(=O)O-(* ¹ ), -CONH-(* ¹ ) (where "* ¹ " is a bond with R ¹ a bonding site) or a phenyl group, R ³ represents a hydrogen atom or a methyl group, and R ¹ , R ² and n have the same meanings as R ¹ , R ² and n in the formula (1).

As Z ¹ in the formula (2), preferably -C(=O)O-(* ¹ ), -CONH-(* ¹ ) (where "* ¹ " is a bonding site bonded to R ¹ ) Point), more preferably -C(=O)O-(* ¹ ).

The content of the repeating unit represented by the formula (2) in the specific polymer of the present invention is usually from 0.1 to 80% by mass, preferably from 1 to 50% by mass, more preferably from 5 to 40% by mass, based on the total of the repeating units. More preferably, it is 7 to 30% by mass, and particularly preferably 10 to 25% by mass. Such a method is preferable because it is easy to obtain the desired effect of the present invention.

The alicyclic hydrocarbon group which the specific polymer of the present invention has is preferably an alicyclic hydrocarbon group having 4 to 30 carbon atoms, more preferably an alicyclic hydrocarbon group having 4 to 18 carbon atoms, more preferably a carbon atom. A 4 to 12 alicyclic hydrocarbon group. The alicyclic hydrocarbon group includes a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridged cyclic hydrocarbon group, a spirohydrocarbyl group, a cyclic anthracene hydrocarbon group and the like.

As the alicyclic hydrocarbon group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a t-butylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group, a decahydro-2-naphthyl group can be illustrated. , tricyclo [5.2.1.0 ^2,6] decan-8-yl, pentadecyl rings, isobornyl, adamantyl, dicyclopentanyl, dicyclopentenyl, tris cyclopentyl , tricyclopentenyl and the like.

These alicyclic hydrocarbon groups may further have an alkyl group, a halogen atom, a carboxyl group, a carbonyl group or the like as a substituent. The alkyl group may, for example, be the same as the above, and is preferably an alkyl group having 1 to 4 carbon atoms. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Among these alicyclic hydrocarbon groups, preferred are a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridged cyclic hydrocarbon group, more preferably a cyclohexyl group, a cyclohexenyl group, an adamantyl group, a dicyclopentyl group or a bicyclic ring. Pentenyl, tricyclopentyl, tricyclopentenyl, these groups may or may not be substituted.

The specific polymer of the present invention preferably has an alicyclic hydrocarbon group in the side chain, and specifically, preferably has a repeating unit represented by the following formula (3).

[Formula (3), Z ² represents -O -, - CO -, - C (= O) O - (* 2), - CONH - (* 2) ( wherein, "* ^2" is a bond and R ⁴ a bonding site), or a group selected from the group consisting of -O-, -CO-, -C(=O)O-, and -CONH-, in combination with an alkanediyl group, R ⁴ Represents a substituted or unsubstituted alicyclic hydrocarbon group, and R ⁵ represents a hydrogen atom or a methyl group].

The alkanediyl group in Z ² may, for example, be the same group as described above, preferably an alkanediyl group having 2 to 3 carbon atoms, more preferably an ethylidene group or a propane-1,2-diyl group. Propane-1,3-diyl.

Wherein Z ^{2 is} preferably -C(=O)O-(* ² ), -CONH-(* ² ) (wherein "* ² " is a bonding site bonded to R ⁴ ) or -C (=O) a group of O- combined with an alkanediyl group, more preferably -C(=O)O-(* ² ) or -C(=O)O- combined with an alkanediyl group Group.

Further, as the alicyclic hydrocarbon group in R ⁴ , the same groups as described above can be exemplified, and preferred embodiments are also as described above.

The content of the repeating unit represented by the formula (3) in the specific polymer of the present invention is usually 0.1 to 60% by mass, preferably 1 to 50% by mass, more preferably 5 to 35% by mass in all the repeating units. More preferably, it is 7 to 25% by mass. Such a form is preferable because it is easy to obtain the desired effect of the present invention.

The polymerizable unsaturated group which the specific polymer of the present invention has may, for example, be a vinyl group, a (meth)acryl fluorenyl group, an allyl group or the like. Among them, a (meth) acrylonitrile group is preferred. Further, the specific polymer preferably has a polymerizable unsaturated group in the side chain.

The iodine value of the specific polymer of the present invention is preferably from 5 to 100 g/100 g, more preferably from 10 to 80 g/100 g, still more preferably from 20 to 70 g/100 g, and particularly preferably from 30 to 60 g/100 g. Here, the "iodine value" in the present invention means a value measured by a method described later.

The specific polymer of the present invention is not particularly limited as long as it is a group having a group represented by the formula (1), a substituted or unsubstituted alicyclic hydrocarbon group, and a polymerizable unsaturated group, and more preferably has a carboxyl group or a phenolic property. A polymer having an acidic functional group such as a hydroxyl group. With such a form, alkali developability can be imparted to the specific polymer of the present invention. The acidic functional group is preferably a carboxyl group. When the specific polymer is a polymer having an acidic functional group, the acid value thereof is preferably from 1 to 200 mgKOH/g, more preferably from 30 to 170 mgKOH/g, still more preferably from 60 to 150 mgKOH/g, particularly preferably 80~100mgKOH/g. Here, the "acid value" in the present invention means the number of mg of KOH required to neutralize 1 g of the nonvolatile component other than the solvent of the specific polymer solution.

In the present invention, as the specific polymer, for example, at least one selected from the group consisting of the following polymers can be used.

(A-1) A polymerizable unsaturated compound containing (a1) a group represented by the formula (1), (a6) a polymerizable unsaturated compound having a substituted or unsubstituted alicyclic hydrocarbon group, and (a2) a polymer obtained by reacting a copolymer of a monomer having a hydroxyl group polymerizable unsaturated compound (hereinafter referred to as "precursor copolymer (1)") with (a3) an unsaturated isocyanate compound (hereinafter, The term "polymer (A-1)"), (A-2) is a polymerizable unsaturated compound containing (a1) a group represented by the formula (1), (a6) having a substituted or unsubstituted fat. a copolymer of a cyclic hydrocarbon group-containing polymerizable unsaturated compound and (a4) an unsaturated carboxylic acid monomer (hereinafter sometimes referred to as "precursor copolymer (2)") and (a5) have an epoxy group B A polymer obtained by reacting a polymerizable unsaturated compound (hereinafter sometimes referred to as "polymer (A-2)"), and (A-3) containing (a1) a group represented by formula (1) a polymerizable unsaturated compound of the group, (a6) a polymerizable unsaturated compound having a substituted or unsubstituted alicyclic hydrocarbon group, and (a5) a polymerizable unsaturated compound having an epoxy group. a polymer obtained by reacting a copolymer (hereinafter sometimes referred to as "precursor (3)") with (a4) an unsaturated carboxylic acid (hereinafter, sometimes referred to as "polymer (A-3)" ").

In the following, (a1) a polymerizable unsaturated compound having a group represented by the formula (1), and (a2) a polymerizable unsaturated group having a hydroxyl group. a polymerizable property of a compound, (a3) unsaturated isocyanate compound, (a4) unsaturated carboxylic acid, (a5) a polymerizable unsaturated compound having an epoxy group, and (a6) a substituted or unsubstituted alicyclic hydrocarbon group The saturated compound is referred to as "compound (a1)", "compound (a2)", "compound (a3)", "compound (a4)", "compound (a5)", and "compound (a6)". In the following, the polymerizable unsaturated compound other than the above compounds (a1) to (a6) may be referred to as "compound (a7)".

As the compound (a1), for example, a compound represented by the following formula (4) can be exemplified.

[In the formula (4), R ^1, R ² and n of formula ⁽¹⁾ R 1, R ² and n have the same meanings, R ³ of the formula R (2) ³ is the same meaning. ]

The compound represented by the formula (4), more specifically, EO-modified 2-ethylhexyl acrylate (n≒2, trade name: ARONIX M-120), or the like, manufactured by Toagosei Co., Ltd. ; butoxydiethylene glycol methacrylate (n≒2, trade name: LIGHT ESTER BC), methoxy polyethylene glycol methacrylate (n≒9, trade name: LIGHT ESTER 130MA), A Oxypolyethylene glycol methacrylate (n≒30, trade name: LIGHT ESTER 041MA), ethoxy-diethylene glycol acrylate (n=2, trade name: LIGHT ACRYLATE EC-A), methoxy Base-triethylene glycol acrylate (n=3, trade name: LIGHT ACRYLATE MTG-A), methoxy-polyethylene glycol acrylate (n=9, trade name: LIGHT ACRYLATE 130A), dipropylene glycol monomethyl Ether methacrylate (n=2), above, manufactured by Kyoeisha Chemical Co., Ltd.; methoxy polyethylene glycol monoacrylate (n≒9, trade name: BLEMMER AME-400), lauryloxy polymerization Ethylene glycol monoacrylate (n≒4, trade name: BLEMMER ALE-200), methoxy polyethylene glycol methacrylate (n≒2, trade name: BLEMMER PME-100), methoxy polyethylene two Methacrylate (n≒4, trade name: BLEMMER PME-200), methoxy polyethylene glycol methacrylate (n≒9, trade name: BLEMMER PME-400), methoxypolyethylene glycol Methacrylate (n≒23, trade name: BLEMMER PME-1000), methoxy polyethylene glycol methacrylate (n≒90, trade name: BLEMMER PME-4000), octyloxy polyethylene glycol Polypropylene glycol monomethacrylate (R ² is a combination of exoethyl (n≒8) and 1,3-propanediyl (n≒6), trade name: BLEMMER 50POEP-800B), above, Japanese oil and fat shares limited Company system; methoxy polyethylene glycol acrylate (n≒9, trade name: NK ESTER AM-90G), methoxy polyethylene glycol acrylate (n≒13, trade name: NK ESTER AM-130G) , methoxy polyethylene glycol methacrylate (n≒2, trade name: NK ESTER M-20G), methoxy polyethylene glycol methacrylate (n≒4, trade name: NK ESTER M- 40G), methoxy polyethylene glycol methacrylate (n≒9, trade name: NK ESTER M-90G), methoxy polyethylene glycol methacrylate (n≒23, trade name: NK ESTER M-230G), above, Xinzhongcun Chemical Industry Co., Ltd. System and so on. Further, "n" in the paragraphs [0038] to [0041] represents the average degree of polymerization.

In the compound (a1), a polyethylene glycol (meth) acrylate having a linear alkyl group having 1 to 6 carbon atoms at the terminal and a polyethylene glycol having a branched alkyl group having 3 to 10 carbon atoms at the terminal. The (meth) acrylate is preferably a compound having a desired effect, and particularly preferably a compound of the above formula (4), wherein R ¹ is an exoethyl group, R ² is a methyl group, and n=4; R ¹ is a compound in which an ethyl group is extended, R ² is a methyl group, and n = 9; and R ¹ is a compound in which an ethyl group is extended, R ² is a 2-ethylhexyl group, and n = 2. Incidentally, R ³ may be a hydrogen atom or a methyl group.

The compound (a1) may be used singly or in combination of two or more.

Further, as the compound (a2), for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, or (meth)acrylic acid can be exemplified. 2-hydroxybutyl ester, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 7-hydroxyheptyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 9-hydroxydecyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 11-hydroxyundecyl (meth)acrylate, (methyl) a hydroxyalkyl (meth) acrylate such as 12-hydroxydodecyl acrylate; 2-(6-hydroxyhexyloxy)ethyl (meth) acrylate or 3-(meth) acrylate 6-hydroxyhexyloxy)propyl ester, 4-(6-hydroxyhexyloxy)butyl (meth)acrylate, 5-(6-hydroxyhexyloxy)pentyl (meth)acrylate, ( (6-hydroxyhexyloxy)alkyl (meth)acrylate such as 6-(6-hydroxyhexyloxy)hexyl methacrylate; polyethylene glycol mono(meth) acrylate, a polyalkylene glycol mono(meth)acrylate such as polypropylene glycol mono(meth)acrylate; 4-hydroxyphenyl (meth) acrylate, N-p-hydroxyphenyl maleimide, p-hydroxy-α-methyl styrene, 5-hydroxymethyl decene, 5-hydroxy decene, and the like.

A commercially available product of a mixture of (6-hydroxyhexyloxy)alkyl methacrylate and 2-hydroxyethyl methacrylate is represented by a trade name, and examples thereof include PLACCEL FM1D and FM2D (manufactured by Daicel Chemical Industries). .

Further, 2-(3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-ethyl (meth)acrylate and 3-(3-hydroxy-2,2 (meth)acrylate are exemplified. -Dimethyl-propoxycarbonyloxy)-propyl ester, 4-(3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-butyl (meth)acrylate, (methyl ) 5-(3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-pentyl acrylate, 6-(3-hydroxy-2,2-dimethyl-propoxy)(meth)acrylate (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-alkyl (meth)acrylate, etc., such as carbonylcarbonyl)-hexyl ester.

A commercial product of a mixture of (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-alkyl (meth)acrylate and 2-hydroxyethyl methacrylate, represented by a trade name For example, HEMAC1 (manufactured by Daicel Chemical Industries) or the like can be exemplified.

Further, 4-hydroxy-cyclohexyl (meth)acrylate, 4-hydroxymethyl-cyclohexylmethyl (meth)acrylate, 4-hydroxyethyl-cyclohexylethyl (meth)acrylate, ( 3-hydroxy-bicyclo[2.2.1]hept-5-en-2-yl methacrylate, 3-hydroxymethyl-bicyclo[2.2.1]hept-5-ene-2-(meth)acrylate Methyl ester, 3-hydroxyethyl-bicyclo[2.2.1]hept-5-en-2-ylethyl (meth)acrylate, 8-hydroxy-bicyclo(methyl)acrylate [2.2.1]hept-5-en-2-yl ester, 2-hydroxy-octahydro-4,7-methyl bridge-indol-5-yl (meth)acrylate, 2-hydroxyl (meth)acrylate Methyl-octahydro-4,7-methyl bridge-indol-5-yl methyl ester, 2-hydroxyethyl-octahydro-4,7-methyl bridge-indol-5-ylethyl (meth)acrylate, 3-hydroxy-adamantan-1-yl (meth)acrylate, 3-hydroxymethyl-adamantan-1-yl (meth)acrylate, 3-hydroxyethyl-adamantane (meth)acrylate A hydroxyalkyl (meth)acrylate having an alicyclic structure such as -1-ethylethyl ester; 1,2-dihydroxyethyl (meth)acrylate; 2,3-dihydroxy (meth)acrylate Propyl ester, 1,3-dihydroxypropyl (meth)acrylate, 3,4-dihydroxybutyl (meth)acrylate, 3-[3-(2,3-dihydroxypropoxy)(meth)acrylate A polyhydroxyalkyl (meth)acrylate such as 2-hydroxypropoxy]-2-hydroxypropyl ester.

In particular, the compound (a2) used for the synthesis of the precursor copolymer (1) is preferably 2-hydroxyethyl (meth)acrylate from the viewpoint of copolymerization reactivity and reactivity of the compound (a3). 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-(6-hydroxyhexyloxy)ethyl (meth)acrylate, 2-(3) (meth)acrylate -hydroxy-2,2-dimethyl-propoxycarbonyloxy)-ethyl ester, 4-hydroxymethyl-cyclohexylmethyl (meth)acrylate, 3-hydroxymethyl-methyl methacrylate Alkyl-1-ylmethyl ester, 2,3-dihydroxypropyl (meth)acrylate, and the like.

The compound (a2) may be used singly or in combination of two or more.

The above compound (a3) is a compound having an ethylenically unsaturated bond and an isocyanate group, and specific examples thereof include, for example, 2-(meth)acryloxyphenyl isocyanate and 2-(p-vinylphenyl). Propane-2-yl isocyanate, 2-(methyl) propylene oxiranyl ethyl isocyanate, 3-(A Acryloxypropyl isocyanate, 4-(methyl)propenyloxybutyl isocyanate, 6-(methyl)propenyloxyhexyl isocyanate, 8-(methyl)propenyloxyoctyl isocyanate , 10-(meth) propylene decyl decyl isocyanate, 1,1-[bis(methyl) propylene methoxymethyl]ethyl isocyanate, 1,1,1-[tri(meth) propylene oxime Oxymethylmethyl]methyl isocyanate, 2-(2-isocyanate ethoxy)ethyl (meth)acrylate, 2-[2-(2-isocyanate ethoxy)ethoxy](meth)acrylate Ester, 2-[2-[2-(2-isocyanate ethoxy)ethoxy]ethoxy]ethyl (meth)acrylate, 2-(2-isocyanatepropoxy)(meth)acrylate Ester, 2-[2-(2-isocyanatepropoxy)propoxy]ethyl (meth)acrylate, and the like.

In the above-mentioned compound (a3), a commercially available product of 2-propenyloxyethyl isocyanate is represented by a brand name, and Karenz AOI (manufactured by Showa Denko Co., Ltd.) can be exemplified as 2-methylpropenyloxy group. Commercially available product of ethyl isocyanate, which is a commercial name of Karenz MOI (manufactured by Showa Denko Co., Ltd.), and 2-(2-isocyanate ethoxy)ethyl methacrylate, by trade name For example, Karenz MOI-EG (manufactured by Showa Denko Co., Ltd.), which is a commercial product of 1,1-(bisacryloxymethyl)ethyl isocyanate, which is represented by a trade name, can be exemplified by Karenz BEI (Showa Electric Co., Ltd.).

Among these compounds (a3), from the viewpoint of reactivity with the compound (a2), 2-(meth)acryloxyethyl isocyanate and 4-(meth)acryloxybutyl isocyanate are preferred. (Methyl) 2-(2-isocyanate ethoxy)ethyl methacrylate, 1,1-[bis(meth)acryloxymethyl]ethyl isocyanate.

The compound (a3) may be used singly or in combination of two or more.

Further, as the compound (a4), for example, an unsaturated monocarboxylic acid such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid or cinnamic acid; maleic acid, maleic anhydride, fumaric acid, and clothing can be exemplified; Unsaturated dicarboxylic acid or anhydride thereof such as citric acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid; mono[2-(methyl)acryloxyethyl) succinate, adjacent Mono[(methyl)acryloxyalkylene] ester of a divalent or higher polycarboxylic acid such as mono-2-[methyl)propenyloxyethyl]ester; ω-carboxypoly A mono(meth)acrylate or the like of a polymer having a carboxyl group and a hydroxyl group at both terminals, such as a lactone mono(meth)acrylate.

When these compounds (a4) are used in the synthesis of the precursor copolymer (2), (meth)acrylic acid, succinic acid mono [2-(methyl) propylene is preferred from the viewpoint of copolymerization reactivity and ease of availability. Oxyloxyethyl]ester, ω-carboxypolycaprolactone mono(meth)acrylate.

On the other hand, when the compound (a4) is used for the reaction with the precursor copolymer (3) to synthesize the polymer (A-3), it is preferred from the viewpoints of reactivity with the compound (a5), ease of availability, and the like. It is (meth)acrylic acid.

The compound (a4) may be used singly or in combination of two or more.

Further, as the compound (a5), for example, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, ( 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, (methyl) )Acrylic 2-shrinkage (meth) acrylate having an epoxy group such as glyceryl ethoxyethyl ester, 3-glycidoxypropyl (meth) acrylate or 4-glycidoxybutyl (meth) acrylate; - glycidyl ethacrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 6,7-epoxyheptyl α-ethyl acrylate, etc. Α-alkyl acrylate; 1-vinyl-2,3-epoxycyclohexane, 1-vinyl-3,4-epoxycyclohexane, o-vinylbenzyl glycidyl ether, A vinyl compound having an epoxy group such as vinylbenzyl glycidyl ether or p-vinylbenzyl glycidyl ether.

In the compound (a5), when used for the synthesis of the precursor copolymer (3) and for the reaction with the precursor copolymer (2) to synthesize the polymer (A-2), it is preferred to have the epoxy group B. The (meth) acrylate is preferably glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, or (meth)acrylic acid 4 from the viewpoint of easily obtaining a desired effect. - glycidyloxybutyl ester or 3,4-epoxycyclohexylmethyl (meth)acrylate.

The compound (a5) may be used singly or in combination of two or more.

Further, as the compound (a6), for example, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, and 2-(methyl)propene oxime hexahydrophthalate can be exemplified. (meth) acrylate having a substituted or unsubstituted cycloalkyl group such as ethyl ethyl ester (for example, manufactured by Kyoeisha Chemical Co., Ltd.: LIGHT ESTER HO-HH); 2-ethyl (meth) acrylate -2-adamantyl ester, dicyclopentanyl (meth)acrylate (for example, manufactured by Hitachi Chemical Co., Ltd.: FANCRYL FA-513AS, or FANCRYL FA-513M), isobornyl (meth)acrylate (For example, Kyoritsu Chemical Co., Ltd.: LIGHT ESTER IB-X), dicyclopentenyl (meth)acrylate (for example, manufactured by Hitachi Chemical Co., Ltd.: FANCRYL FA-511AS), (methyl Dicyclopentenyloxyethyl acrylate (for example, manufactured by Hitachi Chemical Co., Ltd.: FANCRYL FA-512AS, or FANCRYL FA-512M), tricyclo(methyl) acrylate-[5.2.1.0 ^2,6 ] - decyl (meth) acrylate, tricyclo - [5.2.1.0 ^2,6] - decyl acrylate group or the like having a substituted or unsubstituted bridged cyclic hydrocarbon (meth) acrylate Esters and the like.

Among these compounds (a6), cyclohexyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, (A) are preferred. Isobornyl acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclo(methyl) acrylate - [5.2.1.0 ^2,6 ] - oxime ester.

The compound (a6) may be used singly or in combination of two or more.

In addition, the compound (a7) is a polymerizable unsaturated compound other than the above-mentioned compounds (a1) to (a6) copolymerizable in the precursor copolymers (1) to (3), and specific examples thereof include, for example, Malay. N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-benzylmaleimide, N- Cyclohexylmaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimine butyrate, N-amber醯imino-6-maleimide caproate, N-succinimide-3-maleimide N-position substituted maleimide such as ester, N-(acridinyl)maleimide; styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-ethylene Toluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylphenol, m-vinylphenol, p-vinylphenol, o-vinylbenzyl An aromatic vinyl compound such as a vinyl ether, m-vinylbenzyl methyl ether or p-vinylbenzyl methyl ether; a terpene such as a terpene or a 5-chlorodecene; an anthracene or a 1-methyl group. Anthraquinones such as hydrazine; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth)acrylic acid alkyl (meth)acrylate such as isobutyl (meth)acrylate, dibutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate Ester; phenyl (meth) acrylate, aryl (meth) acrylate such as benzyl (meth) acrylate; 2-phenoxyethyl (meth) acrylate, epoxy for cumenyl phenol Ethane modification (methyl) (meth) acrylate having an aromatic ring structure and an alkylene oxide structure such as an enoate; allyl (meth) acrylate; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate Vinyl carboxylate; vinyl ether; vinyl ether; unsaturated ether such as vinyl ethyl ether; (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide Base compound (Methyl) acrylamide, unsaturated decylamine such as α-chloropropene decylamine; aliphatic conjugated diene such as 1,3-butadiene, isoprene or chloroprene; a macromonomer having a mono(meth)acrylonitrile group at the end of the polymer molecular chain, such as styrene, poly(methyl) methacrylate, poly(meth) acrylate, or polyoxyalkylene Wait.

The compound (a7) may be used singly or in combination of two or more.

In the present invention, as the compound (a7), a N-position-substituted maleimide, an aromatic vinyl compound, a terpene, an alkyl (meth)acrylate, or an aryl (meth)acrylate is preferred. , (meth)acrylic acid allyl ester, (meth) acrylate having an aromatic ring structure and an alkylene oxide structure (excluding the compound (a1)), particularly preferably N-phenylmaleimide , N-cyclohexylmaleimide, styrene, α-methylstyrene, terpene, methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl ester, benzyl (meth)acrylate, allyl (meth)acrylate.

The copolymerization ratio of the compound (a1) in the precursor copolymer (1) is usually from 0.1 to 80% by mass, preferably from 1 to 50, more preferably from 5 to 40% by mass, even more preferably in all the repeating units. 7 to 30% by mass, particularly preferably 10 to 25% by mass. The copolymerization ratio of the compound (a6) in the precursor copolymer (1) is usually 0.1 to 60% by mass, preferably 1 to 50% by mass, more preferably 5 to 35% by mass, still more preferably 7 to 25% by mass. %. The copolymerization ratio of the compound (a2) in the precursor copolymer (1) is usually from 5 to 70% by mass, preferably from 10 to 50% by mass, more preferably from 15 to 40% by mass.

The copolymerization ratio of the compound (a1) in the precursor copolymer (2) is usually from 5 to 80% by mass, preferably from 1 to 50, more preferably from 5 to 40 in all the repeating units. The mass% is more preferably 7 to 30% by mass, and particularly preferably 10 to 25% by mass. The copolymerization ratio of the compound (a6) in the precursor copolymer (2) is usually from 0.1 to 60% by mass, preferably from 1 to 50% by mass, more preferably from 5 to 35% by mass, still more preferably from 7 to 25% by mass. %. The copolymerization ratio of the compound (a4) in the precursor copolymer (2) is usually from 5 to 70% by mass, preferably from 15 to 55% by mass, more preferably from 25 to 45% by mass.

The copolymerization ratio of the compound (a1) in the precursor copolymer (3) is usually from 5 to 80% by mass, preferably from 1 to 50, more preferably from 5 to 40% by mass, still more preferably from 7 to 30% by mass, More preferably, it is 10 to 25% by mass. The copolymerization ratio of the compound (a6) in the precursor copolymer (3) is usually from 0.1 to 60% by mass, preferably from 1 to 50% by mass, more preferably from 5 to 35% by mass, still more preferably from 7 to 25% by mass. %. The copolymerization ratio of the compound (a5) in the precursor copolymer (3) is usually from 5 to 80% by mass, preferably from 15 to 70% by mass, more preferably from 25 to 60% by mass.

Further, in the precursor copolymer (1), the compound (a4) may be further copolymerized to impart alkali solubility, and the compound (a2) may be further copolymerized in the precursor copolymers (2) and (3). The copolymerization ratio of the compound (a4) in the precursor copolymer (1) is preferably from 10 to 40% by mass, more preferably from 15 to 35% by mass. Further, the copolymerization ratio of the compound (a2) in the precursor copolymers (2) and (3) is preferably from 1 to 20% by mass, and more preferably from 3 to 15% by mass.

When the copolymerization ratio of the compounds (a1) to (a6) is set to the above range in the synthesis of the precursor copolymers (1) to (3), the polymers (A-1) to (A-3) can be used. When it is not gelled, it is synthesized at a desired conversion ratio, and it is preferable to contain a desired curable effect of the curable composition of the obtained polymers (A-1) to (A-3). .

The reaction of the hydroxyl group of the precursor copolymer (1) in the synthesis of the polymer (A-1) with the compound (a3) can be carried out in a solution containing the precursor copolymer (1), as needed in the catalyst and A method in which the compound (a3) is added and reacted in the presence of a polymerization inhibitor is carried out. As the solution containing the precursor copolymer (1), the polymer solution in the case of synthesizing the precursor copolymer (1) can be used as it is, or the precursor copolymer (1) can be temporarily separated from the polymer solution and dissolved in the solvent. in.

The amount of the compound (a3) to be used is preferably from 30 to 100 mol%, more preferably from 45 to 100 mol%, based on the total amount of the hydroxyl groups of the precursor copolymer (1). In such a manner, the storage stability of the polymer solution and the curable composition is improved, and the desired effect can be easily obtained.

The reaction of the carboxyl group possessed by the precursor copolymer (2) in the synthesis of the polymer (A-2) with the compound (a5) can be carried out by using the precursor copolymer (2) in place of the precursor copolymer (1), Further, the compound (a5) was used instead of the compound (b3), and the synthesis of the above polymer (A-1) was carried out. The amount of the compound (a5) to be used is preferably from 30 to 100 mol%, more preferably from 50 to 100 mol%, based on the total of the carboxyl groups of the precursor copolymer (2). As the catalyst, for example, tetrabutylammonium bromide, triethylamine or the like can be used.

When the polymer (A-2) is synthesized, the amount of the compound (a5) to be used may be adjusted so that the unreacted carboxyl group remains, thereby imparting alkali solubility to the polymer (A-2).

The reaction of the epoxy group having the precursor copolymer (3) in the synthesis of the polymer (A-3) with the compound (a4) can be carried out by using the precursor copolymer (3) in place of the precursor copolymer (1). ), additionally using compound (a4) The compound (a3) was used in addition to the synthesis of the above polymer (A-1). The amount of the compound (a4) to be used is preferably from 30 to 100 mol%, more preferably from 50 to 100 mol%, based on the total of the epoxy group of the precursor copolymer (3). As the catalyst, the same catalyst as that used in the synthesis of the polymer (A-2) can be used.

When the polymer (A-3) is synthesized, the hydroxyl group produced by the reaction of the precursor copolymer (3) and the compound (a4) may be further reacted with a polybasic acid anhydride such as a dibasic acid anhydride or a tetrabasic acid dianhydride, thereby A carboxyl group is introduced into the polymer (A-3) to impart alkali solubility.

As such a polybasic acid anhydride, for example, maleic anhydride, fumaric anhydride, citraconic anhydride, mesaconic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and hexahydrogen can be exemplified. An anhydride of a dibasic acid such as phthalic anhydride, methylhexahydrophthalic anhydride, norbornene dianhydride, phthalic anhydride or naphthalene-2,3-dicarboxylic anhydride; cyclohexane-1, a monobasic acid of a polybasic acid such as a tribasic acid such as 2,4-tricarboxylic anhydride or trimellitic anhydride; a cyclobutane tetracarboxylic dianhydride, a cyclopentane tetracarboxylic dianhydride, a cyclohexane tetracarboxylic dianhydride, and a norbornene; Alkene carboxylic acid dianhydride, pyromellitic dianhydride, biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, naphthalene-1, 4, 5, a dianhydride or the like of a polybasic acid having a tetrabasic acid or the like such as 8-tetracarboxylic dianhydride or indole-3,4,9,10-tetracarboxylic dianhydride.

The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography (GPC, eluent: tetrahydrofuran) of the specific polymer is preferably from 3,000 to 50,000, more preferably from 5,000 to 30,000.

Further, the ratio (Mw/Mn) of the Mw of the specific polymer to the polystyrene-equivalent number average molecular weight (hereinafter referred to as "Mn") measured by gel permeation chromatography (GPC, eluent: tetrahydrofuran) is preferred. It is 1~5, more preferably 1~4. By setting Mw within the above range, it is easy to suppress occurrence of scum and film residue on the unexposed portion of the substrate or the light shielding layer.

In the present invention, the specific polymers may be used singly or in combination of two or more.

In the present invention, the content of the specific polymer is usually 5 to 800 parts by weight, preferably 10 parts by weight based on 100 parts by weight of the (C) coloring agent, in the coloring curable composition containing the coloring agent (C) to be described later. ~500 parts by weight. By adopting such a form, it is easy to achieve a desired color density when a film is formed. In addition, when the curable composition which does not contain the (C) coloring agent mentioned later is comprised, the content ratio of the specific polymer is 5 to 70 mass %, and is preferably 5 to 60 mass % in the solid content of the curable composition. Here, the "solid content" in the present specification means a component other than the solvent (B).

- (B) Solvent -

The curable composition of the present invention is prepared in the form of a liquid composition in combination with (B) a solvent.

The above-mentioned solvent can be appropriately selected and used as long as it disperses or dissolves the component (A) and other components constituting the curable composition, does not react with these components, and has moderate volatility.

As such a solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol can be exemplified. Monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl Ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol Mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. (poly) alkyl glycol monoalkyl ether; methyl lactate, ethyl lactate and other alkyl lactate; methanol, ethanol, propanol Butanol, isopropanol, isobutanol, tert-butanol, octanol, 2-ethylhexanol, cyclohexanol, etc. (cyclo)alkyl alcohols; ketone alcohols such as diacetone alcohol; ethylene glycol Monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Ester, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, etc. (poly)alkylene glycol monoalkyl ether Acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone Ketones such as 3-heptanone; diacetate such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate; methyl 3-methoxypropionate , 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl Alkoxycarboxylates such as propionate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate Ester, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, C Other esters such as methyl ketone, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutanoate, etc.; aromatic hydrocarbons such as toluene and xylene Examples; N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and the like decylamine or indoleamine.

Among these solvents, from the viewpoints of solubility, pigment dispersibility, coatability, and the like, (poly)alkylene glycol monoalkyl ethers, alkyl lactates, and (poly)alkylene glycols are preferred. Alkyl ether acetates, other ethers, ketones, diacetates, alkoxycarboxylates, other esters, particularly preferably propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether Acid ester, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone , 2-heptanone, 3-heptanone, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, isobutyl acetate, n-amyl formate , isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate and the like.

In the present invention, the solvent may be used singly or in combination of two or more. When used in combination, it is preferably a combination of (poly)alkylene glycol monoalkyl ethers and (poly)alkylene glycol monoalkyl ether acetates, (poly)alkylene glycol monoalkyl A combination of ether acetates and alkoxycarboxylates.

The content of the solvent is not particularly limited, and the total concentration of each component other than the solvent of the curable composition is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass. By becoming such a form, In the case of preparing a coloring curable composition containing a coloring agent (C) to be described later, a coloring curable composition having good dispersibility and stability can be obtained.

-(C) colorant -

The curable composition of the present invention may further contain (C) a colorant. Thereby, for example, it can be a color-curable composition for forming a coloring layer of a color filter. Here, the "colored layer" refers to each color pixel, black matrix, or the like used in the color filter. The coloring agent can be used without particular limitation as long as it has coloring properties, and the color and material can be appropriately selected depending on the use of the curable composition. When the curable composition of the present invention is used in the formation of the coloring layer of the color filter, since the color filter requires high color purity, brightness, contrast, and the like, it is preferably at least 1 selected from the group consisting of a pigment and a dye. As a coloring agent.

As the above pigment, an organic pigment or an inorganic pigment may be used as a preferred specific example of the organic pigment, and is represented by a color index (CI) name, and examples thereof include CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, and CI. Pigment Red 242, CI Pigment Red 254, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Blue 15:6, CI Pigment Blue 80, CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139 , CI Pigment Yellow 150, CI Pigment Yellow 180, CI Pigment Yellow 211, CI Pigment Orange 38, CI Pigment Violet 23, and the like. As a preferable specific example of an inorganic pigment, carbon black, titanium black, etc. are illustrated.

The pigment is preferably a lake pigment. Specifically, an isomeric acid, a heteropoly acid, a triarylmethane dye, and a lake color dye can be exemplified. A lake pigment. A triarylmethane-based lake pigment is disclosed in, for example, Japanese Laid-Open Patent Publication No. 2011-186043. The xanthene lake pigment is disclosed, for example, in JP-A-2010-191304.

Further, as the dye, a xanthene dye, a triarylmethane dye, a cyanine dye, an anthraquinone dye, an azo dye, or the like is preferable. More specifically, JP-A-2010-32999, JP-A-2010-254964, JP-A-2011-138094, International Publication No. 10/123071, and JP-A-2011-116803 An organic dye described in, for example, JP-A-2011-174987, JP-A-2011-174987, and the like.

In the present invention, each of the pigment and the dye may be used singly or in combination of two or more.

In the present invention, the pigment can be used by recrystallization, reprecipitation, solvent cleaning, sublimation, vacuum heating or a combination thereof. Further, the pigment can be used by modifying the surface of the particles with a resin as required. Further, the organic pigment can be used by refining the primary particles by so-called salt polishing. As a method of salt polishing, for example, the method disclosed in Japanese Laid-Open Patent Publication No. Hei 08-179111 can be employed.

When a pigment is used as the colorant in the present invention, a dispersant or a dispersing aid may be used together as desired. As the dispersing agent, for example, a suitable dispersing agent such as a cationic type, an anionic type or a nonionic type can be used, and a polymer dispersing agent is preferable. Specifically, an acrylic copolymer, a polyurethane, a polyester, a polyethyleneimine, a polyallylamine, etc. can be illustrated.

Such a dispersing agent can be obtained commercially, for example, as an acrylic dispersing agent, for example, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK), etc. A urethane-based dispersing agent, for example, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, BYK), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.) As a polyethyleneimine-based dispersing agent, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.) or the like can be exemplified, and as the polyester-based dispersing agent, AJISPERPB821, AJISPER PB822, AJISPER PB880, and AJISPER PB881 (above Ajinomoto Fine-) can be exemplified. Techno Co., Ltd.).

Further, specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and a sulfonic acid derivative of quinacridone.

The content of the coloring agent (C) is usually from 5 to 70% by mass, preferably 5, based on the solid content of the curable composition, from the viewpoint of forming a pixel having high luminance, excellent color purity, or a black matrix having excellent light-shielding properties. ~60% by mass. In addition, the curable composition of the present invention has an effect of being excellent in developability even when the concentration of the colorant is high, and it is possible to form a color filter with a high product yield. For example, the colorant concentration can be made 30% by mass. The above is further 35 mass% or more, and particularly 40 mass% or more.

- (D) polymerizable compound -

The curable composition of the present invention may further contain (D) a polymerizable compound (wherein the component (A) is not included). This way It is preferable because the curability of the curable composition of the present invention can be improved.

The polymerizable compound in the present invention means a compound having two or more polymerizable groups (excluding the above component (A)). As the polymerizable group, for example, an ethylenically unsaturated group, an epoxyethyl group, an oxetanyl group, an N-alkoxymethylamino group or the like can be exemplified. In the present invention, the polymerizable compound is preferably a compound having two or more (meth)acryl fluorenyl groups or a compound having two or more N-alkoxymethylamino groups.

Specific examples of the compound having two or more (meth)acryl fluorenyl groups include polyfunctional (meth) acrylate and caprolactone modified by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid. Polyfunctional (meth) acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, polyfunctional polyurethane obtained by reacting a hydroxyl group-containing (meth) acrylate with a polyfunctional isocyanate A polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate, a (meth) acrylate having a hydroxyl group, and an acid anhydride.

Here, as the aliphatic polyhydroxy compound, for example, a 2-membered aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol, or polypropylene glycol; glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol can be exemplified; A trivalent or higher aliphatic polyhydroxy compound. As the (meth) acrylate having a hydroxyl group, for example, 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, or the like can be exemplified. Pentaerythritol penta (meth) acrylate, glyceryl dimethacrylate, and the like. As the above polyfunctional The cyanate ester may, for example, be toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate or the like. Examples of the acid anhydride include an acid anhydride of a dibasic acid such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, and pyromellitic anhydride. A tetrabasic dianhydride such as biphenyltetracarboxylic dianhydride or benzophenone tetracarboxylic dianhydride.

In addition, as the caprolactone-modified polyfunctional (meth) acrylate, for example, a compound described in paragraphs [0015] to [0018] of JP-A-11-44955 can be exemplified. As the above polyalkylene oxide-modified polyfunctional (meth) acrylate, at least one modified bisphenol A di(meth) acrylate selected from the group consisting of ethylene oxide and propylene oxide can be exemplified. At least one modified isocyanuric acid tri(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide, and at least one modified from at least one selected from the group consisting of ethylene oxide and propylene oxide Methylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate modified from at least one selected from the group consisting of ethylene oxide and propylene oxide, selected from the group consisting of ethylene oxide and epoxy At least one modified pentaerythritol tetra(meth)acrylate in propane, at least one modified dipentaerythritol penta (meth) acrylate selected from the group consisting of ethylene oxide and propylene oxide, selected from At least one modified dipentaerythritol hexa(meth)acrylate or the like of ethylene oxide and propylene oxide.

In addition, examples of the compound having two or more N-alkoxymethylamino groups include a compound having a melamine structure, a benzoguanamine structure, and a urea structure. It should be noted that the melamine structure and the benzoguanamine structure refer to three having 1 or more Ring or phenyl substituted three The chemical structure of the ring as a basic skeleton also includes the concept of melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N', N', N", N"-hexa(alkoxymethyl) melamine, N. , N, N', N'-tetrakis (alkoxymethyl) benzoguanamine, N, N, N', N'-tetrakis (alkoxymethyl) glycoluril, and the like.

Among these polymerizable compounds, a polyfunctional (meth) acrylate or a caprolactone-modified polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound having 3 or more members with (meth)acrylic acid is preferred. Ester, polyfunctional polyurethane (meth) acrylate, polyfunctional (meth) acrylate having carboxyl group, N, N, N', N', N", N"-hexa (alkoxy) Methyl) melamine, N, N, N', N'-tetrakis(alkoxymethyl)benzamide. From the viewpoints of high strength of the colored layer, excellent surface smoothness of the colored layer, and difficulty in generation of scum, film residue, etc. on the unexposed portion of the substrate and the light-shielding layer, three or more aliphatic polyhydroxy compounds and (methyl group) Among the polyfunctional (meth) acrylates obtained by the reaction of acrylic acid, particularly preferred are trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyfunctional having a carboxyl group. Among the (meth) acrylates, a compound obtained by reacting a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, dipentaerythritol pentaacrylate, and succinic anhydride is particularly preferred.

In the present invention, the (D) polymerizable compound may be used singly or in combination of two or more.

In the coloring curable composition containing the (C) coloring agent, the content of the (D) polymerizable compound in the present invention is usually 5 to 500 parts by mass based on 100 parts by mass of the (A) specific polymer. Good for 20~300 parts by mass. By becoming such a way, it is possible to obtain sufficient hardness. In addition, when the alkali developability is imparted to the curable composition of the present invention, the alkali developability is good, and scum, film residue, and the like are less likely to occur on the unexposed portion of the substrate or on the light shielding layer. In addition, when the curable composition containing no coloring agent (C) is contained, it is usually 10 to 1500 parts by mass, preferably 30 to 1000 parts by mass, per 100 parts by mass of the (A) specific polymer.

-(E) Photopolymerization Initiator -

The curable composition of the present invention may contain (E) a photopolymerization initiator. Thereby, it is possible to impart radiation sensitivity to the curable composition. The photopolymerization initiator used in the present invention is obtained by exposure of radiation such as visible light, ultraviolet light, far ultraviolet ray, electron beam, or X-ray to cause polymerization of the (D) component and any (D) polymerizable compound which can be arbitrarily added. The active species of the compound.

As such a photopolymerization initiator, for example, a thioxanthone compound, an acetophenone compound, a biimidazole compound, and the like can be exemplified. Compound, O-mercapto oxime compound, sulfonium salt compound, benzoin compound, benzophenone compound, α-diketone compound, polycyclic guanidine compound, diazo compound, quinone a sulfonate compound or the like.

In the present invention, the photopolymerization initiator may be used singly or in combination of two or more. The photopolymerization initiator is preferably selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, and three At least one of a compound and an O-mercapto lanthanide compound. Further, it is preferred to use two or more kinds selected from these compounds in combination.

In a preferred photopolymerization initiator of the present invention, specific examples of the thioxanthone-based compound include thioxanthone and 2-chlorothioxanthone. 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4 2-Diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like.

Further, as a specific example of the above acetophenone-based compound, 2-methyl-1-[4-(methylthio)phenyl]-2- can be exemplified Tropicpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenyl-phenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Phenidophenyl)butan-1-one and the like.

Further, as a specific example of the biimidazole-based compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole can be exemplified. 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4, 6-Trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

In the case where a biimidazole-based compound is used as the photopolymerization initiator, it is preferred to use a hydrogen donor in combination from the viewpoint of improving the sensitivity. The term "hydrogen donor" as used herein refers to a compound which provides a hydrogen atom by exposure to a radical generated by a biimidazole compound. As the hydrogen donor, for example, 2-mercaptobenzothiazole or 2-mercaptobenzophenone can be exemplified. A mercaptan such as a thiol-based hydrogen donor, an amine-based hydrogen donor such as 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone . In the present invention, the hydrogen donor may be used alone or in combination of two or more. Further, from the viewpoint of improving the sensitivity, one or more kinds of thiol-based hydrogen donors and one or more amine-based hydrogen donors are preferably used. Used in combination.

In addition, as the above three Specific examples of the compound can be exemplified by 2,4,6-tris(trichloromethyl). , 2-methyl-4,6-bis(trichloromethyl) are all three , 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-three , 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl) are all three 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-all 2-[2-(3,4-Dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl) are all three , 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-three Three with a halomethyl group a compound.

Further, as a specific example of the O-indenyl lanthanide compound, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzamide), 1- [9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethanone 1-(O-acetamidine), 1-[9-ethyl-6 -(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-ethanone 1-(O-acetamidine), 1-[9-ethyl- 6-{2-Methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene}-9H-indazol-3-yl]-ethanone 1-(O-acetamidine) and the like. As a commercial item of the O-mercapto fluorene-based compound, NCI-831, NCI-930 (above, manufactured by ADEKA CORPORATION), or the like can be used.

In the present invention, when a photopolymerization initiator other than a biimidazole-based compound such as an acetophenone-based compound is used, a sensitizer may be used in combination. As such a sensitizer, for example, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-di Ethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5- Bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethyl Amino) chalcone and the like.

In the present invention, the content of the (E) photopolymerization initiator is preferably 0.01 to 120 with respect to 100 parts by mass of the total of (A) the specific polymer and optionally the (D) polymerizable compound and (F) the binder resin. The mass fraction is particularly preferably from 1 to 100 parts by mass. By adopting such an embodiment, it is possible to sufficiently harden by exposure, and the formed pattern is less likely to fall off from the substrate during development.

-(F) Adhesive Resin -

The curable composition (F) of the present invention may contain a binder resin (excluding the above component (A)). Thereby, the alkali solubility of the curable composition, the adhesion to the substrate, the storage stability, and the like can be improved. The binder resin is not particularly limited as long as it does not correspond to the component (A), and is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as a "carboxy group-containing polymer") is preferable, and for example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer" (hereinafter, referred to as "unsaturated monomer") is exemplified. F1)") a copolymer with another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (f2)").

The same monomer as the above-mentioned compound (a4) may be used singly or in combination of two or more kinds as the unsaturated monomer (f1).

Further, as the unsaturated monomer (f2), for example, an N-position substituted maleimide such as N-phenylmaleimide or N-cyclohexylmaleimide; styrene; An aromatic vinyl compound such as α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether or decene; methyl (meth)acrylate, N-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, Polyethylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2~10) (Meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclic [5.2.1.0 ^{2, 6} ] decane-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono(meth) acrylate, 4-hydroxyphenyl (meth) acrylate, Ethylene oxide modified (meth) acrylate of alkenylphenol, (A Glycidyl acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(methyl) propylene methoxymethyl] oxetane, 3-[( (Meth) acrylate such as methyl) propylene methoxymethyl]-3-ethyloxetane; cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclic [5.2.1.0 ^{2 a} vinyl ether ^{such as 6} :decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether or 3-(vinyloxymethyl)-3-ethyloxetane; a macromonomer having a mono(meth)acrylonitrile group at the end of the polymer molecular chain, such as polystyrene, poly(methyl) methacrylate, poly(meth) butyl acrylate, or polyoxyalkylene oxide Body and so on.

These unsaturated monomers (f2) may be used singly or in combination of two or more.

Specific examples of the copolymer of the unsaturated monomer (f1) and the unsaturated monomer (f2), for example, JP-A-7-140654 Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A copolymer disclosed in JP-A-2004-101728, and the like.

In the present invention, the binder resin may be used singly or in combination of two or more kinds.

In the present invention, when the (F) binder resin is used, the content thereof is 0.01 to 100 parts by mass, preferably 0.1 to 70 parts by mass, per 100 parts by mass of the (A) specific polymer. Such a method is preferable because it is easy to obtain the desired effect of the present invention.

Further, when the total content of the (F) binder resin and the (A) specific polymer is constituting the colored curable composition containing the (C) colorant, it is usually 5 to 800 with respect to 100 parts by weight of the (C) colorant. The parts by weight are preferably 10 to 500 parts by weight. Further, when the curable composition which does not contain the (C) coloring agent is formed, the content ratio of the (F) binder resin and the (A) specific polymer is 5 to 70% by mass in the solid content of the curable composition. Good is 5~60% by mass.

-additive-

The curable composition of the present invention may contain various additives as needed.

Examples of the additive include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly(fluoroalkyl acrylate); surfactants such as fluorine-based surfactants and lanthanoid surfactants; and ethylene; Trimethoxy decane, vinyl triethoxy decane, vinyl tris (2-methoxy) Ethyloxy)decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethyl Oxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-( 3,4-Epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyl An adhesion promoter such as trimethoxydecane or 3-mercaptopropyltrimethoxydecane; 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-3rd An antioxidant such as an phenol; an ultraviolet absorber such as 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole or an alkoxybenzophenone; Anti-agglomerating agent such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5- Residue improver such as amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; succinic acid single [2-(methyl)propenyloxyethyl]ester Phthalate, mono [2- (meth) Bing Xixi oxyethyl] ester, and the like to improve the developing property, ω- carboxy-polycaprolactone mono (meth) acrylate.

When the curable composition of the present invention is used as the coloring curable composition, the colored curable composition can be produced by a suitable method, and as a preparation method thereof, for example, JP-A-2008-58642, JP-A-KOKAI The method disclosed in Japanese Laid-Open Patent Publication No. 2010-132874. In the case where both the dye and the pigment are used as the coloring agent, as disclosed in Japanese Laid-Open Patent Publication No. 2010-132874, the following method may be employed: after the dye solution is passed through the first filter, the first filter is used. The dye solution is mixed with a separately prepared pigment dispersion or the like to obtain The colored composition was prepared by a second filter. Further, a method may be employed in which the dye, the component (A), and other components used as needed are dissolved in a solvent, so that the solution obtained by the first filter is passed through the solution of the first filter. It was mixed with the separately prepared pigment dispersion so that the obtained coloring composition was prepared by the second filter. Further, a method may be employed in which the dye solution of the first filter, the component (A), and other components used as needed are mixed by the first filter. The solution was dissolved, and the solution obtained by the second filter was further mixed with the separately prepared pigment dispersion liquid by the second filter, so that the obtained colored composition was prepared by the third filter.

[Cured film and its formation method]

The cured film of the present invention is formed using the curable composition of the present invention. The cured film of the present invention is not particularly limited. For example, each color pixel, black matrix, protective film, spacer, insulating film, or the like constituting the color filter can be exemplified. Hereinafter, these will be described in detail.

As a method of forming the coloring layer constituting the color filter, the first method can be exemplified. First, on the surface of the substrate, a light shielding layer (black matrix) is formed as needed to divide a portion where the pixels are formed. Next, a liquid composition of the colored curable composition of the present invention containing, for example, a blue coloring agent is applied onto the substrate, and then prebaked to evaporate the solvent to form a coating film. Next, the coating film was exposed through a photomask, and then developed with an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Thereafter, a pixel array in which blue pixel patterns (colored cured films) are arranged in a predetermined arrangement is formed by post-baking.

Next, each colored curable composition containing a green or red coloring agent is applied, coated, prebaked, exposed, developed, and post-baked in the same manner as described above, and sequentially formed on the same substrate. A green pixel array and a red pixel array. Thereby, a color filter in which a pixel array of three primary colors of blue, green, and red is disposed on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above order.

Further, the black matrix can be formed by forming a desired pattern by a photolithography method using a metal thin film of chromium or the like which is formed by sputtering or vapor deposition, and a curable composition in which a black coloring agent is dispersed can be used and formed. The above pixels are formed in the same manner. The curable composition of the present invention can be preferably used in the formation of the above black matrix.

Examples of the substrate used in forming the coloring layer include glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide, polyimine, and the like.

Further, for these substrates, an appropriate pretreatment such as drug treatment, plasma treatment, ion plating, sputtering, gas phase reaction method, or vacuum vapor deposition using a decane coupling agent or the like can be performed in advance.

When the curable composition is applied to a substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a bar coating method may be employed, and it is particularly preferable to use spin coating. Method, slit die coating method.

Prebaking is usually carried out by combining vacuum drying and heat drying. Drying under reduced pressure is usually carried out until it reaches 50 to 200 Pa. In addition, the conditions of heat drying are usually about 1 to 10 minutes at 70 to 110 °C.

The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, in terms of the film thickness after drying.

As a light source for forming radiation used when at least one of the pixel and the black matrix is selected, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp can be exemplified. Light source such as low-pressure mercury lamp, argon ion laser, YAG laser, XeCl excimer laser, nitrogen laser and other laser light sources. As the light source for exposure, an ultraviolet LED can also be used. Radiation having a wavelength in the range of 190 to 450 nm is preferred.

The exposure amount of the radiation is generally preferably from 10 to 10000 J/m ² .

Further, as the alkali developing solution, for example, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0 is preferred. An aqueous solution of -7-undecene, 1,5-diazabicyclo-[4.3.0]-5-decene.

A water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the alkali developer in an appropriate amount. It should be noted that after alkali development, water washing is usually carried out.

As the development treatment method, a shower development method, a spray development method, a dip development method, a puddle development method, or the like can be used. The developing conditions are preferably 5 to 300 seconds at normal temperature.

The post-baking conditions are usually about 10 to 60 minutes at 180 to 280 °C.

The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.

In addition, as a second method of forming the coloring layer constituting the color filter, a pixel of each color obtained by an inkjet method, which is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2000-310706, and the like. method. In this method, first, a partition wall having a light blocking function is formed on the surface of the substrate. Next, in the formed partition, for example, a liquid composition of the thermosetting composition of the present invention containing a blue coloring agent is ejected by an inkjet device, and then prebaked to evaporate the solvent. Next, the coating film is exposed as needed, and then post-baked to be cured to form a blue pixel pattern.

Next, each of the thermosetting compositions containing a green or red coloring agent was used in the same manner as described above, and a green pixel pattern and a red pixel pattern were sequentially formed on the same substrate. Thereby, a color filter in which pixel patterns of three primary colors of blue, green, and red are arranged on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above order.

The partition wall not only has a light-shielding function, but also functions to prevent the thermosetting composition of each color discharged into the partition from being mixed, and therefore has a thicker film thickness than the black matrix used in the first method described above. Therefore, the partition wall is usually formed using a curable composition in which a black coloring agent is dispersed.

The substrate used for forming the color layer, the light source of the radiation, and the method and conditions of the prebaking and postbaking are the same as those of the first method described above. Thus, the film thickness of the pixel formed by the ink jet method is the same as the height of the partition wall.

It is also possible to form a color filter in which a transparent conductive film is formed by sputtering after forming a protective film as needed on the pixel pattern thus obtained. After the transparent conductive film is formed, a spacer is further formed to form a color filter. The protective film and the spacer are usually formed using a radiation-sensitive composition, and may also be a spacer having a light-shielding property (black spacer). At this time, a colored radiation-sensitive composition in which a black coloring agent is dispersed is used. The curable composition of the present invention can be preferably used in the formation of the above protective film or spacer. The conditions for forming the protective film and the spacer are the same as those for the colored layer described above.

Since the color filter of the present invention thus obtained has extremely high luminance and color purity, it is extremely useful in color liquid crystal display elements, color image sensor elements, color sensors, organic EL display elements, electronic paper, and the like.

[display component]

The display element of the present invention comprises the cured film of the present invention. As the display element, a color liquid crystal display element, an organic EL display element, electronic paper, or the like can be exemplified.

The color liquid crystal display element having the cured film of the present invention may be of a transmissive type or a reflective type, and an appropriate structure may be employed. For example, a structure in which a color filter, a driving substrate, and a substrate on which the color filter is formed are opposed to each other via a liquid crystal layer may be formed on a substrate different from a driving substrate on which a thin film transistor (TFT) is disposed. Further, a substrate on which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed, and an ITO (tin-doped indium oxide) electrode or IZO (indium oxide and The mixture of zinc oxide) has a structure in which the substrate of the electrode is opposed to the liquid crystal layer. The latter structure has the ability to significantly increase the opening The advantage of obtaining a bright and high-definition liquid crystal display element. In the latter configuration, the black matrix and the spacer may be formed on either side of the substrate on which the color filter is formed or on the side of the substrate on which the ITO electrode is formed. Further, the cured film of the present invention can be used as an interlayer insulating film constituting a driving substrate on which a thin film transistor (TFT) is disposed.

The color liquid crystal display element including the cured film of the present invention may include a backlight unit having a white LED as a light source in addition to a CCFL (Cold Cathode Fluorescent Lamp). As a white LED, for example, a white LED in which a red LED, a green LED, and a blue LED are mixed by color to obtain white light can be exemplified, and a combination of a blue LED, a red LED, and a green phosphor is white to obtain white light by color mixing. LED, a combination of a blue LED, a red illuminating phosphor, and a green illuminating phosphor, a white LED that obtains white light by color mixing, and a white LED that is white light by a color mixture of a blue LED and a YAG-based phosphor. A white LED that combines a blue LED, an orange illuminating phosphor, and a green illuminating phosphor to obtain white light by color mixing, and combines an ultraviolet LED, a red luminescent phosphor, a green luminescent phosphor, and a blue luminescent phosphor. A white LED or the like which obtains white light by color mixing.

A color liquid crystal display element having the cured film of the present invention can be a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, or an IPS (In-Planes Switching) type. A suitable liquid crystal mode such as a VA (Vertical Alignment) type or an OCB (Optically Compensated Birefringence) type.

In addition, the organic EL display element having the cured film of the present invention may have a suitable structure. For example, the structure disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242 can be exemplified.

Further, the electronic paper having the cured film of the present invention may have a suitable structure, and for example, a structure disclosed in Japanese Laid-Open Patent Publication No. 2007-41169 can be exemplified.

[dry film]

The dry film of the present invention is formed using the curable composition of the present invention. The dry film of the present invention is obtained by applying the curable composition of the present invention to a colorless transparent carrier film and drying it.

As the colorless transparent carrier film, low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP), polyester (PE), polyethylene terephthalate (PET) can be used. , polycarbonate (PC), polyarylate and other films. The physical properties and coating conditions of the curable composition are affected by moisture. Therefore, the carrier film is preferably a resin film having low moisture permeability, and more preferably a film such as polyethylene terephthalate, polyethylene or polypropylene.

The thickness of the carrier film is usually in the range of 15 to 100 μm, preferably in the range of 15 to 75 μm. The carrier film having a thickness in the above range is excellent in coatability, adhesion, rollability, toughness, cost, and the like. In consideration of coatability, adhesion, roll coating properties, toughness, cost, and the like, a polyethylene terephthalate film having a thickness of 15 to 100 μm, preferably 15 to 40 μm is more preferable.

The coating of the curable composition to the carrier film can be carried out using a reverse roll coater, a gravure roll coater, a comma coater, a curtain coater, a rod. A known device such as a coater is used. The drying temperature of the curable composition is preferably a temperature at which the components contained in the curable composition are thermally reacted rather than activated. Specifically, it is 180 ° C or less, preferably 150 ° C or less, more preferably 140 ° C or less.

[Examples]

Hereinafter, embodiments of the present invention will be further specifically described by way of examples. However, the invention is not limited to the following examples.

<Measurement of Mw and Mw/Mn>

Mw and Mn of the polymer obtained in each of the following Synthesis Examples were measured by gel permeation chromatography (hereinafter abbreviated as GPC) of the following formula.

Device: GPC-104 (made by Showa Denko Co., Ltd.).

Column: KD-G, KF-603, KF-602, KF-601 are used in combination.

Mobile phase: tetrahydrofuran.

<Measurement of acid value>

The acid value of the polymer obtained in each of the following Synthesis Examples was measured by the following method.

0.5 g of the polymer solution was weighed to the unit of 1 mg and dispensed into a glass container. After diluting to 50 mL with propylene glycol monomethyl ether acetate, phenolphthalein was added, and titration was carried out with a 0.1 N aqueous solution of potassium hydroxide, and the color was pink. The blank test was carried out in the same manner, and the acid value (unit: mgKOH/g) was calculated from the amount of the 0.1 N ethanolic potassium hydroxide aqueous solution dropped from the polymer and the blank test.

<Measurement of iodine value>

The iodine value of the polymer obtained in each of the following Synthesis Examples was measured in accordance with the method specified in JIS K 0070:1992. The measured value is represented by a value obtained by converting the amount of iodine bound to 100 g of the resin into a value of g number.

<Synthesis of specific polymer and binder resin> Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 194.4 parts by mass of cyclohexanone was charged and replaced with nitrogen. Heating to 80 ° C, at this temperature, 60 parts by weight of propylene glycol monomethyl ether acetate, 60 parts by mass of methacrylic acid, 30 parts by mass of butyl methacrylate, EO modified acrylic acid 2-B were added dropwise over 2 hours. 30 parts by mass of hexyl hexanoate (M-120, manufactured by Toagosei Co., Ltd.) and 18 parts by mass of cyclohexyl methacrylate, and 45.6 parts by mass of propylene glycol monomethyl ether and 2,2'-azobis (2) , a mixed solution of 10.8 parts by mass of 4-dimethylvaleronitrile, and the polymerization was maintained at this temperature for 1 hour. Thereafter, the temperature of the reaction solution was raised to 90 ° C, and polymerization was further carried out for 1 hour, whereby a resin (1) solution was obtained. The obtained resin (1) was Mw = 8300, Mn = 4500, and Mw / Mn = 1.84.

374.0 parts by mass of a resin (1) solution, 1.91 parts by mass of tetrabutylammonium bromide, and 0.43 parts by mass of 4-methoxyphenol were placed in a flask equipped with a cooling tube and a stirrer, and air bubbling was performed. The mixture was heated to 110 ° C, and 56.1 parts by mass of a glycidyl methacrylate (68 mol % with respect to methacrylic acid) was added dropwise thereto at this temperature for 15 minutes, and the addition reaction was carried out for 9 hours while maintaining the temperature. Next, the solution was cooled to room temperature, and cyclohexanone was added so that the nonvolatile content was 40% by mass, whereby a resin (A-1) solution was obtained. The obtained resin (A-1) was Mw=14,200. Mn = 6800, Mw / Mn = 2.09, and iodine value was 43.5 g / 100 g. The resin (A-1) is a specific polymer.

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 1216 parts by mass of cyclohexanone was charged and replaced with nitrogen. The mixture was heated to 80 ° C, and 160 parts by mass of cyclohexanone, 160 parts by mass of butyl methacrylate, and 2-ethylhexyl acrylate-modified acrylate (manufactured by Toagosei Co., Ltd.) were added dropwise at this temperature for 2 hours. M-120) 160 parts by mass, a mixed solution of 120 parts by mass of tricyclo-[5.2.1.0 ^2,6 ]-mercapto (meth) acrylate and 480 parts by mass of glycidyl methacrylate and cyclohexanone 224 mass A mixed solution of 56 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was allowed to stand at this temperature for 1 hour. Thereafter, the temperature of the reaction solution was raised to 90 ° C, and polymerization was further carried out for 1 hour, whereby a resin (2) solution was obtained. The obtained resin (2) was Mw = 7200, Mn = 4000, and Mw / Mn = 1.80.

In a flask equipped with a cooling tube and a stirrer, 966 parts by mass of a resin (2) solution, 6.15 parts by mass of tetrabutylammonium bromide, and 1.08 parts by mass of 4-methoxyphenol were charged and air bubbling was performed. The mixture was heated to 110 ° C, and 109.2 parts by mass of methacrylic acid (100 mol% relative to glycidyl methacrylate) was added dropwise thereto at this temperature to obtain a resin (3) solution. The obtained resin (3) was Mw = 9600, Mn = 5,500, and Mw / Mn = 1.75.

In a flask equipped with a cooling tube and a stirrer, 433 parts by mass of a resin (3) solution and 16.0 parts by mass of tetrahydrophthalic anhydride were charged, and the mixture was heated and stirred at 100 ° C for 6 hours under air bubbling conditions to carry out an addition reaction. . Next, the solution was cooled to room temperature to have a nonvolatile content of 45% by mass. The cyclohexanone was added in such a manner that a resin (A-2) solution was obtained. The obtained resin (A-2) had Mw=11300, Mn=6300, Mw/Mn=1.79, and an iodine value of 53.6 g/100 g. The resin (A-2) is a specific polymer.

Synthesis Example 3

In a flask equipped with a cooling tube and a stirrer, 144 parts by mass of cyclohexanone was charged and replaced with nitrogen. Heating to 80 ° C, at this temperature, 48 parts by mass of cyclohexanone, 28.8 parts by mass of methacrylic acid, 18 parts by mass of butyl methacrylate, 18 parts by mass of methyl methacrylate, and EO were added dropwise over 2 hours. Mixture of 18 parts by mass of 2-ethylhexyl acrylate (M-120, manufactured by Toagosei Co., Ltd.), 18 parts by mass of cyclohexyl methacrylate, and 37.2 parts by mass of 2,3-dihydroxypropyl methacrylate The solution and a mixed solution of 48 parts by mass of cyclohexanone and 8.4 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) were polymerized at this temperature for 1 hour. Thereafter, the temperature of the reaction solution was raised to 90 ° C, and polymerization was carried out for 1 hour. Next, the solution was cooled to room temperature, and cyclohexanone was added so that the nonvolatile content was 33% by mass, whereby a resin (A-3) solution was obtained. The obtained resin (A-3) had Mw = 10,700, Mn = 5,600, and Mw / Mn = 1.91. The resin (A-3) does not have a polymerizable unsaturated group and does not belong to a specific polymer.

Synthesis Example 4

In a flask equipped with a cooling tube and a stirrer, the total amount of the resin (A-3) solution was added, and after the temperature of the solution was raised to 90 ° C, 2-methylpropene oxime was added dropwise over 15 minutes under air bubbling conditions. 34.3 parts by mass of oxyethyl isocyanate (Karenz MOI manufactured by Showa Denko Co., Ltd.) (mole number of 95% relative to 2,3-dihydroxypropyl methacrylate) and 4-methoxyphenol 0.36 a mixture of parts by mass, maintaining the temperature The addition reaction was carried out for 1.5 hours. Next, the solution was cooled to room temperature, and cyclohexanone was added so that the nonvolatile content was 36% by mass, whereby a resin (A-4) solution was obtained. The obtained resin (A-4) had Mw = 12,800, Mn = 6000, Mw / Mn = 2.13, and an iodine value of 36.0 g / 100 g. The resin (A-4) is a specific polymer.

Synthesis Example 5

In the synthesis of the resin (1) of Synthesis Example 1, except that a methyl group-modified polyethylene glycol methacrylate (manufactured by Nippon Oil Co., Ltd.: BLEMMER PME-200) was used instead of EO-modified acrylic acid 2-ethylhexyl A resin (4) solution was obtained in the same manner as the synthesis of the resin (1) except for the ester (manufactured by Toagosei Co., Ltd., M-120).

Next, in the synthesis of the resin (A-1) of Synthesis Example 1, a resin (A-5) solution was obtained in the same manner as the synthesis of the resin (A-1) except that the resin (4) was used instead of the resin (1) solution. (solid content concentration = 40% by mass). The obtained resin (A-5) had Mw = 12,300, Mn = 6000, Mw / Mn = 2.05, and an iodine value of 48.5 g / 100 g. The resin (A-5) is a specific polymer.

Synthesis Example 6

In the synthesis of the resin (2) of Synthesis Example 2, in addition to the terminal methyl-modified polyethylene glycol methacrylate (manufactured by Nippon Oil Co., Ltd.: BLEMMER PME-200), EO-modified acrylic acid 2-ethylhexyl was used. A resin (5) solution was obtained in the same manner as the synthesis of the resin (2) except for the ester (manufactured by Toagosei Co., Ltd., M-120). The obtained resin (5) was Mw = 7000, Mn = 4,100, and Mw / Mn = 1.71.

Next, in the synthesis of the resin (3) of Synthesis Example 2, the same as the synthesis of the resin (3) except that the resin (5) solution was used instead of the resin (2) solution. A solution of the resin (6) was obtained. The obtained resin (6) had Mw = 9800, Mn = 5,600, and Mw / Mn = 1.75.

Next, in the synthesis of the resin (A-2) of Synthesis Example 2, a resin (A-6) solution was obtained in the same manner as the synthesis of the resin (A-2) except that the resin (6) solution was used instead of the resin (3) solution ( Solid content concentration = 45 mass%). The obtained resin (A-6) had Mw=11300, Mn=5800, Mw/Mn=1.95, and an iodine value of 57.6 g/100 g. The resin (A-6) is a specific polymer.

Synthesis Example 7

In Synthesis Example 3, a terminal methyl group-modified polyethylene glycol methacrylate (manufactured by Nippon Oil Co., Ltd.: BLEMMER PME-200) was used instead of EO-modified 2-ethylhexyl acrylate (manufactured by Toagosei Co., Ltd.). A resin (7) solution was obtained in the same manner as in Synthesis Example 3 except for M-120.

Next, in the synthesis example 4, a resin (A-7) solution (solid content concentration = 36%) was obtained in the same manner as in Synthesis Example 4 except that the resin (7) solution was used instead of the resin (A-3) solution. The obtained resin (A-7) had Mw = 12,600, Mn = 6000, Mw / Mn = 2.10, and an iodine value of 44.0 g / 100 g. The resin (A-7) is a specific polymer.

Synthesis Example 8

In Synthesis Example 3, a resin (8) solution was obtained in the same manner as in Synthesis Example 3 except that cyclohexyl methacrylate was not used.

Next, in the synthesis example 4, a resin (A-8) solution (solid content concentration = 36%) was obtained in the same manner as in Synthesis Example 4 except that the resin (8) solution was used instead of the resin (A-3) solution. The obtained resin (A-8) had Mw = 11,000, Mn = 5,300, Mw / Mn = 2.08, and an iodine value of 131 g / 100 g. The resin (A-8) does not have a substituted or unsubstituted alicyclic hydrocarbon group and does not conform to a specific polymer.

Synthesis Example 9

In Synthesis Example 3, EO-modified acrylic acid-p-alkenylphenol ester (manufactured by Toagosei Co., Ltd., M-110) was used instead of EO-modified 2-ethylhexyl acrylate (manufactured by Toagosei Co., Ltd., M- A resin (9) solution (solid content concentration = 36%) was obtained in the same manner as in Synthesis Example 3 except for 120.

Next, in Synthesis Example 4, a resin (A-9) solution (solid content concentration = 36%) was obtained in the same manner as in Synthesis Example 4 except that the resin (9) solution was used instead of the resin (A-3) solution. The obtained resin (A-9) had Mw = 11700, Mn = 5,800, Mw / Mn = 2.02, and an iodine value of 124 g / 100 g. The resin (A-9) does not have a group represented by the formula (1) and does not belong to a specific polymer.

Synthesis Example 10

In a flask equipped with a cooling tube and a stirrer, 80 parts by mass of propylene glycol monomethyl ether acetate was placed and replaced with nitrogen. Heating to 80 ° C, at this temperature, 50 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, and 15 parts by mass of 2-hydroxyethyl methacrylate were added dropwise over 2 hours. And a mixed solution of 28 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, and 15 parts by mass of mono(2-propenyloxyethyl) succinate, and A mixed solution of 20 parts by mass of propylene glycol monomethyl ether acetate and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was polymerized at this temperature for 1 hour. Thereafter, the temperature of the reaction solution was raised to 90 ° C, and polymerization was further carried out for 1 hour, whereby a resin (A-10) solution (solid content concentration = 40% by mass) was obtained. The obtained resin (A-10) had Mw = 10,500, Mn = 5,900, and Mw / Mn = 1.78. Incidentally, the resin (A-10) corresponds to (F) a binder resin.

Synthesis Example 11

In a flask equipped with a cooling tube and a stirrer, 1216 parts by mass of cyclohexanone was charged and replaced with nitrogen. The mixture was heated to 80 ° C, and 160 parts by mass of cyclohexanone, 160 parts by mass of butyl methacrylate, and dipropylene glycol monomethyl ether methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) were added dropwise at this temperature for 2 hours. 160 parts by mass, a mixed solution of 120 parts by mass of tricyclo-[5.2.1.0 ^2,6 ]-mercapto (meth) acrylate and 480 parts by mass of glycidyl methacrylate, and 224 parts by mass of cyclohexanone and 2 A mixed solution of 2'-azobis(2,4-dimethylvaleronitrile) of 56 parts by mass, which was allowed to stand at this temperature for 1 hour. Thereafter, the temperature of the reaction solution was raised to 90 ° C, and polymerization was further carried out for 1 hour, whereby a resin (11-1) solution was obtained. The obtained resin (11-1) had Mw = 6800, Mn = 4000, and Mw / Mn = 1.70.

In a flask equipped with a cooling tube and a stirrer, 966 parts by mass of a resin (11-1) solution, 6.15 parts by mass of tetrabutylammonium bromide, and 1.08 parts by mass of 4-methoxyphenol were charged and air bubbling was performed. The mixture was heated to 110 ° C, and 109.2 parts by mass of methacrylic acid (100 mol% relative to glycidyl methacrylate) was added dropwise thereto at this temperature to obtain a resin (11-2) solution. The obtained resin (11-2) had Mw = 10,000, Mn = 5,600, and Mw / Mn = 1.79.

In a flask equipped with a cooling tube and a stirrer, 433 parts by mass of a resin (11-2) solution and 16.0 parts by mass of tetrahydrophthalic anhydride were charged, and the mixture was heated and stirred at 100 ° C for 6 hours under air bubbling conditions. Into a reaction. Next, the solution was cooled to room temperature, and cyclohexanone was added so that the nonvolatile content was 45% by mass, whereby a resin (A-11) solution was obtained. The obtained resin (A-11) had Mw = 13300, Mn = 7300, Mw / Mn = 1.82, and an iodine value of 57.3 g / 100 g. The resin (A-11) is a specific polymer.

<Preparation and evaluation of hardenable composition> Example 1 [Preparation of Red Pigment Dispersion]

5.2 parts by mass of CI Pigment Red 177 as a coloring agent, 7.8 parts by mass of CI Pigment Red 254, and 11.5 parts by mass of BYK-LPN 21116 (manufactured by BYK Co., Ltd.) as a dispersing agent (solid content concentration = 40% by mass), 11.0 were used. A part by mass of the resin (A-1) solution, 63.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent, and 1.5 parts by mass of propylene glycol monomethyl ether, which are mixed by a bead mill. Disperse to prepare a red pigment dispersion (r-1).

[Preparation of red hardening composition]

1240 parts by mass of the red pigment dispersion (r-1) as the coloring agent (C), 40 parts by mass of the resin (A-1) solution as the (A) specific polymer, and pentaerythritol IV as the (D) polymerizable compound 50 parts by mass of acrylate (ARONIX M-450, manufactured by Toagosei Co., Ltd.), 2-benzyl-2-dimethylamino-1-(4-) as a photopolymerization initiator Phenylphenyl)butan-1-one (trade name: IRGACURE 369, manufactured by Ciba Specialty Chemicals Co., Ltd.) 15 parts by mass, ethyl ketone-1-[9-ethyl-6-(2-methylbenzhydryl) -9H-carbazol-3-yl]-1-(O-acetamidine)] (manufactured by BASF Corporation, trade name IRGACURE OXE02) 4.0 parts by mass, MEGAFACE F-554 as a fluorine-based surfactant (limited in DIC shares) 0.65 parts by mass, and 675 parts by mass of propylene glycol monomethyl ether acetate as a solvent (B) and 300 parts by mass of 3-methoxybutyl acetate were mixed to prepare red having a solid concentration of about 15% by mass. Hardenable composition (S-1). In addition, the content ratio of the coloring agent in the red curable composition (S-1) was 45 mass% with respect to the solid content of the red curable composition.

[Evaluation of shedding time]

The red curable composition (S-1) was applied onto a 4 inch-diameter soda glass substrate having a SiO ₂ film on the surface thereof to prevent elution of sodium ions, and then dried at 90 ° C for 1 minute using a hot plate. Prebaking was carried out to form a coating film having a film thickness of 2.5 μm. A developer having a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C was sprayed onto the substrate at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm), whereby the elution end time (braking time) was measured. The evaluation was "A" in less than 25 seconds, "B" in 25 seconds or more and less than 30 seconds, and "C" in 30 seconds or more. The evaluation results are shown in Table 5. Incidentally, the faster the time, the faster the development speed, and the advantage of being able to shorten the production interval of the color filter manufacturing.

[Evaluation of developer solubility test]

Five sheets of a substrate coated with a red curable composition (S-1) on a glass substrate using a slit die coater were prepared, and allowed to stand at room temperature for 20 minutes. The film was prebaked for 1 minute using a hot plate at 90 ° C to form a coating film having a film thickness of 2.0 μm. Next, the substrate was cooled to room temperature. 30 g of a 0.04 mass% potassium hydroxide aqueous solution was weighed in a petri dish having a diameter of 200 mm, and five substrates coated with the red curable composition (S-1) were immersed and developed, and the eluted aqueous solution was transferred to a 50 mL screw bottle. The elution was dropped on a glass substrate, and the insoluble matter was observed by an optical microscope. The precipitate was confirmed by the initial evaluation, and the precipitate was confirmed after the initial evaluation, but the precipitate was confirmed as "X" after 3 days. Unconfirmed by initial evaluation The case where the precipitate was turbid after 3 days was evaluated as "△", and the case where the precipitate was confirmed after the initial evaluation and after 3 days was evaluated as "○". The evaluation results are shown in Table 5. It can be said that if the evaluation is good, the color filter can be formed at a high product yield.

[Evaluation of water spots]

The red curable composition (S-1) was applied onto a glass substrate using a slit die coater, and then allowed to stand at room temperature for 20 minutes. The film was prebaked for 1 minute using a hot plate at 90 ° C to form a coating film having a film thickness of 2.0 μm. Next, after the substrate was cooled to room temperature, the coating film on the substrate was exposed to radiation including wavelengths of 365 nm, 405 nm, and 436 nm at a exposure amount of 400 J/m ² using a high pressure mercury lamp through a photomask. Thereafter, a developing solution composed of a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C was sprayed onto the coating film on the substrate at a developing pressure of 1.5 kgf/cm ² (nozzle diameter: 1 mm) until the coating film of the unexposed portion was completely formed. After peeling, it was further carried out for 5 seconds to carry out shower development. Next, ultrapure water was sprayed at a washing pressure of 1.5 kgf/cm ² (nozzle diameter: 1 mm) for 60 seconds to carry out a rinsing treatment to form a dot pattern of 200 μm × 200 μm.

After the moisture on the surface of the substrate on which the dot pattern was formed was removed by a hair dryer, 20 dot patterns were observed using an optical microscope. The case where water spots were observed in 10 or more patterns of 20 patterns was evaluated as "×", and the case where water spots were observed in 1 to 9 patterns was evaluated as "△", and water spots were not observed at all. The evaluation of the case was evaluated in the form of "○". The evaluation results are shown in Table 5.

[Evaluation of pattern defects]

The red curable composition (S-1) was applied onto a glass substrate using a slit die coater, and then allowed to stand at room temperature for 20 minutes. The film was prebaked for 1 minute using a hot plate at 90 ° C to form a coating film having a film thickness of 2.0 μm. Next, after the substrate was cooled to room temperature, the coating film on the substrate was exposed to an illuminance of 17 mW, including 365 nm, 405 nm, and at a exposure amount of 400 J/m ² using a high pressure mercury lamp through a mask having a stripe pattern having a width of 90 μm. The radiation of each wavelength of 436 nm was expanded, and the distance between the substrate and the mask was expanded to 350 μm to perform exposure. Thereafter, in the developing nip 1.5kgf / cm ² (nozzle diameter 1mm) by a developing solution 0.04 mass% potassium hydroxide aqueous solution composed of 23 ℃ discharged to the coating film on the substrate, until the unexposed portions of the coating film is completely peeled off After 30 seconds, the shower development was carried out. Then, ultrapure water was sprayed at a washing pressure of 1.5 kgf/cm ² (nozzle diameter: 1 mm) for 60 seconds to carry out a rinsing treatment, and then the moisture on the surface of the substrate on which the stripe pattern was formed was removed by a blower, thereby forming 90 μm. Stripe pattern of width.

Five stripe patterns described above were observed using an optical microscope. The case where 10 or more defects were observed in the five stripe patterns was evaluated as "x", the case where 1 to 9 defects were observed was evaluated as "△", and the case where the defect was not observed at all was evaluated as The form of "○" was evaluated. The evaluation results are shown in Table 5.

[Examples 2 to 7 and Comparative Examples 1 to 3]

In the same manner as in Example 1, except that the type and amount of the polymer solution and the solvent were changed as shown in Table 1, red pigment dispersion liquids (r-2) to (r-10) were prepared.

In the same manner as in Example 1, except that the type and amount of the red pigment dispersion liquid and the polymer solution were changed as shown in Table 2, a red curable composition (S-2) to (S-2) was prepared. S-10). Further, the obtained red curable compositions (S-2) to (S-10) were evaluated in the same manner as in Example 1. The results are shown in Table 5.

In addition, in Table 1, each component is as follows.

R177: C.I. Pigment Red 177

R254: C.I. Pigment Red 254

LPN21116: BYK-LPN21116 (manufactured by BYK)

PGMEA: propylene glycol monomethyl ether acetate

PGME: propylene glycol monomethyl ether

In addition, in Table 2, each component is as follows.

D-1: pentaerythritol tetraacrylate (manufactured by Toagosei Co., Ltd., ARONIX M-450)

E-1: 2-benzyl-2-dimethylamino-1-(4- Porphyrin phenyl) butan-1-one (trade name: IRGACURE 369, manufactured by Ciba Specialty Chemicals)

E-2: Ethyl-1-(9-ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl]-1-(O-acetyl)](BASF Company system, trade name IRGACURE OXE02)

G-1: MEGAFACE F-554 (made by DIC Corporation)

B-1: propylene glycol monomethyl ether acetate

B-2: 3-methoxybutyl acetate

Example 8 [Preparation of Green Pigment Dispersion]

9.1 parts by mass of CI Pigment Green 58 as a coloring agent, 3.9 parts by mass of CI Pigment Yellow 138, and BYK-LPN21116 (manufactured by BYK Corporation) as a dispersing agent, 11.5 parts by mass (solid content concentration = 40% by mass), dispersion aid 0.20 parts by mass (manufactured by OODA KASEI Co., Ltd., trade name: α), 11.0 parts by mass of the resin (A-1) solution, 63.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent, and 1.5 parts by mass of propylene glycol monomethyl ether , using a bead mill to mix. The green pigment dispersion (g-1) was prepared by dispersion.

[Preparation of green curable composition]

1190 parts by mass of the green pigment dispersion liquid (g-1) as the coloring agent (C), 93 parts by mass of the resin (A-1) solution as the (A) specific polymer, and pentaerythritol IV as the (D) polymerizable compound 50 parts by mass of acrylate (ARONIX M-450, manufactured by Toagosei Co., Ltd.), 10 parts by mass of ADEKA ARKLS NCI-831 (manufactured by Adeka Co., Ltd.) as a photopolymerization initiator, and MEGAFACE F as a fluorine-based surfactant -554 (manufactured by DIC Corporation) 0.65 parts by mass, and 666 parts by mass of propylene glycol monomethyl ether acetate as (B) solvent, 3-A 400 parts by mass of oxybutyl acetate was mixed to prepare a green curable composition (S-11) having a solid concentration of about 15% by mass. In addition, the content ratio of the coloring agent in the green curable composition (S-11) was 43% by mass based on the solid content of the green curable composition.

The obtained green curable composition (S-11) was evaluated in the same manner as in Example 1. The results are shown in Table 5.

Examples 9 to 14 and Comparative Examples 4 to 6

In the same manner as in Example 8, except that the type and amount of the polymer solution and the solvent were changed as shown in Table 3, green pigment dispersions (g-2) to (g-10) were prepared.

Next, in Example 8, a green curable composition (S-12) was prepared in the same manner as in Example 8 except that the type and amount of the green pigment dispersion liquid and the polymer solution were changed as shown in Table 4. S-20). Further, the obtained green curable compositions (S-12) to (S-20) were evaluated in the same manner as in Example 1. The results are shown in Table 5.

In Table 3, the respective components are as follows.

G58: C.I. Pigment Green 58

Y138: C.I. Pigment Yellow 138

LPN21116: BYK-LPN21116 (manufactured by BYK)

PGMEA: propylene glycol monomethyl ether acetate

PGME: propylene glycol monomethyl ether

In Table 4, the respective components are as follows.

D-1: pentaerythritol tetraacrylate (manufactured by Toagosei Co., Ltd., ARONIX M-450)

E-3: ADEKA ARKLS NCI-831 (made by ADEKA CORPORATION)

G-1: MEGAFACE F-554 (made by DIC Corporation)

B-1: propylene glycol monomethyl ether acetate

B-2: 3-methoxybutyl acetate

<Manufacture of color filters> [Preparation of blue curable composition] Example 15

As a coloring agent, CI Pigment Blue 15:6/CI Pigment Violet 23=95/5 mixture 15.0 parts by mass, Disperbyk-2001 (manufactured by BYK Co., Ltd.) as a dispersing agent, 2.2 parts by mass (solid content concentration = 46% by mass), 8.3 parts by mass of a resin (A-4) solution, 7.5 parts by mass of a resin (A-10) solution, and propylene glycol monomethyl ether acetate/propylene glycol monomethyl ether as a solvent: 67.0 parts by mass of a 9/1 mixed solvent, using a bead mill Machine mix. The blue pigment dispersion (b-1) was prepared by dispersion.

Next, 980 parts by mass of the blue pigment dispersion liquid (b-1) as the coloring agent (C), and 120 parts by mass of the resin (A-4) solution as the (A) specific polymer, as (D) polymerizability 60 parts by mass of pentaerythritol tetraacrylate (ARONIX M-450, manufactured by Toagosei Co., Ltd.), and ethyl ketone-1-[9-ethyl-6-(2-methylbenzhydrazide) as a photopolymerization initiator 10 parts by weight of 9H-carbazol-3-yl]-1-(O-acetyl)] (manufactured by BASF Corporation under the trade name IRGACURE OXE02), MEGAFACE F-554 (DIC) as a fluorine-based surfactant 0.65 parts by mass and 650 parts by mass of propylene glycol monomethyl ether acetate as a solvent (B), 150 parts by mass of 3-methoxybutyl acetate, ethyl 3-ethoxypropionate 50 parts by mass of the mixture was mixed to prepare a blue curable composition (S-21) having a solid concentration of about 15% by mass. In addition, the content ratio of the coloring agent in the blue curable composition (S-21) was 39% by mass based on the solid content of the blue curable composition.

[Formation of a pattern with a protective film layer] Example 16

100 parts by mass of the resin (A-2) solution as the (A) specific polymer, and 200 parts by mass of the pentaerythrine as the (D) polymerizable compound Alcohol tetraacrylate (ARONIX M-450, manufactured by Toagosei Co., Ltd.), 40 parts by mass of a phenol novolac type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name Epikote 152), and 5 parts by mass as adhesion promotion Γ-glycidoxypropyltrimethoxydecane, 0.2 parts by mass of FTX-218 as a surfactant (manufactured by Neos Co., Ltd.), and diethylene glycol methyl b as a solvent (B) The base ether was mixed to prepare a thermosetting composition (S-22) for forming a protective film having a solid concentration of 20% by mass.

Next, the red curable composition (S-2) obtained in Example 2 was applied onto a glass substrate using a slit die coater, and then allowed to stand at room temperature for 20 minutes. The film was prebaked for 1 minute using a hot plate at 90 ° C to form a coating film having a film thickness of 2.0 μm. Next, after the substrate was cooled to room temperature, the coating film on the substrate was exposed to radiation including respective wavelengths of 365 nm, 405 nm, and 436 nm through a photomask using a high pressure mercury lamp at an exposure amount of 400 J/m ² . Thereafter, a developing solution composed of a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C was sprayed onto the coating film on the substrate at a developing pressure of 1.5 kgf/cm ² (nozzle diameter: 1 mm) until the coating film of the unexposed portion was completely formed. The peeling was further carried out for 5 seconds, thereby performing shower development. Next, ultrapure water was sprayed at a washing pressure of 1.5 kgf/cm ² (nozzle diameter: 1 mm) for 60 seconds to carry out a rinsing treatment, and then baked in an oven at 230 ° C for 30 minutes to form a red striped pattern. No water spots were formed on the red stripe pattern.

Next, in the same manner, a green striped pattern was formed using the green curable composition (S-12) of Example 9. Further, a blue striped pattern was formed using the blue curable composition (S-21) of Example 15. No water is produced on these green striped patterns and blue striped patterns spot. The thermosetting composition for forming a protective film (S-22) was applied onto the stripe-like colored pattern thus obtained by using a slit spin coater. The coating film was prebaked in a hot plate at 80 ° C for 2 minutes to form a coating film, and further baked in a clean oven at 180 ° C for 60 minutes to form a protective film having a film thickness of 1.5 μm. The obtained substrate was used as the substrate (1).

[Production of color filter with spacer] Example 17

50 parts by mass of a resin (A-2) solution as the (A) specific polymer, and 200 parts by mass of (D) a polymerizable compound pentaerythritol tetraacrylate (ARONIX M-450, manufactured by Toagosei Co., Ltd.), And 10 parts by mass of 1,9-decane diacrylate, and 5 parts by mass of 2-methyl-1-(4-methylthiophenyl)-2- as a photopolymerization initiator Phenolpropan-1-one (trade name: IRGACURE 907, manufactured by BASF Corporation), ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION) 5 parts by mass, 2,2'-bis(2-chlorophenyl)-4,4 5 parts by mass of '5,5'-tetraphenyl-1,2'-biimidazole and 5 parts by mass of 4,4'-bis(diethylamino)benzophenone, and 5 parts by mass as a close Γ-glycidoxypropyltrimethoxydecane as a promoter, 0.5 parts by mass of FTX-218 (manufactured by NEOS Co., Ltd.) as a surfactant, and 0.5 parts by mass of 4-methoxy as a storage stabilizer The phenol and the propylene glycol monomethyl ether acetate as the solvent (B) were mixed to prepare a curable composition for forming a separator having a solid concentration of about 30% by mass (S-23).

Next, on the substrate (1) on which the striped colored pattern and the protective film were obtained in Example 16, a transparent conductive film was formed by sputtering. Next, the above-described spacer-forming curable composition (S-23) was applied by a slit spin coater, and prebaked on a hot plate at 100 ° C for 3 minutes to form a film having a film thickness of 3.5 μm. The obtained film was exposed with a high-pressure mercury lamp through a reticle of a residual pattern of 10 μm square at an exposure amount of 500 J/m ² . Thereafter, the film was developed at 25 ° C using a 0.05 mass% potassium hydroxide aqueous solution, and then washed with pure water for 1 minute, and further baked in an oven at 180 ° C for 30 minutes to form a separator. Thus, a color filter having a stripe pattern of three colors of red, green, and blue was produced. The obtained color filter was designated as CF (1).

Example 18

In the same manner as in Example 16 except that the resin (A-4) solution was used instead of the resin (A-2) solution, a thermosetting composition for forming a protective film (S-24) was prepared.

Next, a green curable composition (S-17) is used instead of the green curable composition (S-12), and a thermosetting composition (S-24) for forming a protective film is used instead of the thermosetting composition for forming a protective film. A pattern having a protective film layer was formed in the same manner as in Example 16 except for the object (S-22). The obtained substrate was used as the substrate (2).

Example 19

In the same manner as in Example 17, except that the resin (A-1) solution was used instead of the resin (A-2) solution, a curable composition for forming a separator (S-25) was prepared.

Next, the curable composition for forming a spacer (S-25) is used instead of the curable composition for forming a spacer (S-23), and the substrate (2) is used instead of the substrate (1). 17 A color filter was produced in the same manner. The obtained color filter was designated as CF(2).

When CF(1) and CF(2) are manufactured, water spots are not generated on the pixel pattern, so that the color filter can be efficiently manufactured.

Next, two liquid crystal display elements were fabricated using CF (1) or CF (2). The obtained two color liquid crystal display elements exhibited excellent display characteristics and reliability.

<Manufacture of dry film> Example 20

265 parts by mass of a resin (A-2) solution of (A) a specific polymer, and 132 parts by mass of pentaerythritol tetraacrylate (ARONIX M-450, manufactured by Toagosei Co., Ltd.) as a (D) polymerizable compound, Ethyl ketone-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-acetyl)] (photopolymerization initiator) 1 part by mass, bis(2,4,6-trimethylbenzylidene) phenol phosphine oxide (manufactured by BASF Corporation, IRGACURE-819), 3 parts by mass, and (B), manufactured by BASF Corporation, trade name: IRGACURE OXE02) A solvent mixture of propylene glycol monomethyl ether/methyl 3-methoxypropionate = 1/1 was mixed to prepare a curable composition for forming a dry film having a solid concentration of about 35% by mass (S-26).

The obtained curable composition for forming a dry film (S-26) was applied to a PET (polyethylene terephthalate) film at a film thickness of 5 μm using a wire bar, and prebaked on a hot plate at 100 ° C. Bake for 2 minutes. Next, the film formed on the PET film was transferred to a PC (polycarbonate) film using a laminator (roller temperature: 90 ° C).

The resulting film was exposed with a high-pressure mercury lamp through a stripe pattern mask at an exposure amount of 100 J/m ² . Thereafter, after developing at 25 ° C for 50 seconds using a 1% by mass aqueous sodium carbonate solution, it was washed with pure water for 1 minute, followed by post exposure at an exposure amount of 500 J/m ² , and further after 90 minutes in an oven at 135 ° C. Baking, thereby obtaining a dry film.

Using the obtained dry film, a protective film for a touch panel was produced in accordance with the method described in paragraph [0121] of the specification of Japanese Patent No. 4733184. The touch panel with this protective film exhibits excellent adhesion, hardness, and chemical resistance.

Claims (14)

A curable composition comprising (A) a group having a group represented by the following formula (1), a substituted or unsubstituted alicyclic hydrocarbon group, and a polymerizable unsaturated group, and (B) Solvent, In the formula (1), R ¹ represents an alkanediyl group having 2 to 4 carbon atoms, R ² represents an aliphatic hydrocarbon group, n represents an integer of 1 to 100, and * represents a bonding site, wherein when n is 2 or more There may be a plurality of R ^{1 's which} may be the same or different. The curable composition according to claim 1, wherein the (A) polymer is a polymer having a repeating unit represented by the following formula (2), In the formula (2), Z ¹ represents -O-, -CO-, -C(=O)O-(* ¹ ), -CONH-(* ¹ ) or a phenyl group, and R ³ represents a hydrogen atom or a methyl group. , * ¹ to R ¹ is bonded binding site, wherein, R & lt ^1, R ² and n R (1) in the formula ^1, R ² and n have the same meaning. The curable composition according to claim 1, wherein the (A) polymer is a polymer having a repeating unit represented by the following formula (3), In the formula (3), Z ² represents -O-, -CO-, -C(=O)O-(* ² ), -CONH-(* ² ), or selected from -O-, -CO-, - a group in which at least one of C(=O)O- and -CONH- is combined with an alkanediyl group, R ⁴ represents a substituted or unsubstituted alicyclic hydrocarbon group, and R ⁵ represents a hydrogen atom or a methyl group. * ² indicates a bonding site bonded to R ⁴ . The curable composition according to any one of claims 1 to 3, wherein the (A) polymer has an iodine value of 5 to 100 g/100 g. The curable composition according to any one of claims 1 to 3, wherein the aliphatic hydrocarbon group is a linear or branched alkyl group having 1 to 12 carbon atoms. The curable composition according to any one of claims 1 to 3, wherein the polymer further has an acidic functional group. The curable composition according to any one of claims 1 to 3, wherein the polymer has a polymerizable unsaturated group in a side chain. The curable composition according to any one of claims 1 to 3, wherein the polymerizable unsaturated group is a (meth) acrylonitrile group. The curable composition according to any one of claims 1 to 3, further comprising (D) a polymerizable compound, wherein the (D) polymerizable compound does not include the component (A). The curable composition according to any one of claims 1 to 3, which is used for a color filter. The curable composition according to any one of claims 1 to 3, further comprising (C) a colorant. A cured film formed by using the curable composition according to any one of claims 1 to 11. A display element comprising the cured film described in claim 12. A dry film formed by using the curable composition according to any one of claims 1 to 9.