WO2014157427A1

WO2014157427A1 - Curable composition, cured film, color filter, protective film, display device and solid-state imaging element

Info

Publication number: WO2014157427A1
Application number: PCT/JP2014/058700
Authority: WO
Inventors: 福重　裕一; 一真両角; 漢那　慎一
Original assignee: 富士フイルム株式会社
Priority date: 2013-03-26
Filing date: 2014-03-26
Publication date: 2014-10-02

Abstract

A curable composition which contains (A) a compound that has a molecular weight of less than 1,300 and contains at least two ethylenically unsaturated double bonding groups and at least one secondary hydroxyl group, (B) a hyperbranched compound that has a molecular weight of 1,300 or more and (C) at least one initiator that is selected from the group consisting of photopolymerization initiators and thermal polymerization initiators; and a cured film, a color filter, a protective film, a display device and a solid-state imaging element, each of which uses this curable composition.

Description

Curable composition, cured film, color filter, protective film, display device, and solid-state imaging device

The present invention relates to a curable composition, a cured film, a color filter, a protective film, a display device, and a solid-state imaging device. Specifically, the present invention relates to a curable composition having high hardness and low temperature curing characteristics and its use.

Liquid crystal display devices are widely used for display devices that display high-quality images. A substrate for a display device (for example, a color filter substrate, an active matrix substrate, an organic EL display substrate, etc.) has a structure in which structures such as a color filter and a protective film are formed on the substrate. Among these structures, as a method for forming a color filter or a protective film, there is a method of forming by photolithography using a photosensitive curable composition (hereinafter also referred to as “photosensitive resin composition”). It has become mainstream.

As such a photosensitive resin composition, on a substrate with low heat resistance such as a plastic substrate, a pattern having the resolution and chemical resistance required for applications such as a color filter is such that the substrate does not deform. As a material capable of forming a pattern at a temperature, a colored photosensitive resin composition containing a colorant, a resin, and a dendrimer or hyperbranched polymer as a polymerizable compound is disclosed (for example, JP 2012-173546 A). See the official gazette). Although this colored photosensitive resin composition is described that a cured pattern can be obtained by baking a colored pattern formed by pattern exposure and development at a temperature of 25 ° C. or higher and 230 ° C. or lower. In specific examples, it is described that the baking is not performed, and that a colored pattern having excellent solvent resistance can be obtained.

Moreover, as a curable composition used for forming a protective film for preventing scratches and contamination on various substrate surfaces, two or more (meth) acryloyl groups in a molecule such as dipentaerythritol hexaacrylate are used. Disclosed are curable compositions comprising a compound having a photopolymerization initiator, and a multibranched polymer such as a dendrimer or hyperbranched polymer. It is described that a protective film obtained by applying this curable composition to a plastic substrate such as cellulose triacetate and curing with ultraviolet rays has high pencil hardness (see, for example, JP-A-2009-286924).

In general, when a pattern (for example, a pixel of a color filter) or a protective film is formed on a substrate using a curable composition, curing is often insufficient only by exposure with ultraviolet rays or the like, and further heat treatment is performed. May need to be applied. When such heat treatment is performed, a glass substrate having high heat resistance is generally used, but the use of a substrate having excellent flexibility such as a plastic substrate has been desired for a long time.
However, since the plastic substrate has low heat resistance, it is necessary to set the temperature of the heat treatment to a temperature at which the plastic substrate does not deform. Therefore, there is a demand for a curable composition that can form a pattern or protective film having a high hardness at a much lower temperature than in the past.
That is, the present invention relates to a curable composition in which a pattern or protective film having a high hardness is formed at a lower temperature than before, a cured film using the curable composition, a color filter, a protective film, a display device, and It is an object to provide a solid-state imaging device.

Specific means for achieving the above object are as follows.
<1> (A) a compound having a molecular weight of less than 1300 having at least two ethylenically unsaturated double bond groups and at least one secondary hydroxyl group, (B) a hyperbranched compound having a molecular weight of 1300 or more, and (C) photopolymerization. A curable composition comprising at least one initiator selected from the group consisting of an initiator and a thermal polymerization initiator.
<2> The curable composition according to <1>, wherein the (B) multi-branched compound is at least one selected from the group consisting of dendrimers and hyperbranched polymers.

<3> The curable composition according to <1> or <2>, further comprising (D) a resin having an acidic group in the side chain.
<4> The curable composition according to any one of <1> to <3>, further comprising (E) a colorant.
<5> The curable composition according to any one of <1> to <4>, further comprising (F) a refractive index adjusting material.
<6> (F) The curable composition according to <5>, wherein the refractive index adjusting material is at least one kind of inorganic fine particles selected from metal fine particles and metal oxide fine particles.

<7> A cured film obtained by curing the curable composition according to any one of <1> to <6>.
<8> A color filter including the cured film according to <7>.
<9> A protective film including the cured film according to <7>.

<10> A display device including the color filter according to <8>.
<11> A display device including the protective film according to <9>.
<12> A solid-state imaging device including the color filter according to <8>.
<13> A solid-state imaging device including the protective film according to <9>.

According to the present invention, a curable composition in which a pattern having a high hardness or a protective film is formed at a lower temperature than before, a cured film using the curable composition, a color filter, a protective film, a display device, and A solid-state imaging device is provided.

It is explanatory drawing of taper angle (alpha) of an ITO pattern.

Hereinafter, the curable composition of the present invention, and a cured film, a color filter, a protective film, a display device, and a solid-state imaging device using the curable composition will be described in detail.

[Curable composition]
The curable composition of the present invention comprises (A) a compound having a molecular weight of less than 1300 having at least two ethylenically unsaturated double bond groups and at least one secondary hydroxyl group, and (B) a multibranched compound having a molecular weight of 1300 or more. (C) at least one initiator selected from the group consisting of a photopolymerization initiator and a thermal polymerization initiator.
By using the curable composition according to the present invention, the reaction mechanism for obtaining a cured film having a high hardness at a lower temperature than the conventional one is not always clear. However, by including both the secondary hydroxyl group contained in the compound (A) and the (B) multi-branched compound, the curable composition is more highly crosslinked at a low temperature and has high hardness. It is clear that the cured film is formed by comparing the curable composition according to the present invention in the examples described later and the curable composition according to the comparative example. That is, instead of the compound (A), a compound having no molecular weight of less than 1300 (for example, diethylene glycol hexaacrylate) having no secondary hydroxyl group and having at least two ethylenically unsaturated double bond groups, (B) It has the same composition as the curable composition according to the present invention except that it does not contain a hyperbranched compound and the (C) initiator, or the (B) hyperbranched compound. Compared with the curable composition, the curable composition according to the present invention has high ethylenically unsaturated double bonds and high hardness in the obtained cured film even when heated at the same heating temperature.

<(A) Compound having a molecular weight of less than 1300 having at least two ethylenically unsaturated double bond groups and at least one secondary hydroxyl group (hereinafter also referred to as “specific polymerizable compound”)>
The specific polymerizable compound is subjected to the action of the radical derived from the (C) initiator, and at least two ethylenically unsaturated double bond groups of the specific polymerizable compound cause a polymerization reaction to increase the molecular weight. A compound having a molecular weight of less than 1300. Due to the fact that the specific polymerizable compound has at least one secondary hydroxyl group, the polarity of the specific polymerizable compound is improved, and the hydrogen atom adjacent to the secondary hydroxyl group is easily extracted. In combination, the inhibition of the polymerization reaction by oxygen is suppressed and the reaction progress is fast, and the coexistence of the (B) multi-branched compound promotes the polymerization reaction and increases the hardness. It seems that a high cured film can be obtained.

The specific polymerizable compound is preferably a compound having a molecular weight of less than 1300 represented by the following general formula (1).

(In general formula (1), X represents a hydrogen atom or a methyl group. N represents an integer of 2 to 6. A represents a hydrogen atom of n hydroxy groups from an m-valent polyhydric alcohol. Represents an excluded n-valent group, where m represents an integer of 2 or more and 6 or less, and m ≧ n.

The m-valent polyhydric alcohol includes aliphatic alcohols and aromatic polyhydroxy compounds.
Examples of m-valent aliphatic alcohols include ethylene glycol oligomers such as ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1-methyl- 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-dimethylolcyclohexane, 1,2,3-trihydroxypropane, 1,1,1-trimethylolpropane, pentaerythritol And dipentaerythritol.
Examples of the m-valent aromatic polyhydroxy compound include bisfer A and 1,4-dimethanolcyclohexane.
Of these m-valent polyhydric alcohols, aliphatic alcohols are preferred because the lower the viscosity of the system during polymerization, the better the progress of polymerization. On the other hand, when importance is attached to the hardness of the crosslinked film, an aromatic polyhydroxy type may be preferable, and it is preferable to use them properly depending on the required performance.
Hereinafter, preferred specific examples of the compound represented by the general formula (1) will be given.
In addition, although the following compound (35) is not contained in the compound represented by General formula (1), this is also a preferable example of a specific polymerizable compound.

The content of the specific polymerizable compound is suitably 1% by mass or more and 60% by mass or less, preferably 5% by mass or more and 55% by mass or less, preferably 5% by mass or more, based on the total solid content of the curable composition. 40 mass% or less is especially preferable.
When the content of the specific polymerizable compound is 1% by mass or more, when it contains a photopolymerization initiator (C) as an initiator, curing by exposure becomes good, and further, by heat treatment at a low temperature, A cured film having a much higher hardness can be obtained, and when this cured film is used as a protective film, there is little deterioration. On the other hand, if the content of the specific polymerizable compound is in the range of 60% by mass or less, it is easy to adjust the viscosity of the coating liquid to an appropriate range when the curable composition is used as the coating liquid, and curing is performed. It is easy to adjust the hardness of the film and the exposure sensitivity.

[(B) Multi-branched compound]
(B) The hyperbranched compound is a compound having a molecular weight of 1300 or more having a higher-order branched structure having a partial structure such as a comb shape or a star shape repeatedly in two or more stages. (B) Multi-branched compounds include those whose terminal group is a group selected from the group consisting of a carboxyl group, an amino group, an epoxy group, an acryloyl group, and a methacryloyl group. Among these, a particularly preferred terminal group is an acryloyl group or a methacryloyl group. Hereinafter, a compound having a molecular weight of 1300 or more having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group (hereinafter, these groups are also collectively referred to as “(meth) acryloyl group”) as a terminal group. Also referred to as “polymerizable hyperbranched compound”. )
(B) The hyperbranched compound is preferably a polymerizable hyperbranched compound. The polymerizable multi-branched compound preferably has at least 10 terminal (meth) acryloyl groups, more preferably 12 or more and 32 or less.
(B) The hyperbranched compound is a compound having a molecular weight of 1300 or more, but the molecular weight is 1300 or more and 100,000 or less, more preferably 1300 or more and 20000 or less, and particularly preferably 1300 or more and 15000 or less. . When it has a molecular weight of 1300 or more, it means a weight average molecular weight.

In the present invention, it is preferable that the (B) multi-branched compound is selected from the group consisting of a dendrimer and a hyperbranched polymer because a cured film having high hardness can be easily obtained.
A dendrimer has a chemical structure in which a chemical structure constituting a core (hereinafter also referred to as “core part”) is regularly branched to the outside thereof, and has a spherical, highly controlled chemical structure and Has a molecular weight. Hyperbranched polymers have a chemical structure similar to dendrimers, but are not as highly regular branching structures or high molecular weight controls as in dendrimers, and the branches are formed according to a probability distribution and have a broad molecular weight distribution. It is what you have.
Dendrimers and hyperbranched polymers are excellent in solubility, have low viscosity when made into a solution, and have a large number of functional groups (for example, carboxyl group, amino group, epoxy group, acryloyl group, and methacryloyl group). Such a characteristic on the chemical structure is considered to be a factor for obtaining a cured film having a high hardness at a low heating temperature by the combination with the specific polymerizable compound (A).

Dendrimers and hyperbranched polymers are described in, for example, Japanese Patent Application Laid-Open No. 2012-173549, International Publication No. 2008-047620, Japanese Patent Application Laid-Open No. 2012-83594, and the like. These compounds have a core portion, a branched chain portion bonded to the core portion, and an end group bonded to the branched chain portion. The branched chain portion includes a highly branched structure in which a two-dimensional or three-dimensional branched partial structure is repeated two or more steps, and the terminal group has a large number of functional groups (for example, a hydroxy group, a carboxyl group, an amino group). , Epoxy group, acryloyl group, and methacryloyl group). Such dendrimers and hyperbranched polymers are dendritic compounds having a molecular weight of 1300 or more.
The compound constituting the core is preferably synthesized using a branched polyhydric alcohol having three or more chain groups having a methylol group at the end, and further having a chain shape having a methylol group at the end. Those synthesized using a branched polyhydric alcohol having 4 or more groups are particularly preferred.
Preferable specific examples of the polyhydric alcohol include, for example, pentaerythritol, dipentaerythritol, trimethylolpropane and the like. A structure in which branching is repeated by connecting a linking group having a branched structure (hereinafter also referred to as a branched chain portion) to the hydroxy group of the polyhydric alcohol in two or more stages. That is, a branched chain part is bonded to each branched chain end of the branched structure closest to the hydroxy group of the polyhydric alcohol to form a highly branched compound, and at least a part of the functional group described above is formed at the terminal. Are combined. When a group other than a functional group is included at the terminal, these groups include an alkyl group such as a methyl group.
Examples of the core part include structural units represented by the following structures (1) to (4).

[In structure (1), * part represents a binding site with a branched chain part. ]

[In the structure (2), n represents an integer of 0 to 2, and the * part has the same meaning as described above. ]

[In structure (3), the * part has the same meaning as described above. ]

[In structure (4), the * part has the same meaning as described above. ]

The branched chain portion is preferably a structural unit having three or more branched structures, and examples thereof include polyamide, polyester, polyether, polyurethane, and polyurea. Of these, polyester units and polyurethane units are preferred. As the branched chain part, a polyhydroxycarboxylic acid unit is preferable, and a unit represented by the following structure (5) or structure (6) is more preferable.

[In structure (5), * part represents a binding site with a core part or a branched chain unit.

[In structure (6), * part represents a binding site with a core part or a branched chain unit.

The core portion and the branched chain portion may be bonded by a single bond, or may be bonded via a bonding site derived from an alkylene oxide such as ethylene oxide or propylene oxide. In the case of bonding through a bonding site derived from alkylene oxide, it is preferable that the oxygen terminal side of alkylene oxide is bonded to the * part of the branched chain.

The group bonded to the terminal of the multi-branched compound is preferably a group having an ethylenically unsaturated bond, and examples of such a group include a (meth) acryloyl group and a vinyloxy group. Of these, a (meth) acryloyl group is preferable.

Moreover, the alkali-developable multi-branched polymer described in International Publication No. 2008-047620 is more advantageous for pattern formation by alkali development because of increased solubility before curing by radiation.

These compounds can be produced, for example, by a method described in International Publication No. 2008/047620 pamphlet or Japanese Patent Application Laid-Open No. 2008-174518.
The molecular weight or the weight average molecular weight of these compounds is 1300 or more and 100,000 or less, more preferably 1300 or more and 20000 or less, further preferably 1300 or more and 15000 or less. The viscosity at 25 ° C. is preferably 100 Pa · s to 500,000 Pa · s, more preferably 300 to 300,000 Pa · s.

Specifically, for example, compounds represented by the following structural formulas (B-1) to (B-5) can be given.

Also, under the trade names, Esdrimer HU-22 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Biscoat # 1000 (manufactured by Osaka Organic Chemical Co., Ltd., weight average molecular weight: 4000), STAR-501 (manufactured by Osaka Organic Chemical Co., Ltd., weight average Molecular weight: 11000), A-HBR-5 (Shin Nakamura Chemical Co., Ltd., weight average molecular weight: 8000), New Frontier R-1150 (Daiichi Kogyo Seiyaku Co., Ltd., weight average molecular weight: 11500), SN-2301 ( Sartomer, weight average molecular weight: 7500), products sold under the name “Hypertech” manufactured by Nissan Chemical Industries, UR-101 (weight average molecular weight: 8000), Dendron product number 686581 (SIGMA- A product made by ALDRICH, weight average molecular weight: 3803, etc. can be used. Compound selected from the group consisting of chromatography, and the hyperbranched polymer by itself, may be contained in combination of two or more.

(B) The content of the multi-branched compound is preferably 5% by mass or more and 70% by mass or less, and particularly preferably 10% by mass or more and 65% by mass or less, based on the total solid content of the curable composition. .

The curable composition may contain a polymerizable compound (hereinafter also referred to as “additionally polymerizable compound”) that is different from both the (A) specific polymerizable compound and the (B) hyperbranched compound. Such an additional polymerizable compound is a compound that can be polymerized by an active radical or an acid radical generated from (C) an initiator, and examples thereof include a compound having a polymerizable ethylenically unsaturated bond. .
Specifically, for example, a polymerizable compound having at least one ethylenically unsaturated double bond, the components described in paragraphs [0010] to [0020] of JP-A-2006-23696, Mention may be made of the components described in paragraph numbers [0027] to [0053] of 2006-64921. The polymerizable compound is preferably a compound having a terminal ethylenically unsaturated bond, and more preferably selected from compounds having two or more terminal ethylenically unsaturated bonds.

Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and multimers thereof.
In addition, a urethane-added polymerizable compound produced by an addition reaction between an isocyanate and a hydroxyl group is also suitable, such as JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. And the ethylene oxide skeletons described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Urethane compounds having them are also suitable.
Other examples include polyester acrylates, epoxy resins and (meth) described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reacting with acrylic acid. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

Specific examples include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate. , Pentaerythritol tetra (meth) acrylate EO modified products, dipentaerythritol hexa (meth) acrylate EO modified products, etc., and commercially available products include NK ester A-TMMT, NK ester A-TMM-3, and NK oligo UA. -32P, NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix M-305, Aronix M-306, Aronix M-309, Aronix M-450, Aronix M -402, TO-1382, TO-2349 (above, manufactured by Toagosei Co., Ltd.), V # 802 (produced by Osaka Organic Chemical Industry Co., Ltd.), KAYARAD D-330, D-320, D-310, DPHA ( As mentioned above, Nippon Kayaku Co., Ltd.) can be mentioned as a preferable example.
These polymerizable compounds can be used alone or in combination of two or more.

When an additional polymerizable compound is contained in the curable composition, the content is preferably 0.01% by mass or more and 20% by mass or less based on the total mass of the total solid content of the curable composition. 1% by mass to 10% by mass is more preferable, and 0.5% by mass to 8% by mass is particularly preferable.

[(C) initiator]
(C) The initiator is at least one compound selected from the group consisting of a photopolymerization initiator and a thermal polymerization initiator.
(C) When a photopolymerization initiator is contained as an initiator, a patterned cured film can be formed by a lithographic process, which is advantageous when forming a color separation pixel of a color filter. is there. Of course, it is also possible to form a protective film by performing full-surface solid exposure.
(C) Even when a thermal polymerization initiator is contained as an initiator, if an infrared ray such as an infrared laser beam is used as a light source, a patterned cured film can be formed by a lithographic process. Furthermore, it can also be used for formation of a protective film by performing whole surface solid exposure.
(C) When both a photopolymerization initiator and a thermal polymerization initiator are contained as an initiator, for example, a patterned cured film is formed as a light source by a lithographic process using ultraviolet rays as a light source. Heating is preferable because a patterned cured film having a much higher hardness can be obtained.

<(C-1) Photopolymerization initiator>
As the photopolymerization initiator, known compounds can be suitably used. For example, triazine derivatives, oxadiazole derivatives, oxime initiators, acetophenone initiators, titanocene initiators, acylphosphine oxide initiators. Etc. are preferred.
Specifically, for example, the components described in paragraph numbers [0012] to [0020] of JP-A-2006-23696, and the paragraphs [0050] to [0053] of JP-A-2006-64921 are described. Ingredients.

Preferred (C-1) photopolymerization initiators usable in the present invention include, for example, 2-trichloromethyl-5- (p-styrylmethyl) -1,3,4-oxadiazole, 2,4-bis (Trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) -3-bromophenyl] -s-triazine, 7- [2- [4- (3-hydroxymethylpiperidino) -6 -Diethylamino] triazinylamino] -3-phenylcoumarin, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenylketone, 2-hydroxy-2-methyl-1-phenyl -Propan-1-one, 1- [4-2-2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1 {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopro Pan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (η5- 2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzoyloxime), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl And ethanone (O-acetyloxime), a mixture of oxyphenylacetic acid 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid 2- (2-hydroxyethoxy) ethyl ester, and the like.

Among them, 2-trichloromethyl-5- (p-styrylmethyl) -1,3,4-oxadiazole, 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonyl) Methyl) -3-bromophenyl] -s-triazine, 7- [2- [4- (3-hydroxymethylpiperidino) -6-diethylamino] triazinylamino] -3-phenylcoumarin, 2,2- Dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenylketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -Phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane- -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzoyloxime), 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl] ethanone (O-acetyloxime), oxyphenylacetic acid 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid 2- (2-hydroxyethoxy) A mixture of ethyl esters is particularly preferred, but not limited thereto.

Furthermore, it is also preferable to contain at least one photopolymerization initiator having a carbazole structure represented by the following general formula (a).

In general formula (a), R and X each represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 1 to 5. R is preferably an acyl group from the viewpoint of increasing sensitivity, and specifically, an acetyl group, a propionyl group, a benzoyl group, and a toluyl group are preferable. A is an unsubstituted alkylene group, an alkylene group substituted with an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating, An alkylene group substituted with an alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) A substituted alkylene group is preferred.

Ar is preferably a substituted or unsubstituted phenyl group from the viewpoint of increasing sensitivity and suppressing coloring due to heating. In the case of a substituted phenyl group, the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. X is an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkenyl that may have a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. Group, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy group which may have a substituent, a substituent An arylthioxy group which may have an amino group and an amino group which may have a substituent are preferable.
In general formula (a), n is preferably an integer of 1 to 2.

Specific examples of the photopolymerization initiator represented by the general formula (a) include the following exemplary compound (V-3).

<(C-2) Thermal polymerization initiator>
As the thermal polymerization initiator, known compounds can be suitably used. For example, ketone peroxide compounds, peroxyketal compounds, hydroperoxide compounds, dialkyl peroxide compounds, diacyl peroxide compounds, Peroxydicarbonate compounds, peroxyester compounds and the like are used, and these thermal polymerization initiators are disclosed in company product catalogs and the like. In addition, a thermal polymerization initiator containing a hydroxylamine ester described in JP 2012-521573 is preferably used in the present invention. Specific compound examples are as follows.

(C) The content of the initiator is preferably 0.1% by mass or more and 20% by mass or less, and 0.5% by mass or more and 10% by mass or less based on the total amount of the total solid content of the curable composition. More preferably, it is more preferably 1% by mass or more and 5% by mass or less.

[(D) Resin having acidic group in side chain]
The curable composition according to the present invention may contain (D) a resin having an acidic group in the side chain (hereinafter also referred to as “specific resin”).
The specific resin is not particularly limited as long as it has an acidic group in the side chain, but has a branched and / or alicyclic structure in the side chain in addition to the group having an acidic group: Y (y mol%). It preferably contains a group: X (x mol%) and a group having an ethylenically unsaturated group: Z (z mol%), and optionally has other groups (L) (1 mol%). It may be. Moreover, at least 2 or more types of groups selected from X, Y, and Z may be contained in one group in specific resin.

The acidic group is not particularly limited and may be appropriately selected from known ones, and examples thereof include a carboxyl group, a sulfonic acid group, a sulfonamide group, a phosphoric acid group, and a phenolic hydroxyl group. Among these, a carboxy group and a phenolic hydroxyl group are preferable from the viewpoint of excellent developability and water resistance of the cured film.

The monomer used for introducing an acidic group into the side chain of the specific resin (a monomer having an acidic group) is not particularly limited, and styrenes, (meth) acrylates, vinyl ethers, vinyl esters. And those obtained by introducing an acidic group such as the above carboxyl group into (meth) acrylamides and the like, (meth) acrylates, vinyl esters, and those having an acidic group introduced into (meth) acrylamides are preferred. Preferably, an acid group is introduced into (meth) acrylates.
In this specification, when referring to “acryl” and / or “methacryl”, when referring to “(meth) acryl” and / or “acrylate” and / or “methacrylate”, “(meth) )) Acrylate ".

Specific examples of the monomer having an acidic group can be appropriately selected from known ones such as (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, Itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, acrylic acid dimer, addition reaction product of hydroxyl group-containing monomer and cyclic acid anhydride, ω-carboxy-polycaprolactone mono (meth) acrylate Etc. As these, those produced as appropriate may be used, or commercially available products may be used.

Examples of the monomer having a hydroxyl group used in the addition reaction product of the monomer having a hydroxyl group and a cyclic acid anhydride include 2-hydroxyethyl (meth) acrylate. Examples of the cyclic acid anhydride include maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride. Among these, (meth) acrylic acid and the like are preferable in terms of excellent developability and low cost.

The amount of the monomer having an acidic group in the side chain in the specific resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and particularly preferably 20 to 50 mol%. When the group having an acidic group in the side chain is within the above range, good curability and developability can be obtained.
In addition, the acid value suitable as the specific resin varies within a preferable range depending on the molecular structure that can be taken, but is generally preferably 20 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 to 130 mgKOH / g. Particularly preferred is g. When the acid value is within the preferable range, an insulating layer and an overcoat layer excellent in good insulation, transparency, water resistance, alkali resistance and acid resistance can be obtained. For this reason, what is necessary is just to determine the usage-amount of the monomer which has an acidic group in a side chain so that an acid value may become the said range.

Further, as described above, the specific resin may further have a “group having a branched and / or alicyclic structure” or an “ethylenically unsaturated group” in the side chain.
That is, the specific resin in the present invention includes a group having a branched and / or alicyclic structure in the side chain: X (x mol%), a group having an acidic group: Y (y mol%), and ethylenically unsaturated. The group having a group: Z (z mol%) and a copolymer having at least ternary copolymer each having a different copolymer unit, the insulation, transparency and water resistance of the formed resin pattern From the viewpoints of alkali resistance, acid-resistant development residue reduction, and reticulation. Specifically, a copolymer obtained by copolymerizing at least one of the monomers constituting the X, Y, and Z is preferable.

Hereinafter, the “group having a branched and / or alicyclic structure in the side chain” will be described.
Examples of the branched group include branched alkyl groups having 3 to 12 carbon atoms, such as i-propyl group, i-butyl group, s-butyl group, t-butyl group, isopentyl group, and neopentyl group. 2-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, i-amyl group, t-amyl group, 3-octyl, t-octyl and the like. Among these, i-propyl group, s-butyl group, t-butyl group, isopentyl group and the like are preferable, and i-propyl group, s-butyl group, t-butyl group and the like are more preferable.

Examples of the group having an alicyclic structure include an alicyclic hydrocarbon group having 5 to 20 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, an adamantyl group. , Tricyclodecyl group, dicyclopentenyl group, dicyclopentanyl group, tricyclopentenyl group, and tricyclopentanyl group. Among these, a cyclohexyl group, a norbornyl group, an isobornyl group, an adamantyl group, a tricyclodecyl group, a tricyclopentenyl group, a tricyclopentanyl group, and the like are preferable, and a cyclohexyl group, a norbornyl group, an isobornyl group, a tricyclopentenyl group, and the like. Is preferred.

Examples of the monomer containing a group having a branched and / or alicyclic structure in the side chain include styrenes, (meth) acrylates, vinyl ethers, vinyl esters, (meth) acrylamides, and the like ( (Meth) acrylates, vinyl esters and (meth) acrylamides are preferred, and (meth) acrylates are more preferred.

Specific examples of the monomer containing a group having a branched structure in the side chain include i-propyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, (meth ) T-butyl acrylate, i-amyl (meth) acrylate, t-amyl (meth) acrylate, sec-iso-amyl (meth) acrylate, 2-octyl (meth) acrylate, (meth) acrylic acid 3-octyl, t-octyl (meth) acrylate, and the like, among which i-propyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl methacrylate, and the like are preferable, and more preferable. I-propyl methacrylate, t-butyl methacrylate and the like.

Next, a specific example of the monomer containing a group having an alicyclic structure in the side chain is (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Specific examples include (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth) acrylic. Acid-3-methyl-1-adamantyl, (meth) acrylic acid-3,5-dimethyl-1-adamantyl, (meth) acrylic acid-3-ethyladamantyl, (meth) acrylic acid-3-methyl-5-ethyl 1-adamantyl, (meth) acrylic acid-3,5,8-triethyl-1-adamantyl, (meth) acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth) acrylic acid 2- Methyl-2-adamantyl, (meth) acrylic acid 2-ethyl-2-adamantyl, (meth) acrylic acid 3-hydroxy-1-adamantyl, (meth) acrylic acid Tahydro-4,7-mentanoinden-5-yl, octahydro-4,7-mentanoinden-1-ylmethyl (meth) acrylate, (meth) acrylate-1-menthyl, tricyclo (meth) acrylate Decyl, (meth) acrylic acid-3-hydroxy-2,6,6-trimethyl-bicyclo [3.1.1] heptyl, (meth) acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo [ 4.1.0] heptyl, (nor) bornyl (meth) acrylate, isobornyl (meth) acrylate, fuentyl (meth) acrylate, 2,2,5-trimethylcyclohexyl (meth) acrylate, (meth) And cyclohexyl acrylate.
Among these (meth) acrylate esters, cyclohexyl (meth) acrylate, (nor) bornyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylic acid-1-adamantyl, (meth) acrylic acid -2-adamantyl, fuentyl (meth) acrylate, 1-menthyl (meth) acrylate, tricyclodecyl (meth) acrylate, and the like, cyclohexyl (meth) acrylate, (nor) bornyl (meth) acrylate, Particularly preferred are isobornyl (meth) acrylate and 2-adamantyl (meth) acrylate.

The copolymer composition ratio of the respective components of the specific resin is determined in consideration of the glass transition temperature and the acid value, and cannot be generally stated, but “group having a branched and / or alicyclic structure in the side chain” The content of the repeating unit is preferably 10 mol% to 70 mol%, more preferably 15 mol% to 65 mol%, and particularly preferably 20 mol% to 60 mol%. When the content of the repeating unit having a group having a branched and / or alicyclic structure in the side chain is within the above range, good developability is obtained and the developer resistance of the image area is also good.

The “ethylenically unsaturated group” is not particularly limited, but is preferably an allyl group or a (meth) acryloyl group. The connection between the ethylenically unsaturated group and the monomer is not particularly limited as long as it is a divalent linking group such as an ester group, an amide group, or a carbamoyl group. The method for introducing an ethylenically unsaturated group into the side chain can be appropriately selected from known ones. For example, a compound having an acidic group (for example, acrylic acid, methacrylic acid, vinylbenzoic acid, maleic acid, maleic acid) A method of adding a (meth) acrylate having an epoxy group to a monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, etc., a group having a hydroxyl group (for example, 2- Examples thereof include a method of adding (meth) acrylate having an isocyanate group to hydroxyethyl methacrylate, 2-hydroxyethyl acrylate and the like, and a method of adding (meth) acrylate having a hydroxy group to a group having an isocyanate group.

Among these, the method of adding (meth) acrylate having an epoxy group to a repeating unit having an acidic group is most preferable because it is the easiest to produce and is low in cost.
The (meth) acrylate having an ethylenically unsaturated bond and an epoxy group is not particularly limited as long as it has these.

The content of the repeating unit having an “ethylenically unsaturated group in the side chain” is preferably 10 to 70 mol%, more preferably 20 to 70 mol%, particularly preferably 30 to 70 mol%. When the group having an ethylenically unsaturated group in the side chain is within the above range, developability and curability are also good.

The specific resin may contain a repeating unit derived from another monomer in addition to the three kinds of repeating units. Such other monomer is not particularly limited, for example, (meth) acrylic acid ester having no branched and / or alicyclic structure, styrene, vinyl ether, dibasic acid anhydride group, vinyl ester group, And monomers having a hydrocarbon alkenyl group.

There is no restriction | limiting in particular as said vinyl ether group, For example, a butyl vinyl ether group etc. are mentioned.
The dibasic acid anhydride group is not particularly limited, and examples thereof include a maleic anhydride group and an itaconic anhydride group.
There is no restriction | limiting in particular as said vinyl ester group, For example, a vinyl acetate group etc. are mentioned.
There is no restriction | limiting in particular as said hydrocarbon alkenyl group, For example, a butadiene group, an isoprene group, etc. are mentioned.

As the content of the repeating unit derived from the other monomer in the specific resin, the molar composition ratio is preferably 0 mol% to 30 mol%, more preferably 0 mol% to 20 mol%. preferable.

Specific examples of the specific resin include compounds represented by compounds P-1 to P-35 described in paragraph numbers [0057] to [0063] of JP-A-2008-146018.

The specific resin is made from a two-stage process including a monomer (co) polymerization reaction process and an ethylenically unsaturated group introduction process. First, the (co) polymerization reaction is made by a (co) polymerization reaction of various monomers, and is not particularly limited and can be appropriately selected from known ones. For example, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization and the like can be appropriately selected for the active species of polymerization. Among these, radical polymerization is preferable from the viewpoint of easy synthesis and low cost. Moreover, there is no restriction | limiting in particular also about the polymerization method, It can select suitably from well-known things. For example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and the like can be appropriately selected. Among these, the solution polymerization method is more desirable.

The weight average molecular weight of the copolymer suitable as the specific resin is that the strength of the cured film can be improved by including the specific resin, and that a patterned cured film can be easily produced by a lithographic process. In this respect, it is preferably 10,000 to 100,000, more preferably 12,000 to 60,000, and particularly preferably 15,000 to 45,000.

The glass transition temperature (Tg) suitable as the specific resin is preferably 40 to 180 ° C., more preferably 45 to 140 ° C., and particularly preferably 50 to 130 ° C. When the glass transition temperature (Tg) is within the preferred range, an insulating layer and an overcoat layer excellent in good insulation, transparency, water resistance, alkali resistance and acid resistance can be obtained.

The specific resin has a glass transition temperature (Tg) of 40 to 180 ° C. and a weight average molecular weight of 10,000 to 100,000. Good insulation, transparency, water resistance, alkali resistance, acid resistance It is preferable in that an insulating layer and an overcoat layer excellent in the above can be obtained.
Furthermore, among the preferable examples of the specific resin, a resin in which all of the molecular weight, the glass transition temperature (Tg), and the acid value are in the preferable range is more preferable.

The content of the specific resin is preferably 5% by mass to 70% by mass and more preferably 10% by mass to 50% by mass with respect to the total solid content of the curable composition.
Here, the solid content refers to the total amount of other components excluding the solvent in the curable composition.
In addition to the specific resin, the curable composition according to the present invention may contain a resin (other resin) other than the resin having an acidic group in the side chain, as long as the effects of the present invention are not impaired. When other resins are contained, the content thereof is preferably 30 parts by mass or less with respect to 100 parts by mass of the specific resin, and from the viewpoint of the effect, an embodiment including only the specific resin as the resin is more preferable. preferable.

[(E) Colorant]
In the curable composition of the present invention, any of a pigment and a dye can be used as the colorant (E). When the curable composition of the present invention is used as a photosensitive resin composition in a color filter, it is desirable to use a dye for the purpose of obtaining a composition having high luminance. In this case, the dye may be used alone, or a plurality of dyes may be mixed according to the required hue. In many cases, it is difficult to obtain the color required for the color filter in the absorption spectrum obtained with a single dye, so it is practical to use a plurality of dyes.
In general, a pigment having higher heat resistance than the dye can be used in combination with the dye. In particular, in some applications, if the dye does not satisfy the required characteristics, it may be considered that the colorant is composed of only the pigment, although the luminance is reduced.
Regardless of whether a dye or a pigment is used as the colorant, the content of the colorant in the curable composition of the present invention is 0.5 to 70% by mass relative to the total solid content of the composition. Preferably, 1 to 60% by mass is more preferable. When the content of the pigment is within the above range, it is effective to secure excellent color characteristics and achieve both performance as a curable composition.

As the dye, various dyes including those known from Color Index Number can be used. Particularly, barbituric acid azo dyes, pyrimidine azo dyes, pyrazole azo dyes, pyridone azo dyes, xanthene dyes. , Triarylmethane dyes, dipyrromethene dyes, azapyromethene dyes, methine dyes, cyanine dyes, squarylium dyes, phthalocyanine dyes, porphyrin dyes, anthraquinone dyes, merocyanine dyes, benzopyran dyes, indigo dyes One type is preferably used.
Which of the above dyes is used may be appropriately selected depending on a required hue or the like.

<Dye represented by general formula (I)>
As the colorant (E), for example, a dye represented by the general formula (I) can be used.

In the general formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a monovalent substituent, R ⁷ represents a hydrogen atom, A halogen atom, an alkyl group, an aryl group, or a heterocyclic group is represented.

In the general formula (I), examples of the monovalent substituent represented by R ¹ to R ⁶ include a halogen atom (for example, a fluorine atom, a chlorine atom and a bromine atom), an alkyl group (preferably having a carbon number of 1 to 48, more preferably a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group Hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), alkenyl group (preferably). Is an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as a vinyl group, an allyl group, or a 3-buten-1-yl group. An aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably an aryl group having 6 to 24 carbon atoms, such as a phenyl group or a naphthyl group), a heterocyclic group (preferably a carbon group). A heterocyclic group having 1 to 32, more preferably 1 to 18 carbon atoms, such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl Group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group).

Silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, such as trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group, t-hexyldimethylsilyl group) A hydroxyl group, a cyano group, a nitro group, an alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably an alkoxy group having 1 to 24 carbon atoms, such as a methoxy group, an ethoxy group, 1- A butoxy group, a 2-butoxy group, an isopropoxy group, a t-butoxy group, a dodecyloxy group, and a cycloalkyloxy group such as a cyclopentyloxy group and a cyclohexyloxy group), an aryl An oxy group (preferably an aryl having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms) An oxy group, for example, a phenoxy group and a 1-naphthoxy group), a heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group), silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, , Trimethylsilyloxy group, t-butyldimethylsilyloxy group, diphenylmethylsilyloxy group), acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, , Acetoxy group, pivaloyloxy group, benzoyloxy group, dodecanoyloxy group ), An alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, and a cycloalkyl group) Examples of the oxycarbonyloxy group include a cyclohexyloxycarbonyloxy group), an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms). For example, a phenoxycarbonyloxy group).

A carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyl group) An oxy group, an N-ethyl-N-phenylcarbamoyloxy group), a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, Examples thereof include N, N-diethylsulfamoyloxy group and N-propylsulfamoyloxy group), alkylsulfonyloxy group (preferably alkyl having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms). A sulfonyloxy group, for example, a methylsulfonyloxy group, hexadecylsulfonyl An oxy group, a cyclohexylsulfonyloxy group), an arylsulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as a phenylsulfonyloxy group). An acyl group (preferably an acyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexa Noyl group).

An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, 2, 6 -Di-tert-butyl-4-methylcyclohexyloxycarbonyl group), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, ), A carbamoyl group (preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a carbamoyl group, N, N-diethylcarbamoyl group, N- Ethyl-N-octylcarbamo , N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methylN-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group), amino group ( Preferred is an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms. For example, an amino group, a methylamino group, an N, N-dibutylamino group, a tetradecylamino group, a 2-ethylhexylamino group, a cyclohexyl group. Anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as an anilino group and an N-methylanilino group), a heterocyclic amino group (Preferably a heterocyclic amino group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms. And a carbonamido group (preferably a carbonamido group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an acetamido group, a benzamido group, a tetradecanamido group, a pivaloylamido group, a cyclohexaneamido). Group).

Ureido group (preferably a ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, and examples thereof include ureido group, N, N-dimethylureido group and N-phenylureido group), imide. A group (preferably an imide group having 36 or less carbon atoms, more preferably 24 or less carbon atoms, such as N-succinimide group and N-phthalimide group), an alkoxycarbonylamino group (preferably having 2 to 48, more preferably an alkoxycarbonylamino group having 2 to 24 carbon atoms, and examples thereof include a methoxycarbonylamino group, an ethoxycarbonylamino group, a t-butoxycarbonylamino group, an octadecyloxycarbonylamino group, and a cyclohexyloxycarbonylamino group. Aryloxycarbonylamino group An aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms is preferable, and examples thereof include a phenoxycarbonylamino group. A sulfonamide group (preferably having 1 to 48 carbon atoms, more Preferred is a sulfonamide group having 1 to 24 carbon atoms, and examples thereof include a methanesulfonamide group, a butanesulfonamide group, a benzenesulfonamide group, a hexadecanesulfonamide group, and a cyclohexanesulfonamide group.), Sulfamoylamino A group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dipropylsulfamoylamino group, N-ethyl-N-dodecylsulfamoyl group). An amino group), an azo group (preferably having 1 to 32 carbon atoms). An azo group having 1 to 24 carbon atoms is more preferable, and examples thereof include a phenylazo group and a 3-pyrazolylazo group), an alkylthio group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms). An alkylthio group, for example, a methylthio group, an ethylthio group, an octylthio group, a cyclohexylthio group), an arylthio group (preferably an arylthio group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, For example, a phenylthio group), a heterocyclic thio group (preferably a heterocyclic thio group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as a 2-benzothiazolylthio group, 2 -Pyridylthio group, 1-phenyltetrazolylthio group).

An alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably an alkylsulfinyl group having 1 to 24 carbon atoms, such as a dodecanesulfinyl group), an arylsulfinyl group (preferably having 6 to 32 carbon atoms, More preferably, it is an arylsulfinyl group having 6 to 24 carbon atoms, such as a phenylsulfinyl group, and an alkylsulfonyl group (preferably having 1 to 48 carbon atoms, more preferably an alkylsulfonyl group having 1 to 24 carbon atoms). And examples thereof include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, an isopropylsulfonyl group, a 2-ethylhexylsulfonyl group, a hexadecylsulfonyl group, an octylsulfonyl group, and a cyclohexylsulfonyl group. A rusulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, more preferably an arylsulfonyl group having 6 to 24 carbon atoms, such as a phenylsulfonyl group and a 1-naphthylsulfonyl group), a sulfamoyl group (preferably a carbon Sulfamoyl group having 32 or less, more preferably 24 or less carbon atoms, such as sulfamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N— Phenylsulfamoyl group, N-cyclohexylsulfamoyl group), sulfo group, phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenoxy (A phosphonyl group, an octyloxy phosphonyl group, and a phenyl phosphonyl group are mentioned.) Phosphinoylamino group (preferably phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as diethoxyphosphinoylamino group and dioctyloxyphosphinoylamino group) Represents.).

In the case where the monovalent substituent described above is a further substitutable group, it may be further substituted with any of the groups described above. In addition, when it has two or more substituents, those substituents may be the same or different.

In the general formula (I), R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ are each independently bonded to each other to form 5, 6 or 7 members. The ring may be formed. In addition, as a ring formed, either a saturated ring or an unsaturated ring may be sufficient. Examples of the 5-membered, 6-membered, or 7-membered saturated ring or unsaturated ring include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, Examples include a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring, a pyrazine ring and a pyridazine ring, and preferably a benzene ring and a pyridine ring.

In addition, when the formed 5-membered, 6-membered and 7-membered rings are further substitutable groups, they are substituted with any of the groups exemplified as the monovalent substituent in the general formula (I). When it is substituted with two or more substituents, these substituents may be the same or different.
R ¹ and R ⁶ preferably do not form a ring.
In the general formula (I), when R ⁷ is a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, these preferred ranges are the halogen atom, alkyl group, R ¹ to R ⁶ described above, This is the same as the preferred range of the aryl group or heterocyclic group.

Next, the metal atom or metal compound that forms the metal complex compound will be described.
The metal or metal compound may be any metal atom or metal compound capable of forming a complex, and may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, or 2 Valent metal chlorides are included. For example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ Further, metal chlorides such as GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ are also included.
Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B from the viewpoints of stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex Or VO is preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B, or VO is most preferable. Among these, Zn is particularly preferable.

In the metal complex compound in which the structure represented by the general formula (I) is coordinated to a metal atom or a metal compound, preferred embodiments are shown below.
That is, in the general formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, Amino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, azo group, alkylsulfonyl group, arylsulfonyl group, or phosphinoylamino group R ² and R ⁵ are each independently an alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, nitro group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group , Alkylsulfonyl group, arylsulfonyl group, or sulfamo And R ³ and R ⁴ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, carbonamido group, ureido Represents a group, an imide group, an alkoxycarbonylamino group, a sulfonamido group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl A group, an aryl group, or a heterocyclic group, in which the metal atom or metal compound is Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO.

<Dye represented by formula (II)>
(E) As a coloring agent, the dye represented, for example by general formula (II) can be used.

In the general formula (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent.
Examples of the monovalent substituent when R ¹ to R ⁶ represent a monovalent substituent include the monovalent substituents exemplified for R ¹ to R ⁶ in the general formula (I). Is the same.
Note that at least one pair of R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ is bonded to each other to form a 5-membered, 6-membered, or 7-membered saturated ring, Alternatively, an unsaturated ring may be formed. When the formed 5-membered, 6-membered, and 7-membered rings are further substitutable groups, they are further substituted with the substituents described for R ¹ to R ⁶ in the general formula (I). In the case where it is substituted with two or more substituents, these substituents may be the same or different.

When the compound represented by the general formula (II) forms a metal complex, the metal is preferably Zn, Mg, Sc, Fe, Al, Cr, Si, Pt, Pd, Mo, Mn, Cu, Ni , Co, TiO, or VO, more preferably Zn, Mg, Sc, Fe, Al, Mn, Cu, Ni, Co, TiO, or VO, and particularly preferably Zn, Cu, or Co. .

<Dye represented by general formula (III)>
(E) As the colorant, for example, a dye represented by the general formula (III) can be used.

In the general formula (III), R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic carbon atom having 6 to 10 carbon atoms. Represents a hydrogen group.
Examples of the saturated hydrocarbon group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, octyl, 2-ethylhexyl. , Cyclooctyl, nonyl, decanyl, tricyclodecanyl, methoxypropyl, ethoxypropyl, hexyloxypropyl, 2-ethylhexyloxypropyl, methoxyhexyl, ethoxypropyl, and the like. Among them, preferred is an alkyl group having 1 to 9 carbon atoms, and more preferred is an alkyl group having 1 to 8 carbon atoms.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include groups such as phenyl and naphthyl. The aromatic hydrocarbon group having 6 to 10 carbon atoms includes a halogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, —OH, —OR, —SO ₃ ⁻ , —SO ₃ H, —SO ₃ M, —CO _It may be substituted with ₂ H, —CO ₂ R ¹³ , —SO ₃ R ¹³ , —SO ₂ NHR ¹⁴ , or —SO ₂ NR ¹⁴ R ¹⁵ . R and R ¹³ each represent a saturated hydrocarbon group having 1 to 10 carbon atoms, and have the same meaning as the “saturated hydrocarbon group having 1 to 10 carbon atoms” in R ⁸ to R ¹¹ , and the preferred embodiments are also the same. Details of R ¹⁴ , R ¹⁵ , and M will be described later.

Examples of the halogen atom include fluorine, chlorine, bromine and the like.
Examples of the “—SO ₃ R ¹³ ” include methanesulfonyl, ethanesulfonyl, hexanesulfonyl, decanesulfonyl and the like.
Examples of the “—CO ₂ R ¹³ ” include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, isobutyloxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl. , Cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, cyclooctyloxycarbonyl, nonyloxycarbonyl, decanyloxycarbonyl, tricyclodecanyl Oxycarbonyl, methoxypropyloxycarbonyl, ethoxypropyloxy Examples include cicarbonyl, hexyloxypropyloxycarbonyl, 2-ethylhexyloxypropyloxycarbonyl, methoxyhexyloxycarbonyl and the like.

R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, Alternatively, it represents an aromatic heterocyclic group having 5 to 10 carbon atoms, and R ¹⁴ and R ¹⁵ may be bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms. In addition, the aromatic hydrocarbon group and the aromatic heterocyclic group represented by R ¹⁴ and R ¹⁵ are —OH, a saturated hydrocarbon group having 1 to 10 carbon atoms, —OR, —NO ₂ , —CH═ It may be substituted with CH ₂ , —CH═CHR, or a halogen atom. R represents a saturated hydrocarbon group having 1 to 10 carbon atoms. The saturated hydrocarbon group having 1 to 10 carbon atoms has the same meaning as the “saturated hydrocarbon group having 1 to 10 carbon atoms” in the above R ⁸ to R ¹¹ , and the preferred embodiment is also the same.

The linear or branched alkyl group having 1 to 10 carbon atoms represented by R ¹⁴ and R ¹⁵ may be unsubstituted or substituted, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Examples include pentyl, isopentyl, hexyl, 2-ethylhexyl, 1,5-dimethylhexyl, octyl and the like. Of these, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable.

The cycloalkyl group having 3 to 30 carbon atoms represented by R ¹⁴ and R ¹⁵ may be unsubstituted or substituted, and examples thereof include groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl. Is mentioned. Of these, a cycloalkyl group having 3 to 15 carbon atoms is preferable.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ¹⁴ and R ¹⁵ include groups such as phenyl and naphthyl.

Examples of the aromatic heterocyclic group having 5 to 10 carbon atoms represented by R ¹⁴ and R ¹⁵ include aromatic heterocyclic groups having an oxygen atom, a nitrogen atom or the like as a hetero atom, such as a pyrrole ring group and a pyrazine ring. Pyridine ring group, thiazine ring group, triazine ring group, pyran ring group, furan ring group, morpholine ring group, and the like.

The linear or branched alkyl group having 1 to 10 carbon atoms and the cycloalkyl group having 3 to 30 carbon atoms may be substituted. Examples of the substituent when they are substituted include a hydroxyl group, a halogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, an aromatic heterocyclic group having 5 to 10 carbon atoms, —CH═CH ₂ , Or —CH═CHR ⁶ (R ⁶ : a saturated hydrocarbon group having 1 to 10 carbon atoms). The methylene group contained in the cycloalkyl group may be substituted with an oxygen atom, a carbonyl group, or —NR ⁶ — (R ⁶ : a saturated hydrocarbon group having 1 to 10 carbon atoms). The saturated hydrocarbon group having 1 to 10 carbon atoms has the same meaning as the “saturated hydrocarbon group having 1 to 10 carbon atoms” in R ¹ to R ⁴ , and the preferred embodiment is also the same.
The aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted. As the substituent when it is substituted, for example, ethyl, propyl, phenyl, dimethylphenyl, —SO ₃ R (R: a saturated hydrocarbon group having 1 to 10 carbon atoms) or —SO ₂ NHR ¹⁴ is preferable.

Examples of the substituted aromatic hydrocarbon group having 6 to 10 carbon atoms include methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, hexylphenyl, decanylphenyl, fluorophenyl, chlorophenyl, bromophenyl, hydroxyphenyl, Examples include methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, decanyloxyphenyl, and trifluoromethylphenyl.

In addition, when R ¹⁴ and R ¹⁵ are bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms, the heterocyclic ring having 1 to 10 carbon atoms is a saturated hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group , An aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic heterocyclic group having 5 to 10 carbon atoms may be substituted.

Among them, R ¹⁴ and R ¹⁵ are each a branched alkyl group having 6 to 8 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an allyl group, a phenyl group, an aralkyl group having 8 to 10 carbon atoms, carbon A hydroxyl group-containing alkyl group having 2 to 8 carbon atoms, a hydroxyl group-containing aryl group having 2 to 8 carbon atoms, or an alkoxyl group-containing alkyl group having 2 to 8 carbon atoms, an alkoxyl group-containing aryl group having 2 to 8 carbon atoms is preferable, and 2-ethylhexyl is preferable. Particularly preferred.

In —SO ₃ M, M represents a sodium atom or a potassium atom.
R ¹² represents —SO ₃ ^— , —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R, —SO ₃ R, —SO ₂ NHR ¹⁴ , or —SO ₂ NR ¹⁴ R ¹⁵ . . R, R ¹⁴ , R ¹⁵ , and M are as described above, and the preferred embodiments are also the same.

Among them, R ¹² is —CO ₂ H, ethyloxycarbonyl, sulfoxyl, 2-ethylhexyloxypropane sulfamoyl, 1,5-dimethylhexanesulfamoyl, 3-phenyl-1-methylpropanesulfamoyl, iso An embodiment that is propoxypropane sulfamoyl is preferred.

M represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ¹² may be the same or different. n1, n2, n3 and n4 each independently represents 0 or 1. However, the sum of n1 to n4 is 3 or 4.
X represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
a represents an integer of 0 or 1. a = 1 when all of n1 to n4 represent 1 and R ¹² does not represent —SO ₃ ^— , otherwise there is no positive charge on the nitrogen atom, and a = 0 is there. When a = 0, at least one group of R ⁸ to R ¹¹ and R ¹² may exist as an anion group from which one hydrogen atom is removed.

Among the above, an embodiment in which at least one of R ⁸ and R ⁹ or at least one of R ¹⁰ and R ¹¹ is an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms is preferable. More preferably, at least one of R ⁸ and R ⁹ and at least one of R ¹⁰ and R ¹¹ is an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, An embodiment in which at least one of R ⁸ and R ⁹ and at least one of R ¹⁰ and R ¹¹ is an aromatic hydrocarbon group having 6 to 10 carbon atoms is preferred.
Specific examples of the dye represented by the general formula (III) include compounds described in paragraph No. 0010 of Japanese Patent No. 3387541.

<Dye represented by formula (IV)>
(E) As a coloring agent, the dye represented, for example by general formula (IV) can be used.

In the general formula (IV), R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or 6 carbon atoms. Represents 10 to 10 aromatic hydrocarbon groups.

Examples of the saturated hydrocarbon group having 1 to 10 carbon atoms include alkyl groups (for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, Octyl, 2-ethylhexyl, cyclooctyl, nonyl, decanyl, tricyclodecanyl, methoxypropyl, ethoxypropyl, hexyloxypropyl, 2-ethylhexyloxypropyl, methoxyhexyl, ethoxypropyl, etc.), alkenyl group (for example, butenyl group, Straight-chain alkenyl groups such as hexenyl group, pentenyl group, octenyl group). Among them, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 9 carbon atoms is more preferable, and an alkyl group having 1 to 8 carbon atoms is still more preferable.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include groups such as phenyl and naphthyl. The aromatic hydrocarbon group having 6 to 10 carbon atoms includes a halogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a saturated hydrocarbon group having 1 to 10 carbon atoms, —OH, —OR, —SO ₃ ⁻ , It may be substituted with —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R, —SO ₃ R, —SO ₂ NHR.

R represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or a saturated hydrocarbon group having 1 to 10 carbon atoms, and the “aromatic hydrocarbon group having 6 to 10 carbon atoms” in the above R ¹⁶ to R ²¹ ; It is synonymous with “saturated hydrocarbon group having 1 to 10 carbon atoms”, and preferred embodiments are also the same. In addition, the “aromatic hydrocarbon group having 6 to 10 carbon atoms” and the “saturated hydrocarbon group having 1 to 10 carbon atoms” represented by R may be substituted with a halogen atom. The methylene group contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with an oxygen atom, a carbonyl group, or —NR—.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the “—SO ₃ R” include methanesulfonyl, ethanesulfonyl, hexanesulfonyl, decanesulfonyl and the like.

Examples of the “—CO ₂ R” include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, isobutyloxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, Cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, cyclooctyloxycarbonyl, nonyloxycarbonyl, decanyloxycarbonyl, tricyclodecanyloxy Carbonyl, methoxypropyloxycarbonyl, ethoxypropyloxyca Boniru, hexyloxy propyl oxycarbonyl, 2-ethylhexyloxy propyloxy, methoxy hexyloxycarbonyl and the like.

Examples of the “—SO ₂ NHR” include sulfamoyl, methanesulfamoyl, ethanesulfamoyl, propanesulfamoyl, isopropanesulfamoyl, butanesulfamoyl, isobutanesulfamoyl, pentansulfamoyl, isopentane. Sulfamoyl, neopentanesulfamoyl, cyclopentanesulfamoyl, hexanesulfamoyl, cyclohexanesulfamoyl, heptanesulfamoyl, cycloheptanesulfamoyl, octanessulfamoyl, 2-ethylhexanesulfamoyl, 1,5-dimethylhexanesulfamoyl, cyclooctanesulfamoyl, nonanesulfamoyl, decanesulfamoyl, tricyclodecanesulfamoyl, methoxypropanesulfamoyl, ethoxypropyl Pansulfamoyl, propoxypropane sulfamoyl, isopropoxypropane sulfamoyl, hexyloxypropane sulfamoyl, 2-ethylhexyloxypropane sulfamoyl, methoxyhexanesulfamoyl, 3-phenyl-1-methylpropanesulfa Moyl etc. are mentioned.
Examples of the “—OR” include a methoxy group, an ethoxy group, a propoxy group, and a hexyloxy group.
Preferable substituents when the aromatic hydrocarbon group having 6 to 10 carbon atoms is substituted include ethyl, propyl, phenyl, dimethylphenyl, —SO ₃ R, —SO ₂ NHR, and the like. —SO ₃ R and —SO ₂ NHR are as described above.

Specific examples of the substituted aromatic hydrocarbon group having 6 to 10 carbon atoms include methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, hexylphenyl, decanylphenyl, fluorophenyl, chlorophenyl, bromophenyl, and hydroxyphenyl. , Methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, decanyloxyphenyl, trifluoromethylphenyl and the like.
In the —SO ₃ M, M represents a sodium atom or a potassium atom.
R ²² and R ²³ each independently represents a hydrogen atom or a saturated hydrocarbon group having 4 to 8 carbon atoms. Examples of the saturated hydrocarbon group having 4 to 8 carbon atoms include butyl group, heptyl group, hexyl group, octyl group and the like.
R ²² and R ²³ may be bonded to each other to form an aromatic hydrocarbon ring. Preferred examples of the aromatic hydrocarbon ring in this case include a benzene ring and a naphthalene ring.
R ²⁴ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms. The saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ²⁴ has the same meaning as the “saturated hydrocarbon group having 1 to 10 carbon atoms” in R ¹⁶ to R ²¹ . R ²⁴ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
X represents a halogen atom, BF ₄ , PF ₆ , ClO ₄ , N (SO ₂ CF ₃ ) ₂ , or ArSO ₃ . Ar in ArSO ₃ represents an aromatic hydrocarbon group having 6 to 10 carbon atoms. The aromatic hydrocarbon group having 6 to 10 carbon atoms has the same meaning as the “aromatic hydrocarbon group having 6 to 10 carbon atoms” in R ¹⁶ to R ²¹ , and the preferred embodiment is also the same.
Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, and a bromine atom.

The aromatic hydrocarbon group having 6 to 10 carbon atoms represented by Ar is synonymous with the aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ¹⁶ to R ²¹ , and preferred embodiments thereof are also the same. The aromatic hydrocarbon group having 6 to 10 carbon atoms is a halogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a saturated hydrocarbon group having 1 to 10 carbon atoms, —OH, —OR, —SO ₃ ⁻ , It may be substituted with —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R, —SO ₃ R, —SO ₂ NHR, —SO ₂ N (R) ₂ . Among these, as Ar, a phenyl group and a naphthyl group are preferable.
A represents an integer of 0 or 1, and when any of R ¹⁶ to R ²¹ contains —SO ₃ ^— , a = 0, and each of R ¹⁶ to R ²¹ contains —SO ₃ ^— . If not, a = 1. Specific examples of the dye represented by formula (IV) include the following compounds.

<Dye represented by formula (V)>
(E) As a coloring agent, the dye represented, for example by general formula (V) can be used.

In the general formula (V), a plurality of Xs each independently represent a halogen atom. A plurality of R ²⁵ each independently represents a group represented by the following general formula (VI) or general formula (VII). Plural Rs each independently represent a hydrogen atom or a monovalent substituent. M represents Cu, Zn, V (═O), Mg, Ni, Ti (═O), Mg, Sn, or Si. A plurality of a's each independently represents an integer of 0 to 4, a plurality of n's each independently represents an integer of 0 to 4, and a plurality of r's each independently represents an integer of 0 to 4. . However, at least one of the plurality of a is 1 or more, and at least one of the plurality of n is 1 or more. The sum of the plurality of a, the plurality of n, and the plurality of r is 16. When a plurality of R ²⁵ are all the same substituent, a plurality of a are all the same, and a plurality of n are not all the same.

In general formula (VI) and general formula (VII), b R ^26s each independently represents a monovalent substituent selected from the group consisting of the following general formulas (VIII) to (X). R ²⁷ represents a monovalent substituent. b represents an integer of 1 to 5, and c represents an integer of 0 to 4. However, in the general formula (VI), the sum of b and c does not exceed 5. In the general formula (VII), the sum of b and c does not exceed 7. Y represents —O—, —S—, —SO ₂ —, or —NR ²⁸ —. R ²⁸ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.

In general formula (VIII), R ²⁹ represents a hydrogen atom, an alkyl group which may have a substituent, an oxyalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. An alkylamino group which may have a substituent, a dialkylamino group which may have a substituent, an arylamino group which may have a substituent, a diarylamino group which may have a substituent, or a substituent. Represents an alkylarylamino group which may be substituted. In general formula (IX), d represents an integer of 0 to 2, and when d is 0 or 1, R ³⁰ is an alkyl group which may have a substituent, or an aryl group which may have a substituent. And when d is 2, R ³⁰ has an alkyl group which may have a substituent, an aryl group which may have a substituent, a dialkylamino group which may have a substituent, and a substituent. It represents a diarylamino group which may be substituted, or an alkylarylamino group which may have a substituent.

In general formula (X), R ³¹ has an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, and a substituent. An optionally substituted arylcarbonyl group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, R ³² represents a hydrogen atom, an optionally substituted alkyl group, Or the aryl group which may have a substituent is represented.

In the case where the compound represented by the general formula (V) used in the present invention is a mixture of two or more kinds having different numbers of substitutions, a, n and r each mean an average value of the compounds in the mixture.

In the general formula (V), X represents a halogen atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom. Further, when the substitution position of X is the α-position of the phthalocyanine skeleton, the absorption wavelength becomes longer, and it can be suitably used for a green color filter.
A plurality of n's independently represents an integer of 0 to 4, preferably an integer of 1 to 3. The total number of n is preferably 1 to 14, more preferably 6 to 14, and particularly preferably 9 to 12.
R ²⁵ represents a group represented by General Formula (VI) or General Formula (VII), and more preferably a group represented by General Formula (VI).
A plurality of a's each independently represents an integer of 0 to 4, preferably 1 or 2. The total number of a is preferably 1 to 14, particularly preferably 2 to 8, and more preferably 3 to 5.
M represents Cu, Zn, V (═O), Mg, Ni, Ti (═O), Mg, Sn, or Si, and Zn or Cu is preferable.
R represents a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include the substituent T described later. R is preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aryloxy group, more preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a phenoxy group, More preferred is a hydrogen atom.
A plurality of r each independently represents an integer of 0 to 4.

In general formula (V), the substitution position of R in the phthalocyanine skeleton may be either the α-position or the β-position of the phthalocyanine skeleton, but the α-position substitution product has a greater effect of suppressing molecular association and is colored. This is preferable in terms of increasing the extinction coefficient of the composition layer.
R ²⁶ in general formula (VI) and general formula (VII) each independently represents a monovalent substituent selected from the group consisting of general formula (VIII) to general formula (X). A monovalent substituent represented by VIII) or (IX) is preferred.
b is an integer of 1 to 5, preferably 1 or 2. When b is 2 or more, a plurality of R ²⁶ may be the same or different.

R < ²⁷ > in general formula (VI) and general formula (VII) represents a monovalent substituent. The monovalent substituent represented by R ²⁷ can be selected from the substituent T described later, and is a halogen atom (preferably a chlorine atom or a bromine atom), a cyano group, a nitro group, a hydroxyl group, an amino group, an aryl group, or a total carbon. An alkoxycarbonyl group having 2 to 20 carbon atoms, an alkyloxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, or a carbon atom having 6 to 20 carbon atoms An arylthio group, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms are preferable, and a methyl group or a methoxy group is more preferable.
c is an integer of 0 to 4, preferably 0 or 1, and more preferably 0. When c is 2 or more, a plurality of R ³ may be the same or different.

In the general formula (VI) and the general formula (VII), Y is, -O -, - S -, - SO 2 -, or ^{-NR 28} - represents, -O- or -SO ₂ - are preferred, -O -Is more preferable.
By setting Y to —O— or —SO ₂ —, the absorption in the soret band can be shortened, and the absorption contrast tends to be exhibited more effectively.
R ²⁸ represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, An atom or a methyl group is more preferable, and a hydrogen atom is more preferable. Examples of the alkyl group and the like which may have a substituent will be described later.

R ²⁹ in the general formula (VIII) is a hydrogen atom, an alkyl group which may have a substituent, an oxyalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. An alkylamino group which may have a substituent, a dialkylamino group which may have a substituent, an arylamino group which may have a substituent, a diarylamino group which may have a substituent, or a substituent Represents an alkylarylamino group which may have a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a total carbon number of 12 A diarylamino group having 20 to 20 carbon atoms, or an alkylarylamino group having 7 to 20 carbon atoms in total, an alkyl group having 1 to 20 carbon atoms in total, a dialkylamino group having 2 to 20 carbon atoms in total, and 12 to 20 carbon atoms in total. Jary A ruamino group or an alkylarylamino group having 7 to 20 carbon atoms is more preferable, and a diarylamino group having 12 to 20 carbon atoms or a dialkylamino group having 2 to 20 carbon atoms is particularly preferable.

The alkyl moiety and aryl moiety such as the alkyl group and aryl group described above may further have a substituent. As the substituent, an alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, an arylthio group, or a halogen atom is preferable, an alkoxy group is more preferable, and a methoxy group or an ethoxy group is further preferable. Moreover, the aspect which does not have a substituent is also preferable. Examples of the alkyl group and the like which may have a substituent will be described later.

In general formula (IX), d represents an integer of 0 to 2, and when d is 0 or 1, R ³⁰ is an alkyl group which may have a substituent, or an aryl which may have a substituent. And when d is 2, the alkyl group which may have a substituent, the aryl group which may have a substituent, the dialkylamino group which may have a substituent, and the substituent Or a diarylamino group which may be substituted or an alkylarylamino group which may have a substituent. R ³⁰ is preferably a dialkylamino group having 2 to 20 carbon atoms, a diarylamino group having 12 to 20 carbon atoms, or an alkylarylamino group having 7 to 20 carbon atoms when d is 2.

The alkyl moiety and the aryl moiety such as the above-described alkyl group and aryl group may further have a substituent, and examples of the substituent include a substituent T described later, an alkoxy group, an aryl group, an aryloxy group, An alkoxycarbonyl group, an alkylthio group, an arylthio group, a halogen atom or the like is preferable, an alkoxy group is more preferable, and a methoxy group or an ethoxy group is further preferable. Moreover, the aspect which does not have a substituent is also preferable. Examples of the alkyl group and the like which may have a substituent will be described later.

In general formula (X), R ³¹ has an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, and a substituent. Represents an optionally substituted arylcarbonyl group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms , An alkylcarbonyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms, preferably an alkyl having 2 to 20 carbon atoms. More preferred are a carbonyl group, an arylcarbonyl group having 7 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms.

In the general formula (X), R ³² represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, an alkyl group having 1 to 20 carbon atoms or a carbon number of 6 ~ 20 aryl groups are preferred.

Preferred examples of the alkyl group which may have a substituent in the general formulas (VI) to (X) are shown below. Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, Hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group, phenoxyethyl group, benzyl group, phenylethyl group, N-butylaminosulfonylpropyl group, N-butylaminocarbonylmethyl group, N, N-dibutylaminosulfonylpropyl group, ethoxyethoxyethyl group, 2-chloroethyl group can be mentioned, more preferably methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, phenoxyethyl group, benzyl group, Phenylethyl group, N-butyl Examples thereof include aminosulfonylpropyl group, N-butylaminocarbonylmethyl group, N, N-dibutylaminosulfonylpropyl group, and ethoxyethoxyethyl group. Particularly preferred are methyl group, ethyl group, propyl group, tert-butyl group, phenoxyethyl. Group, benzyl group, phenylethyl group, N-butylaminosulfonylpropyl group, N-butylaminocarbonylmethyl group, N, N-dibutylaminosulfonylpropyl group and ethoxyethoxyethyl group.

Preferred examples of the aryl group that may have a substituent in the general formulas (VI) to (X) are shown below. Examples of the aryl group which may have a substituent include a phenyl group, 2-chlorophenyl group, 2-methoxyphenyl group, 4-butoxycarbonylphenyl group, 4-N, N-dibutylaminocarbonylphenyl group, 4-N— And butylaminosulfonylphenyl group, 4-N, N-dibutylaminosulfonylphenyl group, and more preferably phenyl group, 4-butoxycarbonylphenyl group, 4-N, N-dibutylaminocarbonylphenyl group, 4-N- Butylaminosulfonylphenyl group, 4-N, N-dibutylaminosulfonylphenyl group, and particularly preferably phenyl group, 4-butoxycarbonylphenyl group, 4-N, N-dibutylaminocarbonylphenyl group, 4-N, N-dibutylaminosulfonylphenyl group may be mentioned.

Preferred examples of the dialkylamino group which may have a substituent in the above general formulas (VI) to (X) are shown below. Examples of the dialkylamino group which may have a substituent include N, N-dimethylamino group, N, N-dibutylamino group, N, N-di (2-ethylhexyl) amino group, and N-methyl-N-benzyl. Amino group, N, N-di (2-ethoxyethyl) amino group, N.I. N-di (2-hydroxyethyl) amino group may be mentioned.

Preferred examples of the diarylamino group which may have a substituent in the above general formulas (VI) to (X) are shown below. Examples of the diarylamino group that may have a substituent include N, N-diphenylamino group, N, N-di (4-methoxyphenyl) amino group, and N, N-di (4-acylphenyl) amino group. Can be mentioned.

Preferred examples of the alkylarylamino group which may have a substituent in the general formulas (VI) to (X) are shown below. Examples of the alkylarylamino group which may have a substituent include N-methyl-N-phenylamino group, N-benzyl-N-phenylamino group, and N-methyl-N- (4-methoxyphenyl) amino group. Can be mentioned.

Preferred examples of the alkylcarbonyl group which may have a substituent in the above general formulas (VI) to (X) are shown below. Examples of the alkylcarbonyl group which may have a substituent include an acetyl group, a propylcarbonyl group, a heptyl-3-carbonyl group, a 2-ethylhexyloxymethylcarbonyl group, a phenoxymethylcarbonyl group, and a 2-ethylhexyloxycarbonylmethylcarbonyl group. Can be mentioned.

Preferred examples of the arylcarbonyl group which may have a substituent in the above general formulas (VI) to (X) are shown below. Examples of the arylcarbonyl group which may have a substituent include a benzoyl group, a 4-methoxybenzoyl group, and a 4-ethoxycarbonylbenzoyl group.

Preferred examples of the alkylsulfonyl group that may have a substituent in the general formulas (VI) to (X) are shown below. Examples of the alkylsulfonyl group which may have a substituent include a methanesulfonyl group, an octanesulfonyl group, a dodecylsulfonyl group, a benzylsulfonyl group, and a phenoxypropylsulfonyl group.

Preferred examples of the arylsulfonyl group which may have a substituent in the general formulas (VI) to (X) are shown below. Examples of the arylsulfonyl group which may have a substituent include a phenylsulfonyl group, a 2-methoxyphenylsulfonyl group, and a 4-ethoxycarbonylphenylsulfonyl group.

Preferred examples of the alkylsulfonylamino group which may have a substituent in the general formulas (VI) to (X) are shown below. Examples of the alkylsulfonylamino group which may have a substituent include a methylsulfonylamino group, a butylsulfonylamino group, a hydroxypropylsulfonylamino group, a 2-ethylhexylsulfonylamino group, an n-octylsulfonylamino group, and a phenoxyethylsulfonylamino group. And an allylsulfonylamino group.

In the general formulas (VI) to (X), examples of the vinylsulfonylamino group which may have a substituent include a vinylsulfonylamino group and a 1-methylvinylsulfonylamino group.

In the general formulas (VI) to (X), the arylsulfonylamino group which may have a substituent includes a phenylsulfonylamino group, a p-methoxyphenylsulfonylamino group, a p-ethoxycarbonylsulfonylamino group, and the like. Can be mentioned.

In the above general formulas (VI) to (X), the alkylcarbonylamino group which may have a substituent is a methylcarbonylamino group, a 2-ethylhexanoylamino group, an n-heptylcarbonylamino group, an ethoxyethoxy group. Examples include a methylcarbonylamino group.

In the above general formulas (VI) to (X), examples of the arylcarbonylamino group which may have a substituent include a benzoylamino group, a 2-methoxybenzoylamino group, and a 4-vinylbenzoylamino group.

Examples of the substituent T are shown below.
An alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, Hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), alkenyl group (preferably having a carbon number of 2 to 18 alkenyl groups such as vinyl group, allyl group, 3-buten-1-yl group), aryl groups (preferably aryl groups having 6 to 24 carbon atoms such as phenyl group, naphthyl group), heterocyclic ring Group (preferably a heterocyclic group having 1 to 18 carbon atoms such as 2-thienyl group, 4-pyridyl group, 2-furyl group, 2- Limidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), silyl group (preferably a silyl group having 3 to 18 carbon atoms, for example, trimethylsilyl Group, triethylsilyl group, tributylsilyl group, tert-butyldimethylsilyl group, tert-hexyldimethylsilyl group), hydroxyl group, cyano group, nitro group, alkoxy group (preferably an alkoxy group having 1 to 24 carbon atoms, , Methoxy group, ethoxy group, 1-butoxy group, 2-butoxy group, isopropoxy group, tert-butoxy group, dodecyloxy group, cyclopentyloxy group, cyclohexyloxy group), aryloxy group (preferably having 6 to 24 carbon atoms) An aryloxy group such as a phenoxy group, - naphthoxy),

A heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 18 carbon atoms, for example, 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group), silyloxy group (preferably having 1 to 18 carbon atoms) Silyloxy groups such as trimethylsilyloxy group, tert-butyldimethylsilyloxy group, diphenylmethylsilyloxy group), acyloxy groups (preferably acyloxy groups having 2 to 24 carbon atoms, such as acetoxy group, pivaloyloxy group, benzoyl group) Oxy group, dodecanoyloxy group), alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 24 carbon atoms, such as ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, cyclohexyloxycarbonyloxy group), A reeloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 24 carbon atoms such as phenoxycarbonyloxy group), a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 24 carbon atoms such as N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group, N-ethyl-N-phenylcarbamoyloxy group), sulfamoyloxy group (preferably sulfamoyl having 1 to 24 carbon atoms) An oxy group, for example, N, N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group), an alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 24 carbon atoms, for example, methylsulfonyl Oxy group, hexadecyl sulfo Aryloxy group, cyclohexyl sulfonyloxy group), an aryl sulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, e.g., phenylsulfonyl group),

An acyl group (preferably an acyl group having 1 to 24 carbon atoms, for example, formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group), alkoxycarbonyl group (preferably having 2 to 2 carbon atoms) 24 alkoxycarbonyl groups, for example, methoxycarbonyl group, ethoxycarbonyl group, octadecyloxycarbonyl group, cyclohexyloxycarbonyl group, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group), aryloxycarbonyl group (Preferably an aryloxycarbonyl group having 7 to 24 carbon atoms such as phenoxycarbonyl group), carbamoyl group (preferably a carbamoyl group having 1 to 24 carbon atoms such as carbamoyl group, N, N-diethylcarbamoyl group, N-ethyl N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methylN-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group), amino group (preferably Is an amino group having 24 or less carbon atoms, such as an amino group, methylamino group, N, N-dibutylamino group, tetradecylamino group, 2-ethylhexylamino group, cyclohexylamino group), anilino group (preferably 6 To 24 anilino groups, for example, anilino group, N-methylanilino group), heterocyclic amino groups (preferably 1-18 heterocyclic amino groups, for example 4-pyridylamino group), carbonamido groups (preferably 2 To 24 carbonamido groups such as acetamide group, benzamide group, tetra Canamide group, pivaloylamide group, cyclohexaneamide group), ureido group (preferably a ureido group having 1 to 24 carbon atoms, for example, ureido group, N, N-dimethylureido group, N-phenylureido group), imide group (preferably Is an imide group having 24 or less carbon atoms, such as an N-succinimide group or an N-phthalimide group, or an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 24 carbon atoms, such as a methoxycarbonylamino group, ethoxy Carbonylamino group, tert-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group),

An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 24 carbon atoms, such as a phenoxycarbonylamino group), a sulfonamide group (preferably a sulfonamide group having 1 to 24 carbon atoms, such as methanesulfone Amide group, butanesulfonamide group, benzenesulfonamide group, hexadecanesulfonamide group, cyclohexanesulfonamide group), sulfamoylamino group (preferably a sulfamoylamino group having 1 to 24 carbon atoms, for example, N, N -Dipropylsulfamoylamino group, N-ethyl-N-dodecylsulfamoylamino group), azo group (preferably an azo group having 1 to 24 carbon atoms, such as phenylazo group, 3-pyrazolylazo group), alkylthio Group (preferably an alkyl group having 1 to 24 carbon atoms) Group, for example, methylthio group, ethylthio group, octylthio group, cyclohexylthio group), arylthio group (preferably arylthio group having 6 to 24 carbon atoms, for example, phenylthio group), heterocyclic thio group (preferably having 1 carbon atom) A heterocyclic thio group having ˜18, for example, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 24 carbon atoms, For example, dodecanesulfinyl group), arylsulfinyl group (preferably arylsulfinyl group having 6 to 24 carbon atoms, such as phenylsulfinyl group), alkylsulfonyl group (preferably alkylsulfonyl group having 1 to 24 carbon atoms, for example, Methylsulfonyl group, ethylsulfonyl group, propylene A sulfonyl group, a butylsulfonyl group, an isopropylsulfonyl group, a 2-ethylhexylsulfonyl group, a hexadecylsulfonyl group, an octylsulfonyl group, a cyclohexylsulfonyl group), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 24 carbon atoms, Phenylsulfonyl group, 1-naphthylsulfonyl group),

Sulfamoyl group (preferably a sulfamoyl group having 24 or less carbon atoms, such as sulfamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfa group) Moyl group, N-cyclohexylsulfamoyl group), sulfo group, phosphonyl group (preferably phosphonyl group having 1 to 24 carbon atoms, such as phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl group), phosphine group It represents a finoylamino group (preferably a phosphinoylamino group having 1 to 24 carbon atoms, such as a diethoxyphosphinoylamino group or a dioctyloxyphosphinoylamino group).

Further, the substituent T is an alkaline aqueous solution solubilized part, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a sulfonimide group, a phenolic hydroxyl group, an acetoacetamide group, for the purpose of improving developability with respect to an alkaline developer. Substituents such as acetoacetic ester groups and substituents such as alkyl groups, alkyloxy groups, alkylthio groups, aryloxy groups, arylthio groups, alkylsulfonyl groups, arylsulfonyl groups and the like in which these groups are substituted are preferably used. .

When the above-described substituent is a further substitutable group, it may be further substituted with any of the above-described substituents. In addition, when it has two or more substituents, those substituents may be the same or different. However, the substituent in the present invention preferably has a mass per molecule of 500 or less.

<Dyes represented by general formula (XI) to general formula (XII)>
(E) As the colorant, a dye represented by formula (XI) or formula (XII) can be used.

In the general formula (XI), R ³³ , R ³⁴ , R ³⁵ and R ³⁶ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonylamino group, or a carbonylamino group. , A cyano group, an aryl group, or a heteroaryl group, and a plurality of R ³³ and R ³⁴ present in the molecule may be the same as or different from each other.

In general formula (XII), R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , and R ⁴⁰ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, or a sulfonylamino group. , A carbonylamino group, a cyano group, an aryl group, or a heteroaryl group, and a plurality of R ³⁷ present in the molecule may be the same as or different from each other.

Substituents that are more preferable as the structures of the dyes represented by the general formulas (XI) to (XII) will be described. R ³³ in the general formula (XI) and R ³⁷ in the general formula (XII) are preferably an alkyl group, an aryl group, or a cyano group, and the alkyl group and the aryl group may further have a substituent. . Here, examples of the substituent that can be introduced into the alkyl group and the aryl group include an alkoxy group, a thioalkoxy group, a cyano group, and a halogen atom.
R ³³ and R ³⁷ are more preferably a t-butyl group, a phenyl group, or an o-methylphenyl group.

R ³⁵ in general formula (XI) is more preferably a hydrogen atom, and R ³⁶ in general formula (XI) and general formula (XII) is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. . R ³⁴ , R ³⁹ , and R ⁴⁰ are each a hydrogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonylamino group, carbonylamino group, cyano group, aryl group, and heteroaryl group An aryl group having a partial structure selected from a substituted alkyl group, a PEO chain (polyethylene glycol), a PPO chain (polypropylene glycol), an ammonium salt, and a polymerizable group in the structure thereof, An alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonylamino group, or a carbonylamino group is preferable, and a sulfonylamino group having the partial structure is more preferable. A plurality of R ³⁴ present in the molecule may be the same or different from each other, but are preferably the same.
Suitable dyes include the following.

<Dye represented by general formula (XIII)>
(E) As a coloring agent, the dye represented by general formula (XIII) can be used.

In General Formula (XIII), R ⁴¹ and R ⁴² each independently represent a hydrogen atom or a monovalent substituent. R ⁴³ represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group. Q represents a diazo component residue. The dye represented by the general formula (XIII) may form a dimer or more multimer at an arbitrary position.

Specifically, the monovalent substituents represented by R ⁴¹ and R ⁴² are each independently a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an aliphatic group. Oxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, aliphatic oxy group, aryloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, amino group, aliphatic amino group, arylamino group, heterocyclic ring Amino group, acylamino group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, nitro group, aliphatic thio group, arylthio group , Aliphatic sulfonyl group, arylsulfonyl group, sulfamo Group, a sulfo group, an imide group, or a heterocyclic thio group. Among these, aliphatic group, aryl group, heterocyclic group, cyano group, carbamoyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, acyl group, aliphatic oxy group, aryloxy group, aliphatic amino group, or An arylamino group is preferred mainly from the viewpoint of imparting solubility.

Each of these groups may be further substituted, and each monovalent substituent represented by R ¹ to R ⁵ has a total carbon number of 1 to 40, preferably 3 to 25. By setting it as this range, the storage stability of the colored curable composition is good, and a colored curable composition having high brightness can be obtained.

The aliphatic group represented by R ⁴¹ to R ⁴³ may have a substituent, may be saturated or unsaturated, and may be cyclic. Specific examples include alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, alkynyl groups, substituted alkynyl groups, aralkyl groups, and substituted aralkyl groups. The total number of carbon atoms in the aliphatic group is preferably 1-30, and more preferably 1-16. Specific examples of the aliphatic group include, for example, methyl group, ethyl group, butyl group, isopropyl group, t-butyl group, hydroxyethyl group, methoxyethyl group, cyanoethyl group, trifluoromethyl group, 3-sulfopropyl group, Examples include 4-sulfobutyl group, cyclohexyl group, benzyl group, 2-phenethyl group, vinyl group, and allyl group.

The aryl group represented by R ⁴¹ to R ⁴³ may have a substituent, preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 16 carbon atoms. Specifically, for example, phenyl group, 4-tolyl group, 4-methoxyphenyl group, 2-chlorophenyl group, 3- (3-sulfopropylamino) phenyl group, 4-sulfamoyl group, 4-ethoxyethylsulfamoyl And 3-dimethylcarbamoyl group and the like.

The heterocyclic group represented by R ⁴¹ to R ⁴³ may be saturated or unsaturated, and includes the following aromatic heterocyclic groups, including a nitrogen atom, a sulfur atom, an oxygen atom, etc. Including any of the above heteroatoms, may further have a substituent, and is preferably a heterocyclic group having 1 to 30 carbon atoms in total, and a heterocyclic group having 1 to 15 carbon atoms. Is more preferable. Specific examples include 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2-benzoxazolyl group, 2-furyl group and the like.

The carbamoyl group represented by R ⁴¹ to R ⁴³ may have a substituent, is preferably a carbamoyl group having 1 to 30 carbon atoms, and more preferably a carbamoyl group having 1 to 16 carbon atoms. . Specific examples include a methylcarbamoyl group, a dimethylcarbamoyl group, a phenylcarbamoyl group, and an N-methyl-N-phenylcarbamoyl group.

The aliphatic oxycarbonyl group represented by R ⁴¹ to R ⁴³ may have a substituent, may be saturated or unsaturated, may be cyclic, and has a total number of carbon atoms of 2 An aliphatic oxycarbonyl group having 30 to 30 carbon atoms is preferable, and an aliphatic oxycarbonyl group having 2 to 16 carbon atoms in total is more preferable. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, and a 2-methoxyethoxycarbonyl group.

The aryloxycarbonyl group represented by R ⁴¹ to R ⁴³ may have a substituent, preferably an aryloxycarbonyl group having 7 to 30 carbon atoms in total, and an aryloxycarbonyl group having 7 to 16 carbon atoms. Is more preferable. Specific examples include a phenoxycarbonyl group, a 4-methylphenoxycarbonyl group, and a 3-chlorophenoxycarbonyl group.

The acyl group represented by R ⁴¹ to R ⁴³ includes an aliphatic carbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and preferably has a total carbon number of 1 to 30, and has a total carbon number of An embodiment having 1 to 16 is more preferable. Specific examples include an acetyl group, a methoxyacetyl group, a thienoyl group, and a benzoyl group.

The aliphatic sulfonyl group represented by R ⁴¹ to R ⁴³ may have a substituent, may be saturated or unsaturated, may be cyclic, and has a total carbon number of 1 to An embodiment having 30 is preferable, and an embodiment having 1 to 16 total carbon atoms is more preferable. Specifically, a methanesulfonyl group, a methoxymethanesulfonyl, an ethoxyethanesulfonyl group, etc. are mentioned, for example.

The arylsulfonyl group represented by R ⁴¹ to R ⁴³ may have a substituent, and preferably has a total carbon number of 6 to 30, and more preferably has a total carbon number of 6 to 18. Specific examples include benzenesulfonyl and toluenesulfonyl groups.

The sulfamoyl group represented by R ⁴¹ to R ⁴³ may have a substituent, and preferably has a total carbon number of 0 to 30, more preferably a total carbon number of 0 to 16. Specific examples include a sulfamoyl group, a dimethylsulfamoyl group, and a di- (2-hydroxyethyl) sulfamoyl group.

The imide group represented by R ⁴¹ to R ⁴³ may have a substituent and is preferably a 5- to 6-membered imide group. In addition, an embodiment in which the total number of carbon atoms in the imide group is 4 to 30 is preferable, and an embodiment in which 4 to 20 carbon atoms are more preferable. Specific examples include succinimide and phthalimide groups.

The diazo component residue represented by Q means the residue of the diazo component “B—NH ₂ ”. In particular, from the viewpoint of target color reproducibility, Q is preferably an aryl group or an aromatic heterocyclic group. Is preferred.

Here, the aromatic heterocyclic group is an aromatic ring containing any one of hetero atoms such as nitrogen atom, sulfur atom and oxygen atom in the ring, and preferably a 5- to 6-membered ring. The number of carbon atoms in the aromatic heterocyclic group is preferably 1 to 25, and more preferably 1 to 15. Specific examples of the aromatic heterocycle include pyrazole group, 1,2,4-triazole group, isothiazole group, benzoisothiazole group, thiazole group, benzothiazole group, oxazole group, 1,2,4 thiadiazole group. Etc.

In particular, the compound represented by the general formula (XIII) preferably has the following mode.
That is, R ⁴¹ is a cyano group, aliphatic oxycarbonyl group or carbamoyl group, R ⁴² is an aliphatic group, R ⁴³ is an aliphatic group, acyl group, aryl group, aliphatic carbonyl group, aliphatic sulfonyl group Or an arylsulfonyl group, and Q is an aryl group.

As described above, specific examples of the compounds represented by the general formulas (I) to (XIII) include, for example, Japanese Patent Application Laid-Open Nos. 2008-292970, 2010-32999, and 2008-304766. JP 2010-168531, JP 06230210, JP 2010-256598, JP 2012-237996, JP 3387541, JP 2011-164564, JP 2012. Although the compounds described in Japanese Patent No. -32754 can be mentioned, it is not limited to the description of these examples as long as the gist of the present invention is not exceeded.

<Other colorants>
As described above, the colorant of the present invention can be composed of only a pigment for reasons such as using a pigment in combination with a dye, or placing importance on heat resistance.
Conventionally known various inorganic pigments or organic pigments can be used as the pigment, but organic pigments are preferably used from the viewpoint of reliability. Examples of the organic pigment in the present invention include organic pigments described in paragraph [0093] of JP-A-2009-256572.

In particular, the following pigments are suitable from the viewpoint of color reproducibility, but are not limited to these in the present invention. These organic pigments can be used alone or in various combinations in order to increase color purity.

C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279

C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 1 4,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214

C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Cl substituent was changed to OH Stuff, 80
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42
C. I. Pigment Brown 25, 28
C. I. Pigment Black 1, carbon black coated with resin, and the like.
Examples of carbon black include the following carbon black.

Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45 # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B Made by Degussa: Printex3, Printex3OP, Printex30, Printex30OP Printex40, Printex45, P intex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW20 , Color Black S160, Color Black S170

Cabot Corporation: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130 , VULCAN XC72R, ELFTEX-8, Colombian Carbon Corporation: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAV N30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven450, Raven500, Raven780, Raven850, Raven890H, Raven1000, Raven1020, Raven1040, Raven1060U, Raven1080U, Raven1170, Raven1190U, Raven1170, Raven1170U RAVEN7000

In particular, the following pigments are suitable from the viewpoint of color reproducibility, but are not limited to these in the present invention. These organic pigments can be used alone or in various combinations in order to increase color purity.
C. I. Pigment Red 177, 224, 242, 254, 255, 264, C.I. I. Pigment Yellow 138, 139, 150, 180, 185, C.I. I. Pigment Orange 36, 38, 71, C.I. I. Pigment Green 7, 36, 58, C.I. I. Pigment Blue 15: 6, C.I. I. It is effective to use Pigment Violet 23, a carbon black coated with a resin. For example, carbon black described in JP-A No. 09-71733 can be suitably used.

[(F) Refractive index adjusting material]
In recent years, in electronic devices, a tablet-type input device is disposed on the surface of a liquid crystal device or the like, and while referring to an instruction image displayed in an image display area of the liquid crystal device, a finger or There is a type that can input information corresponding to an instruction image by touching a touch pen or the like.
Such an input device (touch panel) includes a resistance film type, a capacitance type, and the like. In the capacitance type input device, for example, an electrode pattern is extended in a direction crossing each other, and a finger or the like is extended. There is a type of detecting the input position by detecting that the capacitance between the electrodes changes when contacted. When using these capacitance-type input devices, for example, the transparent electrode pattern is conspicuous at a position slightly away from the vicinity of regular reflection when the light source is reflected, and there is a problem of visibility such as poor appearance. It was.

The development of a transparent laminate free from the problem of visually recognizing the transparent electrode pattern is underway, which is a transparent protective film using a high refractive index material. It has been studied that this transparent protective film is formed on a plastic substrate in addition to a glass substrate, and it is useful to incorporate a high refractive index material into the curable composition of the present invention.
The curable composition of the present invention preferably contains metal oxide particles as a refractive index adjusting material to be included for the purpose of adjusting such refractive index and light transmittance. Since the metal oxide particles have high transparency and light transmittance, a curable composition having a high refractive index and excellent transparency can be obtained.

The metal oxide particles preferably have a refractive index higher than the refractive index of the curable composition made of a material excluding the particles, and specifically, the refractive index in light having a wavelength of 400 nm to 750 nm. Are more preferably particles having a refractive index of 1.70 or more, particularly preferably particles having a refractive index of 1.90 or more.
Here, the refractive index of light having a wavelength of 400 to 750 nm being 1.50 or more means that the average refractive index of light having a wavelength in the above range is 1.50 or more. It is not necessary that the refractive index of all light having a wavelength is 1.50 or more. The average refractive index is a value obtained by dividing the sum of the measured values of the refractive index for each light having a wavelength in the above range by the number of measurement points.

In addition, the metal of the metal oxide particles includes semimetals such as B, Si, Ge, As, Sb, and Te.
The light-transmitting and high refractive index metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, and Nb. Oxide particles containing atoms such as Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, and Te are preferable. Titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / Tin oxide and antimony / tin oxide are more preferable, titanium oxide, titanium composite oxide and zirconium oxide are more preferable, titanium oxide and zirconium oxide are particularly preferable, and titanium dioxide is most preferable. Titanium dioxide is particularly preferably a rutile type having a high refractive index. The surface of these metal oxide particles can be treated with an organic material in order to impart dispersion stability. Further, Hypertech UR-101 manufactured by Nissan Chemical Industries, Ltd. is also preferably used.

From the viewpoint of the transparency of the curable composition, the average primary particle diameter of the metal oxide particles is preferably 1 to 200 nm, particularly preferably 3 to 80 nm. Here, the average primary particle diameter of the particles refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the longest side is the diameter.
Moreover, the said metal oxide particle may be used individually by 1 type, and can also use 2 or more types together.

The content of the metal oxide particles in the curable composition may be appropriately determined in consideration of the refractive index required for the optical member obtained from the curable composition, light transmittance, and the like. The content is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, based on the total solid content of the composition.
In the curable composition which may contain the high refractive index material of the present invention, the transparent protective film preferably has at least one of ZrO ₂ particles and TiO ₂ particles from the viewpoint of controlling the refractive index, ZrO ₂ particles are more preferred.

(Organic solvent)
The curable composition of the present invention can contain an organic solvent.
The organic solvent is basically not particularly limited as long as it can satisfy the solubility of each of the coexisting components and the applicability when a curable composition is used, and in particular, the solubility of the solids, applicability, It is preferable to select in consideration of safety.

Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. Oxyacetic acid alkyl esters (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specific examples include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate). )), 3-oxypropionic acid alkyl esters, 2-oxypropionic acid alkyl esters, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate , Propyl pyruvate, Seto methyl acetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether. Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.
Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
Preferable examples of aromatic hydrocarbons include toluene and xylene.

These organic solvents are also preferably mixed in a combination of two or more from the viewpoints of the solubility of each of the aforementioned components and, when an alkali-soluble binder is included, the solubility of the components and the improvement of the coated surface. In this case, particularly preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol It is a mixed solution composed of two or more selected from acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

The content of the organic solvent in the curable composition is preferably such that the total solid concentration in the curable composition is 10% by mass to 80% by mass, more preferably 15% by mass to 60% by mass. preferable.

(Surfactant)
The curable composition of the present invention may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant. Specific examples include nonionic surfactants described in paragraph 0058 of JP-A-2009-098616, and among them, fluorine surfactants are preferable.
Other surfactants that can be used in the present invention include, for example, commercially available products such as MegaFuck F142D, F172, F173, F176, F177, F183, F479, F482, and F554. F780, F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (manufactured by DIC Corporation), Florard FC-135, FC -170C, FC-430, FC-431, Novec FC-4430 (manufactured by Sumitomo 3M), Asahi Guard AG7105,7000,950,7600, Surflon S-112, S-113, S-131 S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351, 352, 801, 802 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Footgent 250 (manufactured by Neos Co., Ltd.), etc. Is mentioned.
Further, as the surfactant, the structural unit A and the structural unit B represented by the following formula (W) are included, and the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent is 1, A copolymer having a molecular weight of 000 or more and 10,000 or less can be given as a preferred example.

(In Formula (W), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or carbon number. 1 represents an alkyl group having 4 or less, L represents an alkylene group having 3 to 6 carbon atoms, p and q are weight percentages representing a polymerization ratio, and p is a numerical value of 10% by mass to 80% by mass. Q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and n represents an integer of 1 to 10.

L is preferably a branched alkylene group represented by the following formula (W-2). R ⁵ in Formula (W-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. Two or three alkyl groups are more preferred.
The sum (p + q) of p and q in the formula (W) is preferably p + q = 100, that is, 100% by mass.
The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

These surfactants can be used alone or in combination of two or more.
The addition amount of the surfactant in the curable composition of the present invention is preferably 0.01 to 2.0% by mass, particularly preferably 0.02 to 1.0% by mass in the total solid content of the curable composition. Within this range, the coatability and the uniformity of the cured film are good.

(Adhesion improver)
The curable composition of the present invention may contain an adhesion improving agent.
The adhesion improver improves the adhesion between the inorganic material serving as the support, for example, a silicon compound such as glass, silicon, silicon oxide, and silicon nitride, gold, copper, aluminum, and the cured film of the colored curable composition layer. A compound. Specific examples include silane coupling agents. The silane coupling agent as the adhesion improving agent is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
As the silane coupling agent, a silane coupling agent described in paragraph 0048 of JP-A-2009-98616 is preferable, and γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable. These can be used alone or in combination of two or more.
The content of the adhesion improving agent in the curable composition of the present invention is preferably 0.1 to 20% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the curable composition.

(Crosslinking agent)
It is also possible to supplement the curable composition of the present invention with a crosslinking agent to increase the hardness of the cured layer obtained by curing the curable composition.
The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Substituted with at least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, substituted with one substituent, Phenol compounds, naphthol compounds or hydroxyanthracene compounds are mentioned. Of these, polyfunctional epoxy resins are preferred.
For details such as specific examples of the crosslinking agent, the description in paragraphs [0134] to [0147] of JP-A No. 2004-295116 can be referred to.

(Development accelerator)
A development accelerator can also be added when the alkali solubility of the non-exposed area when the curable composition layer is exposed is promoted and the developability of the curable composition is further improved. The development accelerator is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1000 or less and a low molecular weight phenol compound having a molecular weight of 1000 or less.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, and umbellic acid.

(Other additives)
If necessary, the curable composition of the present invention may further contain various additives such as fillers, polymer compounds other than those described above, ultraviolet absorbers, antioxidants and the like. Examples of these additives include those described in paragraphs [0155] to [0156] of JP-A No. 2004-295116.
The curable composition of the present invention may contain a light stabilizer described in paragraph [0078] of JP-A No. 2004-295116 and a thermal polymerization inhibitor described in paragraph [0081] of the publication.

(Method for preparing curable composition)
The curable composition of the present invention is prepared by mixing the above-described components and optional components as necessary. (E) When a colorant is contained, any of a pigment, a dye, or a mixed system of a pigment and a dye may be used.
In preparing the curable composition, the components constituting the curable composition may be combined at once, or may be sequentially mixed after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a curable composition.
The colored curable composition prepared as described above can be used after being preferably filtered using a filter having a pore size of about 0.01 μm to 3.0 μm.

When the curable composition of the present invention contains a colorant, a colored cured film excellent in hue and contrast can be formed, so that for forming a colored pixel such as a color filter used in a liquid crystal display device, Moreover, it can use suitably as preparation uses, such as printing ink, inkjet ink, and a coating material.

(Color filter and manufacturing method thereof)
The color filter of the present invention is configured by providing a substrate and a colored region made of the colored curable composition of the present invention on the substrate. The colored region on the substrate is composed of colored layers such as red (R), green (G), and blue (B) that form each pixel of the color filter.
The method for producing a color filter of the present invention includes a colored layer forming step (A) in which a colored layer (colored curable composition layer) is formed by applying the above-described colored curable composition on a support, and a step ( An exposure step (B) for forming a latent image by performing pattern-like exposure on the colored layer formed in A), and a developing step for developing the colored layer on which the latent image is formed to form a pattern (C).
Moreover, in the manufacturing method of the color filter of this invention, the aspect which further provided the process (D) which heat-processes with respect to the coloring pattern obtained at the process (C) is preferable.
Hereinafter, the manufacturing method of the color filter of the present invention will be described more specifically.

-Process (A)-
In the method for producing a color filter of the present invention, first, the above-described colored curable composition of the present invention is applied onto a support by spin coating, slit coating, cast coating, roll coating, bar coating, ink jet, or the like. Is applied to form a colored layer, and then the colored layer is dried by heating (pre-baking) or vacuum drying.

Examples of the support include soda glass, alkali-free glass, borosilicate glass, quartz glass, a silicon substrate, and a resin substrate used for liquid crystal display devices. Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the surface.

Examples of the pre-baking condition include a condition of heating at 70 to 130 ° C. for about 0.5 to 15 minutes using a hot plate or an oven.
Moreover, the thickness of the colored layer formed with a colored curable composition is suitably selected according to the objective. In the color filter for liquid crystal display devices, the range of 0.2 μm to 5.0 μm is preferable, and the range of 1.0 μm to 4.0 μm is more preferable. In addition, the thickness of a colored layer is a film thickness after drying.

-Process (B)-
Subsequently, in the method for producing a color filter of the present invention, pattern-like exposure is performed on the colored layer formed on the support. As light or radiation applicable to exposure, g-line, h-line, i-line and various laser beams are preferable, and i-line is particularly preferable. When using the i-line to the irradiation light is ^preferably irradiated at an exposure dose of 5mJ / cm 2 ~ 500mJ / cm 2.

Also, as other exposure light sources, ultrahigh pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various laser light sources, and the like can be used.

-Exposure process using laser light source-
In the exposure method using a laser light source, the irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 410 nm, and more preferably an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm. Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. . The pattern exposure, from the viewpoint of ^{productivity,} preferably in the range of 1mJ / cm 2 ~ 100mJ / cm 2, the range of 1mJ / cm 2 ~ 50mJ / cm 2 is more preferable.

There are no particular restrictions on the exposure apparatus, but commercially available devices such as Callisto (buoy technology), EGIS (buoy technology), and DF2200G (Dainippon Screen) can be used. is there. Further, devices other than those described above are also preferably used.

-Process (C)-
Subsequently, the colored layer after exposure is developed with a developer. Thereby, a colored pattern can be formed. As long as the developing solution dissolves the uncured portion of the colored layer and does not dissolve the cured portion, a combination of various organic solvents or an alkaline aqueous solution can be used. When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted to pH 10-13. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl. Examples include alkaline aqueous solutions such as ammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo- [5.4.0] -7-undecene.
The development time is preferably from 30 seconds to 300 seconds, more preferably from 30 seconds to 120 seconds. The development temperature is preferably 20 ° C. to 40 ° C., more preferably 23 ° C.
Development can be performed by a paddle method, a shower method, a spray method, or the like.
Moreover, after developing using alkaline aqueous solution, it is preferable to wash | clean with water.

In the method for producing a color filter of the present invention, it is also preferable to perform post-exposure by ultraviolet irradiation on a colored pattern (pixel) formed using a colored curable composition.

-Process (D)-
It is preferable to further heat-treat the colored pattern after development or the colored pattern subjected to post-exposure by ultraviolet irradiation as described above. By heating the formed color pattern (so-called post-bake process), the color pattern can be further cured. This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like.
The temperature during the heat treatment is preferably 100 ° C. to 300 ° C., more preferably 120 ° C. to 250 ° C. The heating time is preferably about 10 minutes to 120 minutes.

The colored pattern thus obtained constitutes a pixel in the color filter. In manufacturing a color filter having a plurality of hue pixels, the above-described step (A), step (B), step (C), and step (D) may be repeated in accordance with the desired number of colors.
In addition, whenever formation, exposure, and development of a single color layer are completed (for each color), the step (D) may be performed, or formation, exposure, and formation of all colored layers having a desired number of colors. After the development is completed, the step (D) may be performed collectively.

The color filter obtained by the method for producing a color filter of the present invention (the color filter of the present invention) is excellent in hue and contrast since the colored curable composition of the present invention is used. When used in a liquid crystal display device or the like, it is possible to display an image excellent in spectral characteristics and contrast while achieving a good hue.

<Liquid crystal display device>
The liquid crystal display device of the present invention includes the above-described color filter of the present invention. For the definition of liquid crystal display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Kogyo Kenkyukai 1990)”, “Display Devices (written by Junaki Ibuki, Sangyo Tosho) Issued in 1989). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The color filter of the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention is applied to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can. The color filter of the present invention can also be used for a COA (Color-filter On Array) system.

When the color filter of the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, but further, red, green and blue LED light sources (RGB-LED). By using as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.

<Solid-state imaging device>
The solid-state imaging device of the present invention includes the above-described color filter of the present invention. The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter of the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. .

A transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is provided on a support, and a photo is formed on the photodiode and the transfer electrode. A device having a light-shielding film made of tungsten or the like that is opened only in the light-receiving portion of the diode, and a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion; The color filter of the present invention is provided on the protective film.
Furthermore, it has a condensing means (for example, a microlens etc. The same shall apply hereinafter) on the device protective layer and below the color filter (on the side close to the support), or a condensing means on the color filter. It may be a configuration or the like.

(Protective film formation method)
The protective film of the present invention is formed using the curable composition of the present invention described above.
Since the protective film of the present invention is constituted using the curable composition of the present invention, it is excellent in high hardness and film thickness uniformity even when formed at a low heating temperature or without heat treatment.

The protective film of the present invention may be formed by any method as long as it is a method using the curable composition of the present invention, but can be formed by a method similar to the above-described method for producing a color filter. Here, when the protective film is not patterned, that is, when the protective film is formed as a so-called solid film, a method of exposing the entire surface of the film in the (b) exposure step is preferable. As a curable composition capable of forming a transparent protective film member used for a touch panel or the like, an ITO pattern visibility improving property may be incorporated.

As a method of forming a curable composition layer on a substrate, (a) a coating method of applying a curable composition containing at least the resin, the polymerizable compound, and the photopolymerization initiator described above, and (b) the above-mentioned A transfer-type dry film form in which a transfer material having a curable composition layer is used, and the curable composition layer is laminated and transferred by heating and / or pressurization is preferable.

(A) Coating method The curable composition can be coated by a known coating method such as spin coating, curtain coating, slit coating, dip coating, air knife coating, roller coating, wire bar coating, It can be carried out by a gravure coating method or an extrusion coating method using a popper described in US Pat. No. 2,681,294. Among them, JP 2004-89851 A, JP 2004-17043 A, JP 2003-170098 A, JP 2003-164787 A, JP 2003-10767 A, JP 2002-79163 A, A method using a slit nozzle or a slit coater described in JP 2001-310147 A is suitable.

(B) Transfer method Transfer is performed by using a photosensitive transfer material, for example, a roller or flat plate in which a curable composition layer formed in a film shape on a temporary support is heated and / or pressed on a desired substrate surface. After being bonded together by pressure bonding or thermocompression bonding, the curable composition layer is transferred onto the substrate by peeling off the temporary support. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From the viewpoint, it is preferable to use the method described in JP-A-7-110575.

When the curable composition layer is formed, an oxygen barrier layer (hereinafter also referred to as “oxygen barrier film” or “intermediate layer”) can be further provided between the curable composition layer and the temporary support. . Thereby, exposure sensitivity can be improved. In order to improve transferability, a thermoplastic resin layer having cushioning properties may be provided.
Regarding the temporary support, the oxygen blocking layer, the thermoplastic resin layer, and other layers constituting the photosensitive transfer material and the method for producing the photosensitive transfer material, paragraph numbers [0024] to [0024] of [Japanese Patent Laid-Open No. 2006-23696] The structure and manufacturing method described in [0030] can be applied.

Examples of the substrate on which the curable composition layer is formed include, for example, a transparent substrate (for example, a glass substrate or a plastics substrate), a substrate with a transparent conductive film (for example, an ITO film), and a substrate with a color filter (also called a color filter substrate). And a driving substrate with a driving element (for example, a thin film transistor [TFT]). The thickness of the substrate is generally preferably 700 to 1200 μm.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Unless otherwise specified, “part” and “%” are based on mass.

-Preparation of curable composition 1-
The following components were mixed and dissolved to prepare a curable composition.
Organic solvent 1: Propylene glycol monomethyl ether acetate 77.41 parts Resin having an acidic group in the side chain: Alkali-soluble binder P-1 (1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% below) Solution) 6.31 parts Polymerizable compound 1: Nagase ChemteX Co., Ltd., DA-314 (Exemplary compound (34) 3.1 parts Hyperbranched polymer: Osaka Organic Chemical Co., Ltd., STAR-501 (Weight average molecular weight: 11000) 12.39 parts ・ Polymerization inhibitor: 0.003 part of p-methoxyphenol ・ Initiator 1: CGI Specialty Chemicals, CGI-242
0.45 parts, adhesion improver: 3-methacryloxypropyltrimethoxysilane 0.2 parts, fluorosurfactant: DIC's MegaFuck F-554, 2% solid content propylene glycol monomethyl ether acetate solution)
0.6 parts

-Preparation of curable compositions 2-9 and curable compositions C1-C5 (for comparison)-
In the same manner as the curable composition 1, curable compositions 2 to 9 and curable compositions C1 to C5 having the compositions shown in Table 1 below (unit: parts by mass) were prepared.

-Formation of curable composition layer-
After applying each curable composition on a glass (# 1737; made by Corning) substrate or a polyethylene terephthalate film (PET) substrate by a spin coat method, the one applied to the glass substrate is PET at 120C for 120 seconds. What was apply | coated to the board | substrate was made to volatilize a volatile component by making it dry at 50 degreeC for 120 second, and formed the curable composition layer. The film thickness of the curable composition layer was adjusted to be 2.1 μm. This curable composition layer was irradiated with i-line (wavelength 365 nm). An ultra-high pressure mercury lamp was used as the i-line light source, and solid exposure was carried out so that the irradiation light quantity of the light source was 40 mJ / cm ^{2 after} being converted into parallel light. Then, it heat-processed on the heat processing conditions described in following Table 2, and obtained the cured film. About the cured film of each experiment number, the double bond consumption rate and the pencil hardness were measured by the method described later, and ranked according to the following evaluation criteria. The results are shown in Table 2 below.

<Measurement of double bond consumption rate>
FT-IR apparatus (Thermo Nicolet Japan Ltd., Nicolet 710) ^was used to measure the wavelength region of 400 cm -1 ~ 4000 cm ^-1, was determined peak intensity of 810 cm ^-1 derived from C = C bond. For each cured film, the peak strength (= double bond residual amount) A of the UV uncured product only applied and dried, and the peak strength B of the cured film after UV curing and heat treatment are performed according to the following formula: The double bond consumption rate was calculated.
Formula: Double bond consumption rate = {1- (B / A)} × 100%
"Evaluation criteria"
A: Double bond consumption rate is 80% or more B: Double bond consumption rate is 50% or more and less than 80% C: Double bond consumption rate is less than 50%

<Evaluation of pencil hardness>
As an index of scratch resistance, pencil hardness evaluation described in JIS K 5400 was performed. The cured product sections of each Example and Comparative Example were conditioned for 1 hour at a temperature of 25 ° C. and a relative humidity of 60%, and then n = with a load of 500 g using a 2H test pencil specified in JIS S 6006. An evaluation of 7 was made.
"Evaluation criteria"
A: There are less than 3 scratches.
B: There are 3 or more and less than 5 scratches.
C: There are 5 or more and less than 6 scratches.
D: There are 6 or more scratches.

Table 2 shows the following.
The curable compositions 1 to 9 according to the examples of the present invention have a high double bond consumption rate under any heat treatment conditions and the polymerization is efficient as compared with the curable compositions C1 to C5 according to the comparative examples. A cured film having high pencil hardness is obtained. In particular, a cured film having sufficient pencil hardness can be obtained even in a cured film that is heat-treated at a low temperature of 150 ° C. or a cured film that is cured only by i-line exposure without performing the heat treatment.
Furthermore, even when PET, which is a plastic base, is used as a substrate, a cured film having high hardness is obtained under a heat treatment condition of 130 ° C.

-Preparation of curable composition 10 (containing colorant)-
The following components were mixed, dissolved or dispersed to prepare curable composition 10.
Organic solvent 1: 9 parts of propylene glycol monomethyl ether acetate Organic solvent 2: 25 parts of diethylene glycol ethyl methyl ether Resin having acidic group in side chain: Alkali-soluble binder P-1
6 parts, polymerizable compound 1: manufactured by Nagase ChemteX Corporation, DA-314
1.6 parts hyperbranched polymer: made by Osaka Organic Chemical Co., Ltd., STAR-501
6.4 parts ・ Polymerization inhibitor: 0.003 part of p-methoxyphenol ・ Initiator: 0.26 part of exemplary compound (V-3) ・ Adhesion improver: 0.22 part of 3-methacryloxypropyltrimethoxysilane Fluorine-based surfactant (Megafac F-554 manufactured by DIC, propylene glycol monomethyl ether acetate solution with a solid content of 0.2%)
5 parts-Pigment dispersion A:-25 parts of pigment dispersion 1 with the following formulation-20 parts of pigment dispersion 2 with the following formulation

The pigment dispersion 1 was prepared as follows.
C. I. 12.8 parts of Pigment Blue 15: 6 and 7.2 parts of a dispersant (Solsperse 24000 manufactured by Nihon Lubrizol Co., Ltd.) are mixed with 80.0 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently mixed using a bead mill. Dispersion was carried out to prepare Pigment Dispersion Liquid 1.

The pigment dispersion 2 was prepared as follows.
C. I. 5 parts of Pigment Violet 23 and 5 parts of a dispersant (Solsperse 24000 manufactured by Nihon Lubrizol Corporation) are mixed with 90.0 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently dispersed using a bead mill. Liquid 2 was prepared.

-Preparation of curable compositions 11-20 and curable compositions C-6-C-8-
In the same manner as the preparation of the curable composition 10, the curable compositions 11 to 20 having the composition shown in Table 3 (unit: parts by mass) and the curable compositions C-6 to C-8 (for comparison) Was prepared.
The pigment dispersions 3 to 5 and the dye solutions 1 to 6 used are as follows.

~ Pigment dispersion 3 ~
C. I. 12.8 parts of Pigment Green 58 and 7.2 parts of a dispersant (Solsperse 24000 manufactured by Nihon Lubrizol) are mixed with 80.0 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently dispersed using a bead mill. Thus, a pigment dispersion 3 was prepared.

~ Pigment dispersion 4 ~
C. I. 5 parts of Pigment Yellow 138 and 5 parts of a dispersant (Solsperse 32000 manufactured by Nippon Lubrizol) were mixed with 90.0 parts of propylene glycol monomethyl ether acetate, and the pigment was sufficiently dispersed using a bead mill. Liquid 4 was prepared.

~ Pigment dispersion 5 ~
C. I. 12.8 parts of Pigment Red 254 and 7.2 parts of a dispersant (Solsperse 24000 manufactured by Nippon Lubrizol Corporation) are mixed with 80.0 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently dispersed using a bead mill. Thus, a pigment dispersion 5 was prepared.

The dye solution 1 was prepared by mixing and dissolving the following components.
・ Organic solvent (propylene glycol monomethyl ether acetate)
95 parts · Dye (the following compound (A)) 5 parts

Dye solutions 2 to 6 were prepared in the same manner as the dye solution 1 except that the following compounds (B) to (F) were used as dyes.

-Formation of colored curable composition layer (colored layer)-
After applying the curable composition prepared above on a glass (# 1737; Corning) substrate by a spin coat method, the volatile component is volatilized by drying at room temperature for 30 minutes, thereby coloring the curable composition. A layer (colored curable composition layer A) was formed. This colored curable composition layer was irradiated with i-line (wavelength 365 nm) through a mask having a line / space of 20 μm / 20 μm. An ultra-high pressure mercury lamp was used as the i-line light source, and it was irradiated as parallel light. The amount of irradiation light was 40 mJ / cm ² . Next, the colored curable composition layer irradiated with i-line in a pattern was developed with an aqueous solution of sodium carbonate / sodium bicarbonate (concentration 2.4%, pH 10) at 26 ° C. for 45 seconds, After rinsing with running water for 20 seconds, it was dried to obtain a fine line pattern image. The obtained fine line pattern image was post-baked under the heat treatment conditions shown in Table 4 to obtain a colored cured film (colored layer B) having a pattern thickness of 2 μm.

-Evaluation-
Based on the colored cured film obtained above, the sensitivity of the colored curable composition, the specific resistance of the liquid crystal, the spectral characteristics, the contrast, the adhesion and the chemical resistance were evaluated by the methods described below. The specific resistance and chemical resistance of the liquid crystals were ranked according to the following evaluation criteria. The results are shown in Table 4 below.

(1) Sensitivity The obtained fine line pattern image was photographed with an optical microscope at a magnification of 200 times, and the width of the fine line of the colored line image was measured. Since the width of the fine line becomes thicker as the sensitivity is higher, the width of the fine line width from the mask width is defined as the line width sensitivity. Larger numbers are preferred because of higher sensitivity.

(2) Specific resistance of liquid crystal The colored layer B obtained above was scraped from the substrate, and 9.0 mg of the scraped material was added to 2.00 g of liquid crystal material ZLI-4792 (Merck) and heated at 120 ° C. for 5 hours. did. Then, it filtered and the specific resistance of liquid crystal material was measured with the liquid crystal specific resistance measuring apparatus (model number ADVANTEST R8340 ULTRA HIGH RESISTANCE ME Co., Ltd. product made by Advantest). Since the specific resistance of the liquid crystal material decreases due to the elution of metal ions, the elution of metal ions can be evaluated by the degree of the specific resistance.
<Evaluation criteria>
A: Specific resistance ≧ 1.0 × 10 ¹¹ MΩ, and no seizure failure was observed when the panel was assembled in a liquid crystal display device.
B: Specific resistance <1.0 × 10 ¹¹ MΩ, and a seizure failure occurred when a panel was assembled in a liquid crystal display device.

(3) Spectral characteristics The transmission spectrum of the colored layer B obtained above was measured using a microspectrophotometer OSP-SP200 (trade name) manufactured by Olympus Corporation. From the obtained transmission spectrum, the color coordinate x value, y value, and Y value in the CIE 1931 color system were determined.
The spectral characteristics can be said to have excellent spectral characteristics when the Y value at (x, y) = (0.138, 0.085) is high. It can be said that the larger the Y value, the better the spectral characteristics.

(4) Contrast In addition, when the obtained substrate having each colored layer B is sandwiched between two polarizing films, the luminance values when the polarizing axes of the two polarizing films are parallel and perpendicular are colored. Measured using a luminance meter (Topcon Co., Ltd., model number: BM-5A), and obtained by dividing the luminance when the polarization axes of the two polarizing films are parallel by the luminance when vertical. The value was determined as contrast. The higher the contrast, the better the performance as a color filter for a liquid crystal display device.

(5) Adhesiveness About the colored curable composition layer A obtained above, using an i-line reduction projection exposure apparatus, the colored curable composition layer A has a wavelength of 365 nm, 5, 10, 15, 20, And an exposure dose of 40 mJ / cm ² through a mask having a mask width of 25 μm. After irradiation, the developer was used and developed at 23 ° C. for 60 seconds. Subsequently, after rinsing with running water for 20 seconds, the film was dried by spraying to obtain a fine line pattern image. Image formation was observed by an ordinary method using an optical microscope and SEM photograph observation. The pattern dimension of the thinnest fine line pattern remaining on the substrate was used as the evaluation of adhesion.
It can be said that the thinner the fine wire remains, the better the adhesion.

(6) Chemical resistance (solvent resistance)
Each colored curable composition was applied on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)) using a spinner, and then pre-baked on a hot plate at 90 ° C. for 2 minutes. A 2.1 μm colored layer was formed. The obtained colored layer was exposed on the entire surface with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. so that the integrated irradiation amount was 40 mJ / cm ² (illuminance: 20 mW / cm ² ). This substrate was heated in an oven under the conditions described in Table 4 to obtain a colored cured film.
The chromaticity of the obtained colored cured film was measured. Then, the substrate on which this cured film was formed was immersed in N-methyl-2-pyrrolidone controlled at 23 ° C. for 20 minutes, and then the chromaticity of the colored cured film was measured, and the chromaticity change due to immersion was measured. When this value calculated by ΔE * ab is 3 or less, it can be said that the solvent resistance of the cured film is good.
〔Evaluation criteria〕
A: ΔE * ab before and after immersion is less than 2.0 B: ΔE * ab before and after immersion is 2.0 to 3.0 or less C: ΔE * ab before and after immersion exceeds 3.0

Table 4 shows the following.
The curable compositions 10 to 20 according to the examples of the present invention have excellent sensitivity and spectral characteristics (Y value), high contrast, excellent adhesion, high specific resistance of liquid crystal, and good chemical resistance. I understand that. The effect is effectively manifested under heat treatment conditions at 130 ° C. even when plastic base PET is used as the substrate. In addition, the liquid crystal display device obtained using the curable compositions 10 to 20 did not cause burn-in.
On the other hand, in the case of the curable compositions C6 to C8 as comparative examples, when the heat treatment temperature was as low as 150 ° C., the specific resistance of the liquid crystal was low and the adhesion was low. .

-Preparation of refractive index adjusting member-
[Production of transfer film]
<Formation of thermoplastic resin layer and intermediate layer>
A thermoplastic resin layer having a film thickness of 15 μm is applied on a polyethylene terephthalate film having a thickness of 75 μm as a temporary support using a slit-like nozzle and dried by applying a coating solution for a thermoplastic resin layer having the following formulation H1. Formed. On top of that, an intermediate layer coating solution having the following formulation P1 was applied and dried to form an intermediate layer having a thickness of 1.6 μm.

(Coating solution for thermoplastic resin layer: Formulation H1)
・ Methanol 11.1 parts ・ Propylene glycol monomethyl ether acetate 6.36 parts ・ Methyl ethyl ketone 52.4 parts ・ Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55) /11.7/4.5/28.8, molecular weight = 100,000, Tg≈70 ° C.)
5.83 parts styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63/37, weight average molecular weight = 10,000, Tg≈100 ° C.) 13.6 parts monomer 1 (trade name: BPE -500, Shin-Nakamura Chemical Co., Ltd.)
30% methyl ethyl ketone solution 0.54 parts of 9.1 parts Fluorine-based polymer (the above fluorine-based _polymer, and _{_{_{C 6 F 13 CH 2 CH 2}}} OCOCH = CH 2, H (OCH (CH 3) CH 2) 7 OCOCH = CH ₂ and a copolymer of 40: 55: 5 (mass ratio) of H (OCH ₂ CH ₂ ) ₇ OCOCH═CH ₂ and having a weight average molecular weight of 30,000 (trade name: Megafax F780F, DIC) (Made by Co., Ltd.)

(Coating liquid for intermediate layer: prescription P1)
・ Polyvinyl alcohol (trade name: PVA205, manufactured by Kuraray Co., Ltd., degree of saponification = 88%, polymerization degree 550) 32.2 parts ・ Polyvinylpyrrolidone (trade name: K-30, manufactured by IP Japan Co., Ltd.) 14 .9 parts ・ Distilled water 524 parts ・ Methanol 429 parts

<First curable transparent resin layer>
Next, on the intermediate layer, the curable composition 21, 22, 23, C9, C10 or C11 for the first curable transparent resin layer prepared by the composition described in the following Table 5 (unit is part by mass). The first curable transparent resin layer was formed by applying and drying while changing the coating amount so as to obtain the film thickness after drying described in Table 6 below.

When the first curable transparent resin layer was applied and dried, a section of this first curable transparent resin layer was cut from the surface using a microtome. To 0.1 mg of this slice, 2 mg of KBr powder was added and mixed well under a yellow lamp to obtain a UV uncured product measurement sample in the measurement of the double bond consumption rate described later.

The first curable transparent resin layer of each obtained sample was cured by irradiation with ultraviolet irradiation (exposure amount: 300 mJ / cm ² , light source: methane halide lamp).
A section of the cured film of the first curable transparent resin layer thus obtained was cut from the surface using a microtome. To 0.1 mg of this slice, 2 mg of KBr powder was added and mixed well under a yellow lamp to obtain a measurement sample after coating, drying and curing in the measurement of the double bond consumption rate described later.

(Measurement of double bond consumption rate)
FT-IR apparatus (Thermo Nicolet Japan Ltd., Nicolet 710) ^was used to measure the wavelength region of 400 cm -1 ~ 4000 cm ^-1, was determined peak intensity of 810 cm ^-1 derived from C = C bond. For the first curable transparent resin layer of each sample, the peak intensity (= double bond residual amount) A of the UV uncured product only by coating and drying and the peak intensity B after curing are obtained, according to the following formula: The double bond consumption rate was calculated.
Formula: Double bond consumption rate = {1- (B / A)} × 100%
"Evaluation criteria"
A: Double bond consumption rate is 10% or more B: Double bond consumption rate is less than 10% Note that the double bond consumption rate is an index of the degree of interfacial mixing between the first layer and the second layer.

<Formation of second curable transparent resin layer>
On the first curable transparent resin layer (uncured) described above, the curable composition 24 or C12 described in Table 5 described above has a film thickness after drying described in Table 6 while changing the coating amount. It apply | coated so that it might become, and it dried and formed the 2nd curable transparent resin layer.

<Press bonding of protective film>
In this way, the thermoplastic resin layer having a dry film thickness of 15.1 μm, the intermediate layer having a dry film thickness of 1.7 μm, and the dry film thickness in Table 6 below are provided on the temporary support. The curable transparent resin layer and the second curable transparent resin layer were provided, and finally a protective film (thickness 12 μm polypropylene film) was pressure-bonded.

Transfer films 21 to 23 in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), the first curable transparent resin layer, the second curable transparent resin layer, and the protective film are integrated. Transfer films C9 to C11 were prepared.

(Production of transparent laminate)
Using the above transfer film, a transparent laminate was produced by the following method.

<1. Formation of transparent film>
A transparent film having a refractive index of 1.7 and a film thickness of 65 nm using the curable composition 22 shown in Table 5 above was laminated on a glass transparent substrate having a refractive index of 1.51 by the following method.

(Preparation of transfer material)
On the 75-micrometer-thick polyethylene terephthalate film temporary support body, the coating liquid for thermoplastic resin layers of the above-mentioned prescription H1 was apply | coated and dried using the slit-shaped nozzle. Next, the coating liquid for intermediate layer of the above-mentioned prescription P1 was applied and dried. Furthermore, the curable composition 22 described in Table 5 was applied and dried. In this way, a thermoplastic resin layer having a film thickness of 15.1 μm, an intermediate layer having a film thickness of 1.7 μm, and a transparent curable composition layer having a film thickness of 65 nm are formed on the temporary support, Finally, a protective film (12 μm thick polypropylene film) was pressure-bonded. Thus, a transfer material in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), the transparent curable composition layer, and the protective film were integrated was produced.

(Formation of transparent film)
The protective film of the transfer material is peeled to expose the transparent curable composition layer, and the transparent curable composition layer and the intermediate layer are formed on the glass transparent substrate so that the exposed surface of the transparent curable composition layer is in contact with the transfer material. The thermoplastic resin layer and the PET temporary support were laminated together, and the PET temporary support was peeled off.
Next, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp, the entire surface was exposed from the thermoplastic resin layer side at i line and 40 mJ / cm ² . Next, triethanolamine developer (containing 30% triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation) 10 times with pure water (1 part of T-PD2 and 9 parts of pure water). The mixture was diluted to 30) at 30 C for 60 seconds at a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin and the intermediate layer. Subsequently, air was blown onto the upper surface (transparent curable resin layer side) of the glass transparent substrate to drain the liquid, and then pure water was blown for 10 seconds in a shower to wash, and air was blown onto the glass transparent substrate. Reduced the puddle. Next, the substrate was heat-treated (post-baked) under the conditions shown in Table 6 below, and a cured film (hereinafter referred to as “transparent film”) of the transparent curable composition layer was laminated on the glass transparent substrate. A substrate was obtained.

<2. Formation of transparent electrode pattern>
The glass transparent substrate on which the transparent film is laminated as described above is introduced into a vacuum chamber, and an ITO target (indium: tin = 95: 5 (molar ratio)) with a SnO ₂ content of 10% is used. An ITO thin film having a thickness of 40 nm and a refractive index of 1.82 was formed by DC magnetron sputtering (conditions: substrate temperature 250 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa), and a transparent electrode layer was formed. A front plate was obtained. The surface resistance of the ITO thin film was 80Ω / □.

(Preparation of photosensitive film E1 for etching)
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer composed of the above-mentioned formulation H1 was applied using a slit nozzle and dried. Next, the coating liquid for intermediate | middle layer which consists of the above-mentioned prescription P1 was apply | coated, and it dried. Further, the following photocurable resin layer coating solution for etching: Formulation E1 was applied and dried. Thus, the thermoplastic resin layer having a dry film thickness of 15.1 μm, the intermediate layer having a dry film thickness of 1.6 μm, and the photocurable resin layer for etching having a film thickness of 2.0 μm are formed on the temporary support. A laminate was obtained, and finally a protective film (12 μm thick polypropylene film) was pressure-bonded. Thus, a photosensitive transfer material for etching in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the transparent curable resin layer were integrated was produced.

(Coating liquid for photocurable resin layer for etching: prescription E1)
Methyl methacrylate / styrene / methacrylic acid copolymer (mass ratio = 31/40/29, weight average molecular weight 60000, acid value 163 mgKOH / g)
16 parts Monomer 1 (Brand name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.)
5.6 parts, 0.5 part adduct of tetramethylene oxide monomethacrylate of hexamethylene diisocyanate 7 parts, cyclohexanedimethanol monoacrylate as a compound having one polymerizable group in the molecule: 2.8 parts by mass, 2-chloro -N-butylacridone: 0.42 parts by mass 2,2-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole 2.17 parts malachite green oxalate 02 parts, 0.26 parts of leuco crystal violet, 0.013 parts of phenothiazine, surfactant (trade name: Megafac F-780F, manufactured by DIC Corporation)
0.03 parts · Methyl ethyl ketone 40 parts · 1-methoxy-2-propanol 20 parts The viscosity of the coating solution E1 for photocurable resin layer for etching after removing the solvent at 100 ° C. was 2500 Pa · sec.

(Formation of transparent electrode pattern)
The transparent electrode layer of the front plate was washed, and the photosensitive transfer material for etching from which the protective film was removed was laminated on the surface so that the photocurable resin layer for etching was in contact (base material temperature: 130 ° C., rubber Roller temperature 120 ° C., linear pressure 100 N / cm, conveyance speed 2.2 m / min). After removing the temporary support of the photosensitive photosensitive transfer material for etching, the distance between the exposure mask (quartz exposure mask having a transparent electrode pattern) surface and the photocurable resin layer for etching is set to 200 μm, and the exposure amount Pattern exposure was performed at 50 mJ / cm ² (i-line). Next, a triethanolamine developer (containing 30% by mass of triethanolamine, a trade name: T-PD2 (manufactured by Fuji Film Co., Ltd.) diluted 10 times with pure water) at 25 ° C. for 100 seconds, A surfactant-containing cleaning solution (trade name: T-SD3 (manufactured by FUJIFILM Corporation) diluted 10-fold with pure water) was treated at 33 ° C. for 20 seconds, using a rotating brush and an ultra-high pressure cleaning nozzle. Residue removal was performed, and a post-bake treatment at 130 ° C. for 30 minutes was further performed to obtain a front plate on which a transparent electrode layer and a photocurable resin layer pattern for etching were formed.
The front plate on which the transparent electrode layer and the photocurable resin layer pattern for etching are formed is immersed in an etching bath containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.), treated for 100 seconds, and used for etching. The exposed transparent electrode layer not covered with the photocurable resin layer was dissolved and removed to obtain a front plate with a transparent electrode layer pattern having a photocurable resin layer pattern for etching.
Next, a front plate with a transparent electrode layer pattern with a photocurable resin layer pattern for etching is applied to a resist stripping solution (N-methyl-2-pyrrolidone, monoethanolamine, a surfactant (trade name: Surfynol 465). , Made by Air Products) immersed in a resist stripping tank containing a liquid temperature of 45 ° C., treated for 200 seconds, removed the photocurable resin layer for etching, and formed a transparent film and transparent electrode pattern on a glass transparent substrate. The obtained substrate was obtained.

After imparting conductivity and surface protection to the end of the transparent electrode pattern with Pt coating (about 20 nm thick), using a FEI Nova200 type FIB / SEM compound machine, shape observation of the transparent electrode pattern end (two Next electron image, acceleration voltage 20 kV).
The formed ITO pattern had a tapered shape as shown in FIG. 1, and the taper angle α was about 3 °. FIG. 1 illustrates the taper angle α in the pattern 4.

<3. Formation of first curable transparent resin layer and second curable transparent resin layer>
A transparent film on a glass-made transparent substrate using the substrate obtained by forming a transparent film and a transparent electrode pattern on the glass-made transparent substrate obtained above, and the transfer films 21 to 23 and transfer films C9 to C11 described above. A laminate in which the cured film of the second curable transparent resin layer and the cured film of the first curable transparent resin layer of the transfer film are formed in this order on the transparent electrode pattern by the same method as in the above. Then, the sample was further heat-treated under the conditions shown in Table 6 to obtain 12 types of samples. The following evaluation was performed about these samples.

[Evaluation of transparent laminate]
<Evaluation of visibility of transparent electrode pattern>
A black PET material was adhered to the entire surface of the first curable transparent resin layer of the sample through a transparent adhesive tape (trade name, OCA tape 8171CL, manufactured by 3M Co., Ltd.) to shield the light.
The visibility of the transparent electrode pattern was performed by making light incident on the fluorescent lamp (light source) and the prepared substrate from the glass surface side and visually observing reflected light from the glass surface obliquely in a dark room.

"Evaluation criteria"
A: The transparent electrode pattern is not visible at all.
B: The transparent electrode pattern is slightly visible but hardly visible.
C: A transparent electrode pattern is visible (unclear).
D: Although a transparent electrode pattern can be seen, it is practically acceptable.
E: The transparent electrode pattern is clearly visible (easy to understand).
The obtained results are shown in Table 6 below.

<Evaluation of pencil hardness>
As an index of scratch resistance, pencil hardness evaluation described in JIS K 5400 was performed. The transparent laminated body of each Example and Comparative Example obtained by transferring the transfer film of each Example and Comparative Example to a glass transparent substrate, a substrate having a transparent film and a transparent electrode pattern, and a temperature of 25 ° C. After conditioning at a relative humidity of 60% for 1 hour, n = 7 was evaluated with a load of 500 g using a 2H test pencil specified in JIS S 6006.
"Evaluation criteria"
A: There are less than 3 scratches.
B: There are 3 or more and less than 5 scratches.
C: There are 5 or more and less than 6 scratches.
D: There are 6 or more scratches.
The obtained results are shown in Table 6 below.

From Table 6 above, those provided with cured films of the curable compositions 21 to 23 according to the examples of the present invention have sufficient pencil hardness even at low temperature (150 ° C.) baking while maintaining the visibility of the transparent electrode pattern. It can be seen that
On the other hand, any of the curable compositions C9 to C11 according to the comparative example and a cured film made of the curable composition C12 has good visibility of the transparent electrode pattern, but has low pencil hardness.

The disclosure of Japanese Patent Application No. 2013-064599 filed on March 26, 2013 and the Japanese Patent Application No. 2013-186394 filed on September 9, 2013 are hereby incorporated by reference in their entirety. It is captured. All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually described to be incorporated by reference, Incorporated herein by reference.

Claims

(A) a compound having a molecular weight of less than 1300 having at least two ethylenically unsaturated double bond groups and at least one secondary hydroxyl group;
(B) a hyperbranched compound having a molecular weight of 1300 or more;
(C) at least one initiator selected from the group consisting of a photopolymerization initiator and a thermal polymerization initiator;
A curable composition comprising:
The curable composition according to claim 1, wherein the (B) multi-branched compound is at least one selected from the group consisting of dendrimers and hyperbranched polymers.
Furthermore, (D) The curable composition of Claim 1 or Claim 2 containing resin which has an acidic group in a side chain.
The curable composition according to any one of claims 1 to 3, further comprising (E) a colorant.
The curable composition according to any one of claims 1 to 4, further comprising (F) a refractive index adjusting material.
6. The curable composition according to claim 5, wherein the (F) refractive index adjusting material is at least one kind of inorganic fine particles selected from metal fine particles and metal oxide fine particles.
A cured film formed by curing the curable composition according to any one of claims 1 to 6.
A color filter comprising the cured film according to claim 7.
A protective film comprising the cured film according to claim 7.
A display device including the color filter according to claim 8.
A display device comprising the protective film according to claim 9.
A solid-state imaging device including the color filter according to claim 8.
A solid-state imaging device including the protective film according to claim 9.