JP2012013945A - Colored curable composition, color filter, method for manufacturing color filter, solid imaging element and liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored curable composition comprising a pigment multimer, which is capable of forming a cured film having excellent color purity, light resistance, heat resistance and solvent resistance, as well as reduced color migration and good pattern formation properties.SOLUTION: A colored curable composition comprises (a) a pigment multimer comprising a squarylium compound represented by the following general formula (M) as a partial structure of a pigment site, (b) a polymerizable compound, (c) a photopolymerization initiator, and (d) an organic solvent. In the following general formula (M), A and B each independently represent an aryl group or a heterocyclic group.

Description

  The present invention relates to a colored curable composition containing a dye multimer suitable for the production of a color filter used in a liquid crystal display device, a solid-state imaging device, etc., a color filter and a method for producing the same, and a solid-state imaging device comprising the color filter The present invention also relates to a liquid crystal display element.

One of the methods for producing a color filter used for a liquid crystal display device, a solid-state imaging device or the like is a pigment dispersion method. As this pigment dispersion method, a colored radiation sensitive material in which pigments are dispersed in various photosensitive compositions. There is a method for producing a color filter by a photolithographic method using an adhesive composition. That is, a radiation-sensitive composition is applied onto a substrate using a spin coater, a roll coater, or the like, dried to form a coating film, and the coating film is subjected to pattern exposure and development to obtain a colored pixel. . By repeating this operation for a desired hue, a color filter is produced.
The method described above is stable against light and heat because it uses a pigment, and the positional accuracy is sufficiently secured because patterning is performed by a photolithographic method, and it is suitable as a method for manufacturing a color filter for a color display. It has been widely used.

  On the other hand, a color filter for a solid-state imaging device such as a CCD has recently been desired to have higher definition. The pattern size tends to become finer with higher definition, but it is considered difficult to make the pattern size finer and improve the resolution with the pigment dispersion method that has been widely used. Yes. One reason for this is that, in a fine pattern, coarse particles formed by aggregation of pigment particles cause color unevenness. Therefore, in recent years, the pigment dispersion method that has been widely used so far is not necessarily suitable for applications requiring a fine pattern such as a solid-state imaging device.

Under the background described above, in order to achieve high resolution, it has been conventionally studied to use a dye as a colorant (see, for example, Patent Document 1). However, the dye-containing curable composition has the following new problems. That is,
(1) A dye that is in a molecularly dispersed state is generally inferior in light resistance and heat resistance compared to a pigment that is a molecular assembly.
(2) A dye that is in a molecularly dispersed state is generally inferior in solvent resistance compared to a pigment that is a molecular assembly.
(3) The dye often exhibits an interaction with other components in the curable composition, and it is difficult to adjust the solubility (developability) of the cured part and the non-cured part.
(4) When the molar extinction coefficient (ε) of the dye is low, a large amount of dye must be added. For that purpose, the polymerizable compound (monomer), binder, photopolymerization initiator, etc. in the curable composition The other components must be reduced, and the curability of the composition, the heat resistance after curing, the developability of the (non-) cured part, etc. are reduced.

  Among these problems of dyes, squarylium compounds have been studied as dyes that solve (1) light resistance and heat resistance of dyes and (4) molar extinction coefficient (ε) of dyes (for example, patents). Reference 2 and Patent Document 3).

However, a colored curable composition containing a squarylium compound as a dye has been required to have better light resistance and heat resistance.
Further, as described in the above problem (2), in order to use a dye as a coloring component, it has been required to improve the solvent resistance. The solvent resistance is a performance in which the coloring component in the cured portion does not elute into the solvent and is retained in the film. When an RGB color filter is manufactured by the photolithography method, a resist solution having a different hue is covered on the colored pattern in order to sequentially form each color pattern. At that time, since the coloring component in the cured portion elutes into the colored curable composition of the next color or the dye contained in the colored curable composition of the next color shifts to the colored pixel, a problem of color mixing occurs. In the color filter manufacturing process, very high solvent resistance is required for the cured portion. In this respect, the dye is in a molecularly dispersed state, and is inferior in solvent resistance as compared with a pigment forming an aggregate with a strong intermolecular force.
Furthermore, in the production of a color filter, heat treatment may be performed after the coating, exposure, and development steps in order to increase the degree of curing of the colored pattern. Compared to pigments that are molecular aggregates, dyes that are in a molecularly dispersed state can move with small thermal energy, so they easily transfer to adjacent patterns with different hues, and the fixation of the dye in the cured area is a major issue. there were.

JP-A-6-75375 JP 2002-97383 A JP 2003-35818 A

This invention is made | formed in view of said point, and makes it a subject to achieve the following objectives.
That is, the first object of the present invention is to provide a colored curable composition that is excellent in color purity, light resistance, heat resistance, and solvent resistance, has little color transfer, and can form a cured film with good pattern moldability. There is to do. Furthermore, the second object of the present invention is to provide a color filter having a color pattern excellent in color purity, heat resistance and light resistance even when it is thinned, a method for producing the color filter, and the color filter. An object of the present invention is to provide a solid-state imaging device and a liquid crystal display device.

  As a result of detailed examination of various dyes, the present inventors have found that a squarylium compound having a specific structure has a good hue and a high extinction coefficient, and is excellent in solvent fastness such as solvent solubility, heat resistance, and light resistance. Introducing the squarylium compound structure into the dye multimer, in particular, introducing a polymerizable group into the squarylium compound structure to form a dye multimer as a polymerization component, thereby providing high solvent resistance and reducing color transfer. The knowledge that it is possible to provide a cured film that can be obtained, and can provide a cured film that has excellent pattern-forming properties (low concentration dependency of the alkaline developer) by introducing an alkali-soluble group into the dye multimer as necessary. Thus, the present invention has been achieved based on such findings.

Specific means for solving the above problems are as follows.
<1> (a) a dye multimer comprising a squarylium compound represented by the following general formula (M) as a partial structure of the dye part, (b) a polymerizable compound, (c) a photopolymerization initiator, and (d) A colored curable composition containing an organic solvent.

[In General Formula (M), A and B each independently represents an aryl group or a heterocyclic group. ]
<2> One or more types of the squarylium compound represented by the general formula (M) selected from a compound represented by the following general formula (M-1) and a compound represented by the general formula (M-2) The colored curable composition according to <1>, which is a compound of

[In General Formula (M-1), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , and R ⁸ are each independently a hydrogen atom, a halogen atom, a linear or branched alkyl group, a cyclo Alkyl group, linear or branched alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy Group, acyloxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or aryl Sulfonylamino group, mercapto group, alkylthio group, arylthio Group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, It represents a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group or a silyl group. R ¹ and R ² , R ⁵ and R ⁶ may be connected to each other to form a ring. R ³ and R ⁷ each independently represents a hydrogen atom, a chain alkyl group, a cycloalkyl group, a cycloalkenyl group, an alkynyl group, an aryl group or a heterocyclic group. ]

[In the general formula (M-2), R ²¹ , R ²³ , R ²⁴ , R ²⁵ , R ²⁷ and R ²⁸ are the same as R ¹ , R ³ , R ⁴ , R ⁵ in the general formula (M-1), respectively R ⁷ and ^{R 8} are synonymous. ]
<3> The (a) dye multimer comprises at least one of the structural units represented by the following general formula (A) and general formula (C), or represented by the general formula (D). The colored curable composition according to <1> or <2>, which is a dye multimer.

[In General Formula (A), X ^A1 represents a linking group formed by polymerization, and L ^A1 represents a single bond or a divalent linking group. Dye represents a dye residue obtained by removing one arbitrary hydrogen atom of the squarylium compound represented by the general formula (M). ]

[In the general formula (C), L ^C1 represents a single bond or a divalent linking group, and Dye represents a dye residue obtained by removing two hydrogen atoms of the squarylium compound represented by the general formula (M). n represents an integer of 1 to 4. ]

[In General Formula (D), L ^D1 represents an m-valent linking group, m represents an integer of 2 to 100, and Dye represents an arbitrary hydrogen atom of the squarylium compound represented by General Formula (M). Represents the pigment residue after removal. ]
<4> The colored curable composition according to <3>, wherein the structural unit represented by the general formula (A) is derived from a dye monomer represented by the following general formula (1).

[In General Formula (1), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. L ¹ is —N (R ² ) C (═O) —, —OC (═O) —, —C (═O) N (R ¹² ) —, —C (═O) O—, The group represented by (2), the group represented by the following general formula (3), or the group represented by the following general formula (4) is represented. L ² represents a divalent linking group. m and n each independently represents 0 or 1. Dye is a dye residue obtained by removing one hydrogen atom from the squarylium compound represented by the general formula (M-1), or any hydrogen atom derived from the squarylium compound represented by the general formula (M-2). Represents a dye residue with one atom removed. R ¹² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. ]

[In General Formula (2) to General Formula (4), R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ³ represents a monovalent substituent. k represents an integer of 0 to 4. In the general formula (2) to the general formula (4), * represents a position bonded to the —C (R ¹ ) ═CH ₂ group in the general formula (1), and ** represents L in the general formula (1). ² or Dye (when n = 0) is represented. ]

<5> The colored curable composition according to any one of <1> to <4>, wherein the (a) dye multimer has an alkali-soluble group.
<6> The colored curable composition according to any one of <1> to <5>, further comprising (a-2) (a) a colorant other than the dye multimer.
<7> The colorant other than the (a-2) (a) dye multimer is C.I. I. The colored curable composition according to <6>, which is CI Pigment Blue 15: 6.

<8> A color filter using the colored curable composition according to any one of <1> to <7>.
<9> A step of applying the colored curable composition according to any one of <1> to <7> onto a substrate to form a colored curable composition layer, and the colored curable composition layer. A method for producing a color filter, comprising: exposing in a pattern, and forming a pattern by developing and removing unexposed portions.
<10> The colored curable composition according to any one of <1> to <7>, which is used to form a color filter for a solid-state imaging device.
<11> A solid-state imaging device comprising the color filter according to <8>.
<12> The colored curable composition according to any one of <1> to <7>, which is used to form a color filter for a liquid crystal display element.
<13> A liquid crystal display device comprising the color filter according to <8>.

  In the colored curable composition of the present invention, the pixel pattern is formed in a thin film (for example, a thickness of 1 μm or less), and the micropattern is 2 μm or less (the side length of the pixel pattern viewed from the substrate normal direction is, for example, 0.5 to 2.0 μm). ) Is required, and is particularly effective for forming a color filter for a solid-state imaging device that requires a good rectangular cross-sectional profile.

ADVANTAGE OF THE INVENTION According to this invention, the color curable composition which is excellent in color purity, light resistance, heat resistance, and solvent resistance, has little color transfer, and can form the cured film with favorable pattern moldability can be provided.
Further, according to the present invention, a color filter having a color pattern excellent in color purity, heat resistance, and light resistance even when thinned by using the colored curable composition of the present invention, the color A filter manufacturing method and a solid-state imaging device and a liquid crystal display device including the color filter can be provided.

  Hereinafter, a colored curable composition containing a specific dye multimer according to the present invention, a color filter, a method for producing the color filter, and a solid-state imaging device and a liquid crystal display device provided with the color filter of the present invention Detailed description. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

  The colored curable composition of the present invention contains at least one kind of (a) dye multimer described in detail below as a colorant. The colored curable composition of the present invention is characterized by being cured by heat, light or both, and (b) a polymerizable compound, (c) a photopolymerization initiator, (d) an organic solvent, Can be constituted by using other components such as a binder and a crosslinking agent as required.

  According to the characteristics of the squarylium compound having a specific structure, which is included in the structure of the (a) dye multimer according to the present invention, the colored curable composition of the present invention has a thin pixel pattern (for example, a thickness of 1 μm or less). It is formed. Therefore, the colored curable composition of the present invention is required to have a high definition with a minute size of 2 μm or less (the side length of the pixel pattern viewed from the substrate normal direction is, for example, 0.5 to 2.0 μm). It is particularly suitable for the production of a color filter for a solid-state imaging device that requires a rectangular cross-sectional profile.

In the colored curable composition of this invention, (a) pigment | dye multimer may be used individually by 1 type, and may be used together 2 or more types.
The content of the (a) dye multimer in the colored curable composition of the present invention varies depending on the molecular weight and molar extinction coefficient of the (a) dye multimer, but the total solid content of the colored curable composition is the same. On the other hand, 10 mass%-70 mass% is preferable, 10 mass%-50 mass% is more preferable, 15 mass%-30 mass% is the most preferable.
Here, the “total amount of all solids” refers to the sum of all components excluding the solvent from the colored curable composition.

The colored curable composition of the present invention is characterized by containing a specific (a) dye multimer. First, the dye multimer which is a characteristic component of the present invention will be described.
(A) Dye Multimer The dye multimer according to the present invention is a dye multimer including a dye skeleton derived from a squarylium compound described in detail below as a partial structure. The method for introducing a dye skeleton derived from a squarylium compound into the dye multimer according to the present invention is arbitrary, and a polymer obtained by polymerizing or copolymerizing a polymerizable monomer into which the dye skeleton is introduced is used. Alternatively, after forming a multimer, a dye skeleton may be introduced by a polymer reaction or the like.
Preferred embodiments include the above general formula (A), a multimer comprising at least one structural unit represented by the general formula (C), and the above general formula (A) which is a preferred embodiment of the above general formula (A). Examples include a multimer containing the dye monomer represented by 1) as a polymerization component, and a dye multimer represented by the general formula (D).

<Preferred physical properties of the dye multimer according to the present invention>
The dye multimer derived from the squarylium compound according to the present invention is excellent in color purity, light resistance, heat resistance and solvent resistance, has little color transfer, and can form a cured film with good pattern formability. It can be used for a colored curable composition suitable for forming a colored pattern. From such a viewpoint, if the preferable physical properties of the dye multimer according to the present invention are mentioned, when the dye multimer according to the present invention is applied to a colored curable composition, the present invention is improved from the viewpoint of improving the color pattern forming property. The dye multimer according to the above preferably has an alkali-soluble group.

The method for introducing an alkali-soluble group into the dye multimer according to the present invention is not particularly limited, but can be introduced by synthesizing a dye multimer using a monomer having an alkali-soluble group. The alkali-soluble group can be introduced after the dye multimer is synthesized.
When synthesizing a dye multimer using a monomer having an alkali-soluble group, the dye multimer comprising at least one of the structural units represented by the general formula (A) and the general formula (C) The dye multimer represented by the general formula (D), the dye monomer represented by the general formula (1), and the terminal ethylenically unsaturated bond and represented by the general formula (1) It suffices that at least one of the monomers having a different structure from the dye monomer has an alkali-soluble group. When the structural unit represented by the general formula (A) and the general formula (C), or the dye monomer represented by the general formula (1) is a monomer having an alkali-soluble group, The Dye part (pigment residue) may have an alkali-soluble group. From the viewpoint of synthetic compatibility, at least one other ethylenically unsaturated bond monomer contained as a copolymerization component is included rather than a monomer that forms a structural unit having a Dye portion (dye residue). A monomer having an alkali-soluble group is preferable.

As preferred alkali-soluble group dye polymer of the present invention has a carboxyl group, a sulfonic acid group, a phosphonic acid group, a hydroxyl _{group, -COCH 2 CO -, - COCH} 2 CN, a -SO ₂ CH 2 CO-, Preferred are a carboxy group and a sulfonyl group, and a carboxy group is most preferred.
Examples of preferable monomers of other ethylenically unsaturated bond-containing monomers contained as a copolymer component of the above-mentioned dye multimer include acrylic acid, methacrylic acid, crotonic acid, α-methyl-p- Monocarboxylic acids such as carboxystyrene; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, sulfonic acids such as 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, phosmer M, phosmer PE, phosphonic acid such as Phosmer PP (manufactured by Unichemical Co., etc.), monocarboxylic acid is particularly preferable, and acrylic acid and methacrylic acid are most preferable.

The dye multimer according to the present invention preferably contains an alkali-soluble group having an acid value of 10 to 400 mgKOH / g, and an acid value of 30 to 300 mgKOH / g from the viewpoint of color pattern formation when applied to a colored curable composition. g is more preferable, and an acid value of 50 to 200 mgKOH / g is more preferable.
In the present invention, the acid value is determined by the method described in JIS standard (JIS K 0070: 1992).

  The dye multimer according to the present invention preferably has a solubility in an alkaline solution (pH 9 to 15) of 0.1% by mass or more and 80% by mass or less, and is 0.5% by mass or more and 50% by mass or less. More preferably, the content is 1% by mass or more and 30% by mass. By being in this region, when the colored curable composition of the present invention using the dye multimer is used for an application that requires alkali development such as a color resist, formation of a suitable shape or residue on the substrate Can be reduced.

  The dye multimer according to the present invention is preferably a compound that dissolves in the following organic solvent. Examples of the organic solvent include esters (eg, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate), ethers (eg, methyl cellosolve acetate, ethyl cellosolve acetate). , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), ketones (methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.), aromatic hydrocarbons (for example, toluene, xylene, etc.), and these solvents On the other hand, it is preferable to dissolve 1% by mass or more and 50% or less, more preferably 5% or more and 40% or less, and further preferably 10% or more and 30% or less. By being in this region, when applying the dye multimer according to the present invention to a color resist or the like, it becomes possible to reduce a suitable coating surface shape and a decrease in density due to elution after application of other colors.

  The Tg of the dye multimer according to the present invention is preferably 50 ° C. or higher, and more preferably 100 ° C. or higher. Further, the 5% weight loss temperature by thermogravimetric analysis (TGA measurement) is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and further preferably 200 ° C. or higher. By being in this region, it is possible to reduce the concentration change caused by the heating process when the dye multimer according to the present invention is applied to a color resist or the like.

  The maximum absorption wavelength (λmax) of the dye multimer according to the present invention is preferably 510 nm or more and 590 nm or less, preferably 530 nm or more and 570 nm or less, and more preferably 540 nm or more and 555 nm or less. By being in this region, it is possible to produce a color filter with good color reproducibility when applied to a color resist or the like. Furthermore, the absorbance at the maximum absorption wavelength (λmax) is preferably 1,000 times or more, more preferably 10,000 times or more, with respect to the absorbance at 450 nm of the dye multimer according to the present invention. More preferably, it is 000 times or more. When this ratio is within this range, when the colored curable composition of the present invention is applied to the formation of a colored pattern of a color filter, a filter with higher transmittance is formed, particularly when a blue color filter is produced. I can do it.

Further, the extinction coefficient per unit weight of the dye multimer according to the present invention (hereinafter referred to as ε ^′ ; ε ^′ = ε / average molecular weight, unit: L / g · cm) is preferably 30 or more, and 60 More preferably, it is more preferably 100 or more. By being in this range, when applying the said dye multimer to the colored curable composition of this invention and producing a color filter, a filter with sufficient color reproducibility can be produced.

  Further, it is more preferable that the dye multimer according to the present invention simultaneously satisfies the preferable ranges of the maximum absorption wavelength (λmax) and the extinction coefficient per unit weight of the dye multimer.

<Structure of (a) Dye Multimer of the Present Invention>
Details of the structure of the (a) dye multimer of the present invention will be described below.
The dye multimer according to the present invention includes a squarylium compound represented by the following general formula (M) and a tautomer thereof, in particular, a squarylium compound represented by the following general formula (M-1), which is a preferred embodiment, or It includes a dye skeleton derived from a squarylium compound represented by the general formula (M-2).
<The squarylium compound represented by the general formula (M) and its tautomer>
One aspect of the dye multimer according to the present invention is a dye multimer including a structure derived from a compound represented by the following general formula (M) (squarylium compound) as a partial structure of the dye moiety. In the present invention, the squarylium compound is a general term for compounds having a dye moiety containing a squarylium skeleton in the molecule.

  In general formula (M), A.I. And B represents an aryl group or a heterocyclic group each independently. The aryl group is preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, and examples thereof include phenyl and naphthyl. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group, and examples include pyroyl, imidazoyl, pyrazoyl, thienyl, pyridyl, pyrimidyl, pyridazyl, triazol-1-yl, thienyl, furyl, thiadiazoyl and the like. .

  The compound represented by the general formula (M) is particularly preferably a compound represented by the general formula (M-1) or the general formula (M-2).

In general formula (M-1), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , and R ⁸ are each independently a hydrogen atom, a halogen atom, a linear or branched alkyl group, or cycloalkyl. Group, linear or branched alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group , Acyloxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonyl Amino group, mercapto group, alkylthio group, arylthio , Heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino Represents a group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group or a silyl group.
R ³ and R ⁷ each independently represents a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, a cycloalkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.
R ¹ and R ² , and R ⁵ and R ⁶ may be connected to each other to form a ring.

In the general formula (M-2), R ²¹ , R ²³ , R ²⁴ , R ²⁵ , R ²⁷ and R ²⁸ are R ¹ , R ³ , R ⁴ , R ⁵ , R in the general formula (M-1). ⁷ and R ⁸ have the same meanings.

Below ^{R 1, R 2, R 4} , R 5, the substituents R 6, ^{R 8} can be taken in the general formula (M-1), further described.
A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a linear or branched alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms) For example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably having 3 to 30 carbon atoms, or Examples thereof include unsubstituted cycloalkyl groups such as cyclohexyl and cyclopentyl, and polycycloalkyl groups such as bicycloalkyl groups (preferably substituted or unsubstituted bicycloalkyl groups having 5 to 30 carbon atoms such as bicyclo [ 1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl Or group of polycyclic structures such as tricycloalkyl groups. Preferably monocyclic cycloalkyl group, a bicycloalkyl group, a monocyclic cycloalkyl group is particularly preferred.)

  Linear or branched alkenyl group (straight or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl Group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, such as 2-cyclopenten-1-yl and 2-cyclohexen-1-yl, and a polycycloalkenyl group such as bicyclo An alkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms such as bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] Oct-2-en-4-yl) and tricycloalkenyl groups, with monocyclic cycloalkenyl groups being particularly preferred. Le group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, e.g., ethynyl, propargyl, trimethylsilylethynyl group),

  An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably 5 to 5 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, more preferably the ring-constituting atom is selected from carbon atom, nitrogen atom and sulfur atom And a heterocyclic group having at least one heteroatom of any one of a nitrogen atom, an oxygen atom and a sulfur atom, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. For example, 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydro Sill group, a nitro group, a carboxyl group,

  An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably Is a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 2,4-di-t-amylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having a carbon number of 2 30 substituted or unsubstituted heterocyclic oxy groups, wherein the heterocyclic moiety is Preferably heterocyclic portion described in cyclic group, for example, 1-phenyl-5-oxy, 2-tetrahydropyranyloxy),

  An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy , Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably having 2 to 30 carbon atoms) Or an unsubstituted alkoxycarbonyloxy group such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted group having 7 to 30 carbon atoms). Substituted aryloxycarbonyloxy groups such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

  An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a heterocyclic amino group having 0 to 30 carbon atoms); For example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazin-2-ylamino), acylamino group (preferably formylamino group, carbon number A substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3, 4,5-tri-n-octyloxyphenylcarbonylamino), amino A rubonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl- Methoxycarbonylamino),

  Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino) A sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylamino A sulfonylamino), alkyl or arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as methyl Sulfonylami , Butyl sulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenyl sulfonylamino, p- methylphenyl sulfonylamino), a mercapto group,

  An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms). , For example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, wherein the heterocyclic portion is the above-described heterocyclic group The heterocyclic moiety described in the above is preferable, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfa Yl, N, N- dimethylsulfamoyl, N- acetyl sulfamoyl, N- benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), a sulfo group,

  An alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), an alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl , Ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms) Base Yes, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms) And, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl),

  An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably having a carbon number) 1-30 substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl or hetero A ring azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (the heterocycle portion is the heterocycle described in the above heterocyclic group); Ring portion is preferred), for example, phenylazo, p Chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms such as N-succinimide and N-phthalimide) A phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably substituted having 2 to 30 carbon atoms) Or an unsubstituted phosphinyl group such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl),

  A phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino group ( Preferably, it is a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably substituted with 3 to 30 carbon atoms) Or an unsubstituted silyl group, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl).

  Among the above functional groups, those having a hydrogen atom may have a hydrogen atom portion in the functional group substituted with any of the above groups. Examples of functional groups that can be introduced as a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Specifically, methylsulfonylaminocarbonyl, Examples include p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

R ^{1 to} R ⁸ are each independently preferably a hydrogen atom, an alkyl group, a hydroxy group, an amino group, an aryl group or a heterocyclic group, and R ³ , R ⁴ , R ⁷ and R ⁸ are alkyl groups. More preferably, R ¹ and R ² , and R ⁵ and R ⁶ are connected to each other to form an aryl ring, and R ³ , R ⁴ , R ^7, and R ⁸ have 1 to 20 carbon atoms. Most preferably, R ¹ and R ² , and R ⁵ and R ⁶ are connected to each other to form a benzene ring.

In the general formula (M-2), R ²¹ , R ²³ , R ²⁴ , R ²⁵ , R ²⁷ and R ²⁸ are R ¹ , R ³ , R ⁴ and R ^{5 in the} general formula (M-1), respectively. , R ⁷ and R ⁸ .
In particular, R ²¹ , R ²³ , R ²⁴ , R ²⁵ , R ²⁷ and R ²⁸ are preferably a hydrogen atom, an alkyl group, a hydroxy group, an amino group, an aryl group, or a heterocyclic group, and R ²¹ , R ²³ , R ²⁵ and R ²⁷ are each an alkyl group or an aryl group, and R ²⁴ and R ²⁸ are more preferably a hydroxy group or an amino group, and R ²¹ , R ²³ , R ²⁵ and R ²⁷ are each a carbon number. More preferably, it is a 1-20 alkyl group, and R < ²⁴ > and R < ²⁸ > are hydroxy groups.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ²¹ , R ²³ , R ²⁴ , R ²⁵ , R ²⁷ and R ²⁸ are further substitutable groups. In some cases, it may be substituted with a substituent selected from the monovalent substituents exemplified in the above R ^{4 to} R ⁹ , and when substituted with two or more substituents, The substituents may be the same or different.

  The compound contained as a partial structure in the (a) dye multimer according to the present invention preferably has a structure derived from a squarylium compound represented by the general formula (M-2) from the viewpoint of hue.

The squalium compound represented by the general formula (M) is a structural unit represented by the following general formula (A), general formula (C), a multimer represented by the general formula (D), or general The introduction site in the case of introduction into the monomer represented by formula (1) is not particularly limited, but it is preferably introduced into either A or B from the viewpoint of synthesis compatibility. In particular, the squarylium compounds represented by general formula (M-1) and general formula (M-2) are structural units represented by general formula (A) and general formula (C) described later, and general formula (D). The introduction site in the case of introduction into the monomer represented by the general formula (1) or the monomer represented by the general formula (1) is not particularly limited, but in terms of synthesis compatibility, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ , or R ²¹ , R ²³ , R ²⁴ , R ²⁵ , R ²⁷ and R ²⁸ are preferably introduced at any one site, Most preferably, it is introduced at any one of R ³ and R ⁷ , or R ²³ and R ²⁷ .

As a method for introducing an alkali-soluble group into the dye multimer according to the present invention, an alkali-soluble group is added to one or two or more substituents of A or B of the squarylium compound represented by the general formula (M). The method to introduce is mentioned. In particular, when the squarylium compound is a compound represented by the general formulas (M-1) and (M-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ Alternatively, an alkali-soluble group may be introduced into one or more substituents of R ²¹ , R ²³ , R ²⁴ , R ²⁵ , R ²⁷ and R ²⁸ . Among these substituents, an aspect in which an alkali-soluble group is introduced into any one of R ³ and R ⁷ , or R ²³ and R ²⁷ is most preferable.

  The squarylium compounds represented by the general formula (M), the general formula (M-1), and the general formula (M-2) may be other than the alkali-soluble group as necessary as long as the effects of the present invention are not impaired. It may have a functional group.

The molar extinction coefficient of the squarylium compound represented by the general formula (M) is preferably as high as possible from the viewpoint of film thickness. The maximum absorption wavelength λmax is preferably 520 nm to 580 nm, more preferably 530 nm to 570 nm, from the viewpoint of improving color purity. The maximum absorption wavelength and molar extinction coefficient are measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation).
The melting point of the squarylium compound represented by the general formula (M) is preferably not too high from the viewpoint of solubility. More specifically, the melting point is preferably 50 ° C to 150 ° C.

  The squarylium compound represented by the general formula (M) Chem. Soc. Perkin Trans. 1,2000,599. Can be synthesized by applying the method described in 1. above.

The dye multimer according to the present invention having the preferred dye skeleton will be described. The dye multimer having a dye skeleton derived from the squarylium compound comprises at least one of the structural units represented by the following general formula (A) and general formula (C), or the general formula ( And a dye multimer represented by the following formula (1), which is a more preferable embodiment of the general formula (A), as a polymerization component. These will be described sequentially.
<Structural Unit Represented by General Formula (A)>

In general formula (A), X ^A1 represents a linking group formed by polymerization, and L ^A1 represents a single bond or a divalent linking group. Dye represents a dye residue obtained by removing one arbitrary hydrogen atom of the squarylium compound represented by the general formula (M). Dye and the L ^A1, covalent bonding, ionic bonding, and may be connected at any coordination bonds.

In the general formula (A), X ^A1 represents a linking group formed by polymerization. That is, it refers to a portion that forms a repeating unit corresponding to the main chain formed by the polymerization reaction. Two sites represented by * are repeating units. ^Examples of X ^A1 include a linking group formed by polymerizing a substituted or unsubstituted unsaturated ethylene group, a linking group formed by ring-opening polymerization of a cyclic ether, and preferably an unsaturated ethylene group. It is a linking group formed by polymerization. Specific examples include the following linking groups, but the linking groups formed by polymerization in the present invention are not limited to these.
In addition, in the following (X-1)-(X-15), it represents having connected with ^LA1 in the site ^| part shown by *.

In general formula (A), L ^A1 represents a single bond or a divalent linking group. When L ^A1 represents a divalent linking group, the divalent linking group is a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 30 carbon atoms (for example, a methylene group, an ethylene group, a trimethylene group). , Propylene group, butylene group, etc.), substituted or unsubstituted arylene group having 6 to 30 carbon atoms (for example, phenylene group, naphthalene group, etc.), substituted or unsubstituted heterocyclic linking group, -CH = CH-,- O—, —S—, —NR—, —C (═O) —, —SO—, —SO ₂ —, a linking group represented by the following general formula (2), represented by the following general formula (3) Or a linking group formed by linking two or more of these (for example, —N (R) C (═O) —, — OC (= O)-, -C (= O) N (R)-, -C (= O) O-, here , R represents each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. ] Is represented. The divalent linking group in the general formula (A) is not particularly limited as long as the effects of the present invention can be obtained.

In general formula (A), Dye is a squarylium compound represented by general formula (M), preferably a squarylium compound represented by general formula (M-1) or general formula (M-2). Represents a dye residue obtained by removing one hydrogen atom.
Although the specific example of the structural unit represented by general formula (A) is shown below, this invention is not limited to this.

<Structural Unit Represented by General Formula (C)>
Next, details of the structural unit represented by the general formula (C) will be described.

In the general formula (C), L ^C1 represents a single bond or a divalent linking group, Dye represents a dye residue obtained by removing two hydrogen atoms of the squarylium compound of the general formula (M), A dye residue obtained by removing two arbitrary hydrogen atoms from the squarylium compound represented by the general formula (M-1) or (M-2). n represents an integer of 1 to 4.

In the general formula (C), the divalent linking group represented by L ^C1 is a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 30 carbon atoms (for example, a methylene group, an ethylene group, trimethylene group, propylene group, butylene group), a substituted or unsubstituted arylene group (e.g. having 6 to 30 carbon atoms, a phenylene group, naphthalene group), a substituted or unsubstituted heterocyclic linking group, -CH 2 ₌ CH _{2 -, - O -, -} S -, - NR -, - C (= O) -, - SO -, - SO 2 -, and the linking group formed by linking two or more of these (e.g., -N (R) C (= O)-, -OC (= O)-, -C (= O) N (R)-, -C (= O) O-, -N (R) C (= O And N (R)-) and the like. Here, R in each said formula represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.

Although the specific example used suitably as a bivalent coupling group represented by L ^C1 in general formula (C) below is described, L ^C1 of the present invention is not limited to these.

  Although the specific example of the structural unit represented by general formula (C) is shown below, this invention is not limited to this.

<Dye Multimer Represented by General Formula (D)>
Next, the details of the dye multimer represented by formula (D) will be described.

In the general formula (D), L ^D1 represents an m-valent linking group, m represents an integer of 2 to 100, and Dye is a compound represented by the general formula (M), preferably the general formula (M -1) or a dye residue obtained by removing one arbitrary hydrogen atom of the squarylium compound represented by (M-2).

In the general formula (D), m is preferably 2 to 80, more preferably 2 to 40, and particularly preferably 2 to 10.
In the general formula (D), when m is 2, the divalent linking group represented by L ^D1 is a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 30 carbon atoms (for example, methylene Group, ethylene group, trimethylene group, propylene group, butylene group, etc.), substituted or unsubstituted arylene group having 6 to 30 carbon atoms (for example, phenylene group, naphthalene group, etc.), substituted or unsubstituted heterocyclic linking group, —CH═CH—, —O—, —S—, —NR—, —C (═O) —, —SO—, —SO ₂ —, and a linking group formed by linking two or more thereof. [For example, -N (R) C (= O)-, -OC (= O)-, -C (= O) N (R)-, -C (= O) O-, -N (R) C (= O) N (R)-and the like] are preferred. Here, R in each said formula represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
The m-valent linking group in which m is 3 or more is a substituted or unsubstituted arylene group (1,3,5-phenylene group, 1,2,4-phenylene group, 1,4,5,8-naphthalene group, etc.) And a linking group formed by substituting the divalent linking group using a heterocyclic linking group (for example, 1,3,5-triazine group, etc.), an alkylene linking group or the like as a central mother nucleus.
Although the specific example of the pigment | dye multimer represented by general formula (D) below is shown, this invention is not limited to this.

The dye multimer according to the present invention preferably contains the structural unit represented by the general formula (A) or the general formula (C) as a part thereof. Among these, the general formula (A) It is preferably included as a structural unit represented by
Furthermore, the structural unit represented by the general formula (A) is preferably a structural unit derived from a dye monomer represented by the following general formula (1).
Below, the detail about the pigment | dye monomer represented by General formula (1) is described.

<Dye monomer represented by general formula (1)>
The dye monomer contained as a polymerization component in the dye multimer according to the present invention will be described in detail.
The dye monomer is a compound represented by the following general formula (1).

In the general formula (1), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. L ¹ represents —N (R) C (═O) —, —OC (═O) —, —C (═O) N (R) —, —C (═O) O—, the following general formula (2 ), A group represented by the following general formula (3), or a group represented by the following general formula (4). R in the said coupling group represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, respectively.
L ² represents a divalent linking group. m and n each independently represents 0 or 1. Dye is represented by the dye residue in which one arbitrary hydrogen atom is removed from the squarylium compound represented by the general formula (M), or the general formula (M-1) and the general formula (M-2) described above. Any of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ , or R ²¹ , R ²³ , R ²⁴ , R ²⁵ , R ²⁷ and R ²⁸ This represents a dye residue from which one hydrogen atom of one substituent is removed.

In General Formula (2) to General Formula (4), R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ³ represents a monovalent substituent. k represents an integer of 0 to 4. In the general formula (2) to the general formula (4), * represents a position bonded to the —C (R ¹ ) ═CH ₂ group in the general formula (1), and ** represents the general formula (1). It represents a position bonded with the (case of n = 0) ^{L 2} or Dye in.

In other words, the dye monomer represented by the general formula (1) is generally used in the squarylium compound represented by the general formula (M) or the general formula (M-1) or the general formula (M-2). in the formula ^(1), - a (L 1) m ^-C (R 1) = compound polymerizable group is introduced, represented by _{^{CH 2 - (L 2) n}} .
When both m and n are 0, a —C (R ¹ ) ═CH ₂ group is directly introduced into the squarylium compound. Here, L ¹ , L ² and R ¹ have the same meaning as in the general formula (1).

In the general formula (1), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. When R ¹ is an alkyl group or an aryl group, it may be unsubstituted or substituted.

When R ¹ is an alkyl group, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 6 carbon atoms is preferable. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, octyl group, isopropyl group, cyclohexyl group and the like.
When R ¹ is an aryl group, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 6 to 12 carbon atoms is preferable. Examples of the aryl group include a phenyl group and a naphthyl group.

When R ¹ is a substituted alkyl group or a substituted aryl group, the substituent is preferably a halogen atom (eg, fluorine, chlorine, bromine, iodine), an alkyl group (preferably having 1 to 24 carbon atoms, more preferably carbon). An alkyl group having 1 to 12, for example, methyl, ethyl, propyl, butyl, isopropyl, t-butyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, adamantyl), an aryl group (preferably having 6 to 6 carbon atoms) 24, more preferably an aryl group having 6 to 12 carbon atoms, for example, phenyl, naphthyl), hydroxyl group, cyano group, nitro group, sulfonic acid group, phosphonic acid group, carboxyl group, alkoxy group (preferably having 1 carbon atom) To 24, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms. Si group, for example, methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy group, for example, cyclopentyloxy, cyclohexyloxy), aryloxy group (preferably carbon An aryloxy group having 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms, for example, phenoxy, 1-naphthoxy), an alkoxycarbonyloxy group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, More preferably, it is an alkoxycarbonyloxy group having 2 to 6 carbon atoms, such as ethoxycarbonyloxy, t-butoxycarbonyloxy),

Cycloalkyloxycarbonyloxy (for example, cyclohexyloxycarbonyloxy)), aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 24 carbon atoms, more preferably 7 to 12 carbon atoms, for example, phenoxycarbonyloxy ), A carbamoyloxy group (preferably a carbamoyloxy group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N-butyl Rucarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy), sulfamoyloxy group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 1 carbon atoms). With 6 sulfamoyloxy groups For example, N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), alkylsulfonyloxy group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 1 carbon atoms). 6 alkylsulfonyloxy group, for example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy), arylsulfonyloxy group (preferably having 6 to 24 carbon atoms, more preferably having 6 to 12 carbon atoms) For example, phenylsulfonyloxy), an acyl group (preferably an acyl group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, for example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl ),

  An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl ), An aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, more preferably an aryloxycarbonyl group having 7 to 12 carbon atoms, such as phenoxycarbonyl), a carbamoyl group (preferably having 1 to 24 carbon atoms, more preferably A carbamoyl group having 1 to 12 carbon atoms such as carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methyl − -Phenylcarbamoyl, N, N-dicyclohexylcarbamoyl), carbonamido group (preferably a carbonamido group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, for example, acetamido, benzamido, tetradecanamido, pivaloylamido , Cyclohexaneamide), an imide group (preferably an imide group having 20 or less carbon atoms, more preferably 12 or less carbon atoms, such as N-succinimide and N-phthalimide), a sulfonamide group (preferably having 1 to 24 carbon atoms). More preferably a sulfonamide group having 1 to 12 carbon atoms, such as methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide, cyclohexanesulfonamide), sulfamoylamino group (preferably having 1 to 1 carbon atoms). 24, More preferably, it is a sulfamoylamino group having 1 to 12 carbon atoms, for example, N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino), sulfamoyl group (preferably having 24 or less carbon atoms). And more preferably a sulfamoyl group having 16 or less carbon atoms, such as sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N- Cyclohexylsulfamoyl) and the like.

  Among the above substituents, alkyl groups, aryl groups, hydroxyl groups, sulfonic acid groups, phosphonic acid groups, carboxylic acid groups, alkoxy groups, aryloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, carbamoyloxy groups, A sulfamoyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a carbonamido group, a sulfonamido group, a sulfamoylamino group, and a sulfamoyl group are more preferable. , Hydroxyl group, sulfonic acid group, phosphonic acid group, carboxylic acid group, alkoxy group, aryloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy Group, alkylsulfonyloxy group, arylsulfonyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group are more preferable, hydroxyl group, sulfonic acid group, carboxylic acid group, alkoxy group, alkoxycarbonyloxy group, carbamoyloxy group, A sulfamoyloxy group, an alkylsulfonyloxy group, an acyl group, and an alkoxycarbonyl group are particularly preferable.

  Among the above particularly preferred substituents, a sulfonic acid group, a carboxylic acid group, an alkoxy group, an alkoxycarbonyloxy group, an alkylsulfonyloxy group, and an alkoxycarbonyl group are more preferable, and a sulfonic acid group, a carboxylic acid group, an alkoxy group, and an alkoxycarbonyl group. A group is more preferable, and a sulfonic acid group, a carboxylic acid group, and an alkoxy group are particularly preferable.

R ¹ is preferably a hydrogen atom, an alkyl group or an aryl group, particularly preferably a hydrogen atom or an alkyl group.

When the substituents of the substituted alkyl group and the substituted aryl group of R ¹ are further substitutable groups, they may be substituted with the substituents described above, and may be substituted with two or more substituents. The substituents may be the same or different.

In the general formula (1), L ¹ represents —N (R ² ) C (═O) —, —OC (═O) —, —C (═O) N (R ² ) —, —C (= O) represents O—, a group represented by the following general formula (2), a group represented by the general formula (3), or a group represented by the general formula (4). Here, R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

R ² represents an alkyl group, an aryl group, or a heterocyclic group, and the alkyl group, the aryl group, and the heterocyclic group are the alkyl groups described for the substituted alkyl group and the substituted aryl group in R ¹ . , Aryl group, and heterocyclic group are mentioned as examples, and preferred embodiments are also the same.
The alkyl group, aryl group, and heterocyclic group as R ² may be substituted with the substituent described in the above R ¹ , and when substituted with two or more substituents, The substituents may be the same or different.

Below, in the general formula (1), represented by the group represented by the following general formula represented by L ¹ (2), a group represented by the general formula (3), and general formula (4) The group will be described.

In General Formula (2) to General Formula (4), R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, R ³ represents a monovalent substituent, and k represents 0 to 0 Represents an integer of 4. * Represents the position bonded to the —C (R ¹ ) ═CH ₂ group in the general formula (1), and ** represents L ² or Dye (in the case of n = 0) in the general formula (1). Represents the position to join.

R ² has the same meaning as R ² described in the general formula (1), and the preferred embodiment is also the same.

R ³ represents a hydrogen atom or a substituent, and examples of the substituent represented by R ³ include the substituents described for the substituted alkyl group and substituted aryl group of R ¹ , and preferred embodiments are also the same. It is. k represents 0, 1, 2, 3, 4; When k is 2, 3, or 4, R ³ may be the same or different.
When the substituent of R ³ is a further substitutable group, it may be substituted with the substituent described in the above R ¹ , and when it is substituted with two or more substituents These substituents may be the same or different.

As L ¹ , from the viewpoint of synthesis, —N (R ² ) C (═O) —, —OC (═O) —, —C (═O) N (R ² ) —, —C (= O) O- are preferable, -OC (= O) -, - C (= O) N (R 2) -, - C (= O) O- , more preferably, -C (= O) N ( R 2 )-And -C (= O) O- are more preferable.

Next, L ² in the general formula (1) will be described.
L ² represents a divalent linking group that links L ¹ or —C (R ¹ ) ═CH ₂ group (when m = 0) and Dye.
L ² is preferably an alkylene group, an aralkylene group, an arylene group, —O—, —C (═O) —, —OC (═O) —, OC (═O) O—, —OSO ₂ —, ^{-OC (= O) N (R} 50) -, - N (R 50) -, - N (R 50) C (= O) -, - N (R 50) C (= O) O -, - N (R ⁵⁰ ) C (═O) N (R ⁵¹ ) —, —N (R ⁵⁰ ) SO ₂ —, —N (R ⁵⁰ ) SO ₂ N (R ⁵¹ ) —, —S—, —S—S— _{, -SO -, - SO 2 -} , - SO 2 N (R 50) -, - SO 2 O- and the like. In addition, a plurality of the above divalent linking groups may be bonded to form a new divalent linking group.

R ⁵⁰ and R ⁵¹ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Examples of the alkyl group, aryl group, and heterocyclic group of R ⁵⁰ and R ⁵¹ include the alkyl group, aryl group, and heterocyclic group described above for the substituent of R ¹ , and preferred embodiments are also the same. The alkyl group, aryl group, and heterocyclic group of R ⁵⁰ and R ⁵¹ may be substituted with the substituents described for the substituent of R ¹ , or may be substituted with two or more substituents. These substituents may be the same or different.

When L ² is an alkylene group, an aralkylene group, or an arylene group, it may be unsubstituted or substituted, and when it is substituted, it is substituted with the substituent described for the substituent of R ^1. When it is substituted with two or more substituents, these substituents may be the same or different.
When L ² is an alkylene group, an aralkylene group, or an arylene group, an alkylene group having 1 to 12 carbon atoms, an aralkylene group having 6 to 18 carbon atoms, or an arylene group having 6 to 18 carbon atoms is preferable. An alkylene group having 8 to 8 carbon atoms, an aralkylene group having 6 to 16 carbon atoms, and an arylene group having 6 to 12 carbon atoms are more preferable, and an alkylene group having 1 to 6 carbon atoms and an aralkylene group having 6 to 12 carbon atoms are still more preferable.

As the combination of L ¹ and L ² , L ¹ is —N (R ² ) C (═O) —, —OC (═O) —, —C (═O) N (R ² ) —, — C (= O) O-, L ² is an alkylene group having 1 to 12 carbon atoms, an aralkylene group having 6 to 18 carbon atoms, an arylene group having 6 to 18 carbon atoms, an alkylthioether having 2 to 18 carbon atoms, a carbon number Preferred are an alkylcarbonamide group having 2 to 18 carbon atoms and an alkylaminocarbonyl group having 2 to 18 carbon atoms. More preferably, L ¹ is —OC (═O) —, —C (═O) N (R ² ) —, —C (═O) O—, and L ² is an alkylene group having 1 to 8 carbon atoms, Embodiments of an aralkylene group having 6 to 16 carbon atoms, an arylene group having 6 to 12 carbon atoms, an alkylthioether having 2 to 12 carbon atoms, an alkylcarbonamide group having 2 to 12 carbon atoms, and an alkylaminocarbonyl group having 2 to 12 carbon atoms More preferably, L ¹ is —C (═O) N (R ² ) — or —C (═O) O—, L ² is an alkylene group having 1 to 6 carbon atoms, or 6 to 12 carbon atoms. Are an aralkylene group, an alkylthioether having 2 to 6 carbon atoms, an alkylcarbonamide group having 2 to 6 carbon atoms, and an alkylaminocarbonyl group having 2 to 6 carbon atoms.

Below, in the general formula (1) in ^{_{- (L 2) n - (}} L 1) m -C (R 1) = examples of the polymerizable group represented by CH _2. However, the present invention is not limited to these.

The dye monomer represented by the general formula (1) contained as a polymerization component in the dye multimer according to the present invention may be one kind or two or more kinds.
In addition, when the dye multimer according to the present invention contains another ethylenically unsaturated bond monomer described later as a copolymerization component, the monomer may contain only one kind, and two or more kinds. May be included. In addition, other monomers that may be further included as a copolymerization component may include only one type or two or more types when they are included as a copolymerization component. .

  The dye multimer according to the present invention is a preferable monomer capable of forming the structural unit represented by the general formula (A) and the general formula (C) or the structural unit represented by the general formula (A). The pigment monomer represented by the general formula (1) is 100% by mass (mass%), that is, the structure represented by the general formula (A) and the general formula (C). A polymer formed by polymerization of only units may be used. From the viewpoint of the film thickness, it is preferable that the structural units represented by the general formula (A) and the general formula (C) are contained in a mass ratio (mass%) of 10 mass% to 100 mass%, and 50 mass%. It is more preferable to contain -100 mass%, and it is more preferable to contain 80 mass% to 100 mass%.

  Specific examples of the compound (monomer) represented by the general formula (1) of the present invention [Exemplary compounds (B-1) to (B-34)] are shown below, but the present invention is limited thereto. It is not a thing.

<Monomer having a different structure from the dye monomer that has a terminal ethylenically unsaturated bond and can constitute the structural unit represented by the general formula (A) and the general formula (C)>
The dye multimer according to the present invention preferably constitutes the structural unit represented by the general formula (A) and the general formula (C) and the structural unit represented by the general formula (A) as a polymerization component. The dye monomer represented by the general formula (1), which is a monomer, further has a terminal ethylenically unsaturated bond as a copolymerization component, and is represented by the general formula (A) and the general formula (C). A monomer having a different structure from the monomer that can constitute the structural unit represented by (hereinafter, also referred to as “another ethylenically unsaturated bond monomer”) may be included. Furthermore, a monomer other than the above monomer may be included as a copolymerization component.
The dye multimer according to the present invention has a terminal ethylenically unsaturated bond as a copolymerization component, and can form a constituent unit represented by the general formula (A) and the general formula (C). The monomer may contain a monomer having a different structure (sometimes referred to as “another ethylenically unsaturated bond monomer”).
That is, the dye multimer according to the present invention is represented by the dye monomer capable of forming the structural unit represented by the general formula (A) and the general formula (C) or the general formula (1). A copolymer containing a dye monomer and another ethylenically unsaturated bond monomer having a different structure may be used. At this time, the copolymer may contain only one type of the specific dye monomer according to the present invention, or may contain two or more types, and the other ethylenically unsaturated bond monomer. 1 type may be included and 2 or more types may be included.

The other ethylenically unsaturated bond monomer is a compound having an ethylenically unsaturated bond at least at a terminal portion, and the structural unit represented by the general formula (A) and the general formula (C). There is no particular limitation as long as it is a monomer having a different structure from the dye monomer that can be formed and the dye monomer represented by formula (1).
When applying the dye multimer according to the present invention to a colored curable composition, from the viewpoint of improving the color pattern forming property, the other ethylenically unsaturated bond monomer is added to the terminal ethylenically unsaturated bond, A monomer having an alkali-soluble group is preferable.

Examples of the other ethylenically unsaturated bond monomer having an alkali-soluble group include a vinyl monomer having a carboxyl group and a vinyl monomer having a sulfonic acid group.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, (meth) acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, and the like.

  Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.

  The dye multimer according to the present invention preferably includes a repeating unit derived from a vinyl monomer having an alkali-soluble group as described above. By including such a repeating unit, when the dye multimer according to the present invention is applied to a colored curable composition, the development removability of an unexposed portion is excellent.

  In the dye multimer according to the present invention, the content of the repeating unit derived from the vinyl monomer having an alkali-soluble group is preferably 30 mgKOH / g to 200 mgKOH / g, particularly preferably 50 mgKOH / g to 160 mgKOH / g. . That is, in terms of suppressing the formation of precipitates in the developer, the content of the repeating unit derived from the vinyl monomer having an alkali-soluble group is preferably 50 mgKOH / g or more. When a colored curable composition is constituted using both the dye multimer and the pigment according to the present invention, the formation of secondary aggregates, which are aggregates of primary particles of the pigment, is effectively suppressed, or secondary In order to effectively weaken the cohesive strength of the aggregate, the content of the repeating unit derived from the vinyl monomer having an alkali-soluble group is preferably 50 mgKOH / g to 160 mgKOH / g.

  The vinyl monomer that can be used in the copolymerization with the dye monomer of the present invention is not particularly limited. For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumarate Acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable. In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".

  Among the above other structural units, preferred specific examples include the structural units shown below, but the present invention is not limited thereto.

  Hereinafter, preferred examples of the dye multimer according to the present invention are shown in Table 1 below by clearly indicating the structural unit (the structural unit), the copolymerization mass ratio, and the weight average molecular weight.

Hereinafter, although the synthesis example of a typical pigment | dye multimer is shown below, this invention is not limited to this.
(Synthesis of Dye Multimer P1)

  21.0 g (0.10 mol) of the above compound (i) and 22.6 g of 3,4-dichlorocyclo-3-butene-1,2-dione were dissolved in 200 mL of methylene chloride and stirred for 24 hours. Next, the reaction solution was concentrated and then purified by column chromatography to obtain 6.6 g of the compound (ii). This was added with 100 mL of acetic acid and 20 mL of water, heated at an external temperature of 120 ° C. for 4 hours, cooled, and the purified solid was collected by filtration to obtain 6.2 g of compound (iii). Next, 6.0 g (18.4 mmol) of the compound (iii), 3.87 g (18.4 mmol) of the compound (iv) and 5 g of quinoline were dissolved in 20 mL of 1-butanol and 5 mL of toluene, and the mixture was dissolved at an external temperature of 130 ° C. Water generated while heating for a period of time was removed with a Dean-Stark tube. After cooling, the reaction solution was concentrated and purified by column chromatography to obtain 5.2 g of the dye monomer (B-1). M / z = 499 (Posi)

  Under a nitrogen stream, 10 mL of propylene glycol monomethyl ether acetate (hereinafter referred to as “PGMEA” where appropriate) is heated to 80 ° C., and 5.0 g of the dye monomer (B-1) obtained above and 0.26 g of methacrylic acid. A solution of 0.2 g of azobisisobutyronitrile in 20 mL of PGMEA was added dropwise over 4 hours. This was heated for an additional 2 hours. After cooling, the polymerization solution was added dropwise to 100 mL of hexane, and the precipitated solid was collected by filtration and dried to obtain 4.9 g of a dye multimer (P1).

(Synthesis of Dye Multimer P18)

  14.2 g (0.10 mol) of the above compound (v), 5.47 g (0.048 mol) of 3,4-dihydroxycyclo-3-butene-1,2-dione and 10 g of quinoline 100 mL of toluene, 30 mL of 1-butanol The mixture was heated at an external temperature of 130 ° C. for 24 hours. The reaction solution was allowed to cool and then concentrated, and 11.3 g of the above compound (vi) was obtained by column chromatography. M / z = 363 (Posi)

  Next, 10.9 g (30 mmol) of the obtained compound (vi) and 6.54 g (30 mmol) of pyromellitic anhydride were dissolved in 200 mL of PGMEA, 0.10 g of monobutyltin oxide was added, and the mixture was heated at 100 ° C. for 10 hours. After allowing to cool, the polymerization solution was added to 400 mL of hexane to obtain 15.4 g of a dye multimer (P-18).

(Synthesis of Dye Multimer P20)

  19.6 g (0.10 mol) of the compound (vii) and 22.6 g of 3,4-dichlorocyclo-3-butene-1,2-dione were dissolved in 200 mL of methylene chloride and stirred for 24 hours. Next, the reaction solution was concentrated and then purified by column chromatography to obtain 6.8 g of compound (viii). To this were added 100 mL of acetic acid and 20 mL of water, and the mixture was heated at an external temperature of 120 ° C. for 4 hours and then cooled. The purified solid was filtered to obtain 6.2 g of compound (ix). Next, 5.38 g (18.4 mmol) of compound (ix), 2.87 g (18.4 mmol) of compound (iv) used in the synthesis of the exemplified compound (P1) and 5 g of quinoline in 20 mL of 1-butanol, toluene The water generated by dissolving in 5 mL and heating at an external temperature of 130 ° C. for 4 hours was removed with a Dean-Stark tube. After cooling, the reaction solution was concentrated and purified by column chromatography to obtain 4.2 g of compound (xi). M / z = 431 (Posi)

  Compound (xi) 4.0 g (9.3 mmol), Compound (xii) 0.30 g (1.7 mmol), 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) 5.66 g (37 .2 mmol) and 50 mL of N, N-dimethylacetamide were heated at 80 ° C. for 24 hours under a nitrogen atmosphere. The obtained solution was subjected to liquid separation extraction with ethyl acetate / 1N hydrochloric acid aqueous solution, the oil layer was concentrated and purified by column chromatography to obtain 3.5 g of dye multimer P20.

The molecular weight of the dye multimer according to the present invention is preferably in the range of 3000 to 30000 in terms of weight average molecular weight (Mw), more preferably 5000 to 20000, and most preferably 5000 to 13000.
From the viewpoint of developability in producing a color filter by applying the dye multimer according to the present invention to a colored curable composition, the weight average molecular weight (Mw) of the dye multimer having a polymer structure is 13,000 or less. It is preferable that

(A-2) (a) Colorant other than the dye multimer The colored curable composition of the present invention and the color filter using the colored curable composition are within the range not impairing the effects of the present invention. Coloring agents other than the dye multimers can also be used.
Examples of other colorants that can be used in combination (a-2) include the following colorants.
For example, a triarylmethane-based colorant having an absorption maximum at 550 nm to 650 nm (for example, CI Acid Blue 7, CI Acid Blue 83, CI Acid Blue 90, CI Solvent Blue 38, CI Acid Violet 17, CI Acid Violet 49, CI Acid Green 3, etc.), a xanthene dye having an absorption maximum at 500 nm to 600 nm, such as C.I. I. Acid Red 289 or the like can be used.

  Content of the said triarylmethane type | system | group coloring agent can be used in the range which does not impair the effect of this invention, and is 0.5 mass%-50% with respect to the total solid of the photosensitive coloring curable composition of this invention. It is preferable that it is mass%.

  In order to produce a blue filter array, it is preferable to use a mixture of at least one dye multimer and a phthalocyanine pigment.

(Phthalocyanine pigment)
The phthalocyanine pigment that can be used in the present invention is not particularly limited as long as it is a pigment having a phthalocyanine skeleton. The central metal contained in the phthalocyanine pigment is not particularly limited as long as it is a metal that can form a phthalocyanine skeleton. Among these, magnesium, titanium, iron, cobalt, nickel, copper, zinc, and aluminum are preferably used as the central metal.
Specifically, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 5, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Pigment blue 17: 1, C.I. I. Pigment blue 75, C.I. I. Pigment blue 79, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37, C.I. I. Pigment green 58, chloroaluminum phthalocyanine, hydroxyaluminum phthalocyanine, aluminum phthalocyanine oxide, and zinc phthalocyanine. Among these, from the viewpoint of light resistance and coloring power, C.I. I. Pigment blue 15, C.I. I. Pigment Blue 15: 6, Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2 is preferable. I. Pigment Blue 15: 6 is preferable.

The content of the phthalocyanine pigment in the colored curable composition in the present invention is preferably 10% by mass to 70% by mass, and 20% by mass to 60% by mass with respect to the total solid content component of the colored curable composition. More preferably, 35% by mass to 50% by mass is most preferable.
In addition, the content ratio of the (a) dye multimer and the phthalocyanine pigment is preferably phthalocyanine pigment: squarylium compound = 100: 5 to 100: 100 when expressed by the ratio of the dye multimer derived from the squarylium compound. 100: 15-100: 75 are more preferable, and 100: 25-100: 50 are still more preferable.

When the colored curable composition of this invention contains a pigment, it can contain a dispersing agent.
As the dispersant, a known pigment dispersant or surfactant is used.
As the dispersant, many kinds of compounds are used. For example, phthalocyanine derivatives (commercially available product EFKA-745 (manufactured by Efka)), Solsperse 5000 (manufactured by Nippon Lubrizol Co., Ltd.); organosiloxane polymer KP341 (Shin-Etsu) Chemical Industries, Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 (above, manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, poly Nonionic surfactants such as oxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, W005, W017 (above, manufactured by Yusho Co., Ltd.), etc. Anionic surfactants; EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), D Polymer dispersing agents such as Perth Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (Sannopco Co., Ltd.); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000 , 26000, 28000, etc. (manufactured by Nippon Lubrizol Co., Ltd.); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (above, manufactured by ADEKA Corporation), and Isonet S-20 (manufactured by Sanyo Chemical Co., Ltd.) can be mentioned. In addition, amphoteric dispersants such as Hinoact T-8000E manufactured by Kawaken Fine Chemical Co., Ltd. are also included.

  The content of the dispersant in the colored curable composition of the present invention is preferably 1% by mass to 80% by mass, more preferably 5% by mass to 70% by mass with respect to the pigment, and 10% by mass to 60% by mass. Is most preferred.

(B) Polymerizable compound The colored curable composition of the present invention contains a polymerizable compound.
Examples of the polymerizable compound include addition polymerizable compounds having at least one ethylenically unsaturated double bond. Specifically, it is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. 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 any of chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or a mixture thereof and a (co) polymer thereof.

  As an example of the said monomer and its (co) polymer, the specific example as described in Paragraphs 0058-0065 of Unexamined-Japanese-Patent No. 2008-224982 is mentioned.

  Examples of the compound include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. Those having an aromatic skeleton described in JP-A-2-226149, those containing an amino group described in JP-A-1-165613, and the like are also preferably used.

More specifically, examples of monomers and (co) polymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters thereof, Amides and their (co) polymers, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, And these (co) polymers. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.
As these specific compounds, the compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

  The polymerizable compound is also preferably a compound having at least one addition-polymerizable ethylene group as a polymerizable monomer and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as anurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane acrylates as described in JP-B-37193, polyester acrylates and epoxy resins 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, which are reaction products with (meth) acrylic acid, and mixtures thereof.

  Further, compounds having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group are disclosed in paragraphs [0254] to [0257] of JP-A-2008-292970. The compounds described are also suitable.

  In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the said general formula, n is 0-14 and m is 1-8. A plurality of R and T present in one molecule may be the same or different.
In each of the radical polymerizable monomers represented by the general formulas (MO-1) to (MO-5), at least one of the plurality of Rs is —OC (═O) CH═CH ₂ , or represents an _{-OC (= O) C (CH} 3) = groups represented by CH _2.
Specific examples of the radical polymerizable monomer represented by the above general formulas (MO-1) to (MO-5) include compounds described in paragraph Nos. 0248 to 0251 of JP2007-26979A. Can also be suitably used in the present invention.

  About these polymerizable compounds, the details of usage such as the structure, single use or combination, addition amount and the like can be arbitrarily set in accordance with the final performance design of the colored curable composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Also, from the viewpoint of increasing the strength of the colored cured film, those having three or more functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic acid esters, methacrylic acid esters, styrene compounds, vinyl ether compounds). It is also effective to adjust both sensitivity and intensity by using together. In addition, the selection of the polymerizable compound is also possible with respect to the compatibility and dispersibility with other components (for example, photopolymerization initiator, colorant (pigment), binder polymer, etc.) contained in the colored curable composition. The method of use is an important factor. For example, compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a support.

  The content of the polymerizable compound in the total solid content of the colored curable composition (total content in the case of 2 or more types) is not particularly limited, and is 10 from the viewpoint of more effectively obtaining the effects of the present invention. % By mass to 80% by mass is preferable, 15% by mass to 75% by mass is more preferable, and 20% by mass to 60% by mass is particularly preferable.

(C) Photopolymerization initiator The colored curable composition of the present invention contains (c) a polymerization initiator.
The polymerization initiator in the colored curable composition of the present invention is a compound that is decomposed by light or heat and starts and accelerates polymerization of a polymerizable compound described later, and has absorption in a wavelength region of 300 to 500 nm. It is preferable.

Specific examples of the polymerization initiator include, for example, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, organic boric acid. Examples include compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, acylphosphine (oxide) compounds, and hexaarylbiimidazole compounds.
As the polymerization initiator, an oxime ester compound and a hexaarylbiimidazole compound are particularly preferable from the viewpoints of residue reduction and adhesion between the light shielding film and a surface on which the light shielding film is formed (substrate or the like).

  As a suitable oxime ester compound, a known compound known as a photopolymerization initiator of a photosensitive composition for use in electronic parts can be used. For example, JP-A-57-116047, JP-A-61-24558, JP-A-62-2201859, JP-A-62-286961, JP-A-7-278214, JP-A-2000-80068, JP-A-2001-233842, Special Tables. 2004-534797, JP 2002-538241, JP 2004-359639, JP 2005-97141, JP 2005-220097, WO 2005-080337A1, JP 2002-518732, JP 2001-235858, JP 2005-227525, It can be used by selecting from the compounds described in JP-A-2006-78749.

In general, the oxime ester compound has low sensitivity in the near ultraviolet region such as 365 nm and 405 nm, and thus has low sensitivity. However, it is known that the sensitizer increases the sensitivity in the near ultraviolet region and increases the sensitivity. Yes. Further, it is known that the combined use with cosensitizers such as amines and thiols increases the amount of effective radicals generated, but practically higher sensitivity has been required.
In the present invention, even an oxime ester compound having a small absorption in the near ultraviolet region such as 365 nm or 405 nm can be remarkably increased in sensitivity by using in combination with a sensitizer and reach a practical sensitivity.

  As the oxime ester compound, a compound having a small absorption in the range of 380 nm to 480 nm and a high decomposition efficiency, or a compound having a small absorption in the region by photolysis even if the absorption in the range of 380 nm to 480 nm is large (by-product) The compound whose absorption of a thing is a short wavelength) is preferable.

Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
IRGACURE-OXE01 (manufactured by Ciba Japan) and IRGACURE-OXE02 (manufactured by Ciba Japan) are also preferably used as commercial products.
Preferably, it can also be suitably used for the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A.
Most preferably, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-269979 and the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061 are mentioned.
In the present invention, among oxime ester compounds, 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (o-acetyloxime) -1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone is preferred.

  Specifically, the oxime photopolymerization initiator is preferably a compound represented by the following formula (1). The N—O bond of the oxime may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

(In formula (1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.)
The monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group. , Dodecyl group, okdadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1- Naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2- Methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, and , 3 Nitorofenashiru group can be exemplified.

The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, specifically, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a 9-anthryl group. 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, Xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, tarnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, ASEAN Trirenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, ter Nthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, specifically, an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2 -Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, and And 4-methoxybenzoyl group.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, specifically, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, or a hexyloxy group. Examples thereof include a carbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  Specific examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanyl. Phenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxy Carbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl , 4-fluorophenyl oxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and a 4-methoxy phenyloxy carbonyl group can be exemplified.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
Specifically, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiyl Nyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl Group Midinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolidinyl group Examples include a group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, and thioxanthryl group.

  Specific examples of the optionally substituted alkylthiocarbonyl group include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, and an octadecylthiocarbonyl group. Examples thereof include a group and a trifluoromethylthiocarbonyl group.

  Specific examples of the arylthiocarbonyl group which may have a substituent include a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonyl group, and a 4-phenylsulfanylphenylthiocarbonyl group. 4-dimethylaminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3 -Chlorophenylthiocarbonyl group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenyl Two thiocarbonyl group, and a and a 4-methoxyphenylthiocarbonyl group.

  The monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Of these, the structures shown below are particularly preferred.
In the following structure, Y, X, and n have the same meanings as Y, X, and n in formula (2) described later, and preferred examples are also the same.

Examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cyclohexylene group, and an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, A is an alkylene substituted with an unsubstituted alkylene group or 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. Group, alkylene group substituted with 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) An alkylene group substituted with

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent. Examples of the substituent include the same substituents as those introduced into the substituted aryl group mentioned as specific examples of the aryl group which may have a substituent.
Among these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

In the formula (1), it is preferable in terms of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure. Me represents a methyl group, and Et represents an ethyl group.

  The oxime compound is preferably a compound represented by the following formula (2).

(In formula (2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents 0-5. (It is an integer.)
R, A, and Ar in formula (2) have the same meanings as R, A, and Ar in formula (1), and preferred examples are also the same.

  Examples of the monovalent substituent represented by X include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a heterocyclic group, and a halogen atom. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Among these, X is preferably an alkyl group from the viewpoints of solvent solubility and improvement in absorption efficiency in the long wavelength region.
Moreover, n in Formula (2) represents the integer of 0-5, and the integer of 0-2 is preferable.

Examples of the divalent organic group represented by Y include the structures shown below. In the groups shown below, “” represents the bonding position between Y and an adjacent carbon atom in the formula (2).

  Of these, the following structures are preferable from the viewpoint of increasing sensitivity.

  Furthermore, the oxime compound is preferably a compound represented by the following formula (3).

(In Formula (3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, A
r represents an aryl group, and n is an integer of 0 to 5. )
R, X, A, Ar, and n in the formula (3) are R, X, A,
It is synonymous with Ar and n, respectively, and a preferable example is also the same.

  Specific examples (C-4) to (C-13) of oxime compounds that can be suitably used are shown below, but the present invention is not limited thereto.

  The oxime compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has high absorbance at 365 nm and 455 nm.

From the viewpoint of sensitivity, the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 10,000 to 300,000, more preferably 15,000 to 300,000, and 20,000 to 200,000. 000 is particularly preferred.
A known method can be used for the molar extinction coefficient of the compound. Specifically, for example, in an ultraviolet-visible spectrophotometer (Varian's Carry-5 spectrophotometer), an ethyl acetate solvent is used, and 0.01 g It is preferable to measure at a concentration of / L.

As the hexaarylbiimidazole compound, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. various compounds described in, specifically, 2,2 ^'- bis (o-chlorophenyl) ^-4,4', 5,5 ^'- tetraphenyl biimidazole, ^2,2' - bis (o-bromophenyl )) 4,4 ^{', 5,5'} - tetraphenyl biimidazole, 2,2 ^'- bis (o, p-dichlorophenyl) ^-4,4', 5,5 ^'- tetraphenyl biimidazole, ^2,2' - bis (o-chlorophenyl) -4,4 ^{', 5,5'} - tetra (m-methoxyphenyl) biimidazole, 2,2 ^'- bis (o, ^o' - dichlorophenyl) -4,4 ^', 5, 5 ^'- tetraphenyl Bii Imidazole, 2,2 ^'- bis (o-nitrophenyl) ^-4,4', 5,5 ^'- tetraphenyl biimidazole, ^2,2' - bis (o-methylphenyl) -4,4 ^', 5, 5 ^'- tetraphenyl biimidazole, ^2,2' - bis (o-trifluorophenyl) -4,4 ^{', 5,5'} - tetraphenyl biimidazole.

  The content of the (C) polymerization initiator in the colored curable composition of the present invention is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass in the total solid content of the colored curable composition. 2-20 mass% is especially preferable. A polymerization initiator may be used individually by 1 type, and may use 2 or more types together.

  Depending on the polymerization initiator used, it is preferable to add a chain transfer agent to the colored curable composition of the present invention. Examples of chain transfer agents include N, N-dialkylaminobenzoic acid alkyl esters and thiol compounds. As the thiol-based compound, for example, 2-mercaptobenzothiazole, 2-mercapto-1-phenylbenzimidazole, 3-mercaptopropionic acid and the like can be used alone or in admixture of two or more. In particular, it is preferable to use a combination of a hexaarylbiimidazole compound and a thiol compound from the viewpoint of residue and adhesion.

(D) Organic solvent The colored curable composition of the present invention contains 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 coating property when the colored curable composition is used, and in particular, the solubility of the binder, the coating property, 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 (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate and the like (specifically, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate, 3-ethoxy Ethyl propionate, etc.)), 2-oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (specifically, 2 -Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.)), 2-oxy-2-methylpropionic acid Methyl, ethyl 2-oxy-2-methylpropionate (specifically, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, 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.

  It is also preferable to mix two or more of these organic solvents from the viewpoints of the solubility of each of the above-mentioned components, and the solubility and the improvement of the coating surface state when an alkali-soluble binder is included. 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 colored curable composition is preferably such that the total solid concentration in the composition is 10% by mass to 80% by mass, and more preferably 15% by mass to 60% by mass. .

(Other ingredients)
The colored curable composition of the present invention may further contain other components such as an alkali-soluble binder and a crosslinking agent, in addition to the above-described components, as long as the effects of the present invention are not impaired.

(E) Alkali-soluble resin It is preferable that the colored curable composition of this invention contains alkali-soluble resin further. By containing an alkali-soluble resin, developability and pattern formation are improved.

  The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, etc., acidic cellulose derivatives having a carboxylic acid in the side chain, and polymers having a hydroxyl group added with an acid anhydride. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene monomer Romonoma, mention may be made of polymethyl methacrylate macromonomer.
As the alkali-soluble resin, a compound represented by the following general formula (ED) is also preferable.

(In the formula (ED), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent) It is also preferable that the polymer (a) obtained by polymerizing the monomer component essential to “ether dimer”) is contained as the essential polymer component (A). Thereby, the curable resin composition of this invention can form the cured coating film which was extremely excellent also in heat resistance and transparency. In the general formula (1) showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited. Linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl An alkyl group substituted with an aryl group such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance. Note that R ¹ and R ² may be the same type of substituent or different substituents.

Specific examples of the ether dimer include dimethyl-2,2 ^′ -[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ^′ -[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 ^′ -[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ^′ -[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 ^′ -[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ^′ -[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 ^'- [oxybis (methylene)] bis-2-propenoate, di (t-amyl) ^-2,2' - [oxybis (methylene)] bis-2-Puropeno Over DOO, di (stearyl) -2,2 ^'- [oxybis (methylene)] bis-2-propenoate, di (lauryl) ^-2,2' - [oxybis (methylene)] bis-2-propenoate, di (2 -Ethylhexyl) -2,2 ^' -[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2 ^' -[oxybis (methylene)] bis-2-propenoate, di (1- Ethoxyethyl) -2,2 ^′ -[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ^′ -[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ^′ -[oxybis ( methylene)] bis-2-propenoate, dicyclohexyl-2,2 ^'- [oxybis (methylene)] bis-2-propenoate, di (t- Chill cyclohexyl) -2,2 ^'- [oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) ^-2,2' - [oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 ^′ -[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ^′ -[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 Examples include ^' -[oxybis (methylene)] bis-2-propenoate and di (2-methyl-2-adamantyl) -2,2 ^' -[oxybis (methylene)] bis-2-propenoate. Among these, dimethyl 2,2 ^'- [oxybis (methylene)] bis-2-propenoate, ^diethyl-2,2' - [oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2 ^'- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ^′ -[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be only one kind or two or more kinds.

  Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymer yabenzyl (meth) acrylate / (meth) acrylic acid / other monomeric calanal multi-component copolymers are particularly suitable. In addition, a copolymer of 2-hydroxyethyl methacrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2-hydroxy -3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / Benzyl methacrylate / methacrylic acid copolymer.

Moreover, in order to improve the crosslinking efficiency of the colored curable composition in this invention, it is preferable to use the alkali-soluble resin which has a polymeric group.
As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful.
As an alkali-soluble resin containing these polymerizable groups, an isocyanate group and an OH group are reacted in advance to leave one unreacted isocyanate group and a compound containing a (meth) acryloyl group and an acrylic resin containing a carboxyl group; Urethane-modified polymerizable double bond-containing acrylic resin obtained by the above reaction, unsaturated group-containing acrylic obtained by reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule Resin, acid pendant type epoxy acrylate resin, OH group-containing acrylic resin and polymerizable double bond-containing acrylic resin obtained by reacting a polymerizable double bond, OH group-containing acrylic resin and isocyanate Resin obtained by reacting a compound having a polymerizable group, JP 2002-229207 A And a resin obtained by performing a basic treatment on a resin having an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position described in JP-A-2003-335814 Etc. are preferable.
Moreover, the polymer containing the above-mentioned polymerizable group can be obtained as a commercial product, and specifically, for example, Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (-COOH containing polyurethane acrylic oligomer. Diamond). Shamrock Co. Ltd.,) Biscote R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel Chemical Industries, Ltd.) Daicel USB Co., Ltd.).

The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and most preferably 70 to 120 mgKOH / g.
Further, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and most preferably 7,000 to 20,000.

  As content in the colored curable composition of alkali-soluble resin, 1-15 mass% is preferable with respect to the total solid of this composition, More preferably, it is 2-12 mass%, Most preferably 3 to 10% by mass.

-Crosslinking agent-
The colored curable composition of the present invention can be supplemented with a crosslinking agent to further increase the hardness of the colored cured film obtained by curing the colored 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.
The details of paragraphs 0134 to 0147 of JP-A No. 2004-295116 can be referred to for details such as specific examples of the crosslinking agent.

-Polymerization inhibitor-
In the colored curable composition of the present invention, it is desirable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the colored curable composition. .
Examples of the polymerization inhibitor usable in the present invention, hydroquinone, p- methoxyphenol, di -t- butyl -p- cresol, pyrogallol, t- butyl catechol, benzoquinone, 4,4 ^'- thiobis (3-methyl-6- t-butylphenol), 2,2 ^'- methylenebis (4-methyl -6-t-butylphenol), etc. N- nitrosophenylhydroxyamine cerous salt.
The addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the whole composition.

-Surfactant-
Various surfactants may be added to the colored photosensitive composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

In particular, since the colored photosensitive composition of the present invention contains a fluorosurfactant, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, so that the coating thickness is uniform. And the liquid-saving property can be further improved.
That is, in the case of forming a film using a coating liquid to which a colored photosensitive composition containing a fluorosurfactant is applied, by reducing the interfacial tension between the coating surface and the coating liquid, The wettability is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the colored photosensitive composition.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (above, manufactured by Asahi Glass Co., Ltd.), Solsperse 20000 (Japan Rouble) Zole Co., Ltd.).

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, etc. It is.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.

  Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by Big Chemie.
Only one type of surfactant may be used, or two or more types may be combined.
The addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass and more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the colored photosensitive composition. .

-Other additives-
Various additives, for example, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like can be blended with the colored curable composition as necessary. Examples of these additives include those described in paragraphs [0155] to [0156] of JP-A No. 2004-295116.
In the colored curable composition of the present invention, a sensitizer and a light stabilizer described in paragraph [0078] of JP-A No. 2004-295116, and a thermal polymerization inhibitor described in paragraph [0081] of the same publication. Can be contained.

In the case where the alkali solubility in the non-exposed area is promoted and the developability of the colored curable composition is further improved, the composition has an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less. Is preferably added.
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, other carboxylic acids such as umbellic acid.

[Preparation method of colored curable composition]
The colored curable composition of the present invention is prepared by mixing the aforementioned components.
In preparing the colored curable composition, the components constituting the colored curable composition may be combined at once, or may be sequentially added 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 composition.
The colored curable composition prepared as described above is preferably filtered using a Millipore filter having a pore size of about 0.01 μm to 3.0 μm, more preferably about 0.05 μm to 0.5 μm. Can be used for use.

  Since the colored curable composition of the present invention is excellent in storage stability and can form a colored cured film with excellent light resistance, a liquid crystal display element (LCD) or a solid-state imaging element (for example, CCD, CMOS) Etc.) can be suitably used for forming colored pixels such as color filters and for producing printing inks, inkjet inks, paints, and the like. In particular, it can be suitably used for forming colored pixels for solid-state imaging devices such as CCDs and CMOSs.

≪Color filter and manufacturing method≫
Next, a method for producing a color filter using the colored curable composition of the present invention (a method for producing a color filter of the present invention) will be described.
In the method for producing a color filter of the present invention, first, the colored curable composition layer of the present invention is applied on a support to form a colored curable composition layer. The method for applying is not particularly limited, and examples thereof include a method of applying a coating liquid containing a colored curable composition, a method of transferring a colored curable composition layer previously formed on a temporary support, and the like. The method is preferred.
When applying the coating method, for example, it is applied by a coating method such as spin coating, casting coating, roll coating, etc. to form a colored curable composition layer, and then pre-curing (pre-baking) as necessary. And drying the colored curable composition layer (colored curable composition layer applying step).

  Examples of the support used in the method for producing a color filter of the present invention include soda glass, borosilicate glass (pyrex (registered trademark) glass), quartz glass, and quartz glass used for liquid crystal display elements and the like, and a transparent conductive film thereon. Examples include a deposited substrate and a photoelectric conversion element substrate used for an imaging element, such as a silicon substrate and a complementary metal oxide semiconductor (CMOS) substrate. These substrates may have black stripes that separate pixels. 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.

  In addition, when spin-coating the colored curable composition on the support, in order to reduce the amount of dripping of the liquid, before dropping the colored curable composition, by dropping and rotating an appropriate organic solvent, The familiarity of the colored curable composition with the support can be improved.

  In the step of applying the colored curable composition of the present invention, when a coating method is used, for example, when the colored curable composition adheres to the nozzle of the coating device discharge unit, the piping unit of the coating device, the inside of the coating device, etc. However, it can be easily removed by using a known cleaning solution. In this case, in order to perform more efficient cleaning and removal, it is preferable to use the solvent described above as the cleaning liquid as the solvent contained in the colored curable composition of the present invention.

JP-A-7-128867, JP-A-7-146562, JP-A-8-278737, JP-A-2000-273370, JP-A-2006-85140, JP-A-2006-291191, The cleaning liquids described in JP 2007-2101 A, JP 2007-2102 A, JP 2007-281523 A, and the like can also be suitably used as cleaning liquids for cleaning and removing the colored curable composition of the present invention. it can.
As the cleaning liquid, it is preferable to use alkylene glycol monoalkyl ether carboxylate or alkylene glycol monoalkyl ether.
These solvents that can be used as the cleaning liquid may be used alone or in combination of two or more.
When mixing 2 or more types of solvent, the mixed solvent formed by mixing the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group is preferable. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. The mixed solvent is a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), and the ratio is particularly preferably 60/40.
In addition, in order to improve the permeability of the cleaning liquid to the colored curable composition, the surfactant described above as a surfactant that can be contained in the colored photosensitive composition may be added to the cleaning liquid.

Examples of the prebaking condition include a condition of heating at 70 ° C. to 130 ° C. for about 0.5 minutes to 15 minutes using a hot plate or an oven.
The thickness of the colored curable composition layer formed from the colored curable composition is appropriately selected depending on the purpose, but is generally preferably 0.2 μm to 5.0 μm. More preferably, it is 3 μm to 2.5 μm, and most preferably 0.3 μm to 1.5 μm. In addition, the thickness of the coloring curable composition layer here is a film thickness after prebaking.

Then, in the manufacturing method of the color filter of this invention, the coloring curable composition layer formed on the support body is exposed to pattern shape (exposure process).
The pattern exposure is not particularly limited, such as exposure through a mask and scanning exposure, but exposure through a mask is preferable when a high-resolution pattern is formed.
As light or radiation applicable to the exposure step, g-line, h-line, i-line, KrF light, and ArF light 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 ^{100mJ / cm 2 ~10000mJ / cm 2} .
The exposed colored curable composition layer can be heated at 70 ° C. to 180 ° C. for about 0.5 minutes to 15 minutes using a hot plate or oven before the next development processing.
The exposure can be performed while flowing nitrogen gas in the chamber in order to suppress oxidation fading of the coloring material in the colored curable composition layer.

Then, it develops with a developing solution with respect to the coloring curable composition layer after exposure (development process). Thereby, a negative or positive colored pattern (resist pattern) can be formed.
As long as the developer dissolves the uncured portion (unexposed portion) of the colored curable composition layer and does not dissolve the cured portion (exposed portion), a combination of various organic solvents or an alkaline aqueous solution may be used. it can. When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted to pH 11 to 13, more preferably pH 11.5 to 12.5. In particular, an alkaline aqueous solution prepared by adjusting tetraethylammonium hydroxide so that its concentration is 0.001% by mass to 10% by mass, preferably 0.01% by mass to 5% by mass can be used as the developer.
The development time is preferably 30 seconds to 300 seconds, more preferably 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. The cleaning method is also appropriately selected according to the purpose. While rotating a support such as a silicon wafer substrate at a rotational speed of 10 rpm to 500 rpm, pure water is supplied from the ejection nozzle in a shower shape from above the rotation center. A rinsing process can be performed.

  Thereafter, if necessary, post-heating and / or post-exposure may be performed on the formed pattern (resist pattern) to accelerate the curing of the pattern (post-curing step).

-UV irradiation process-
Ultraviolet irradiation process, the pattern after performing a developing process in the pattern formation step, ultraviolet light 10 times more light quantity of the exposure amount [mJ / cm ^2] in the exposure process before development [mJ / cm ^2] Irradiate (UV light). Between the development process in the pattern formation step and the heat treatment described later, the pattern (dye-containing negative curable composition) after development is irradiated with UV light for a predetermined time, so that the color when heated later It is possible to effectively prevent migration, and light resistance is improved.

As a light source for irradiating UV light, for example, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a DEEP UV lamp, or the like can be used. Among them, the irradiated ultraviolet light includes light having a wavelength of 275 nm or less, and the irradiation illuminance [mW / cm ² ] of the light having a wavelength of 275 nm or less is 5% or more with respect to the integrated irradiation illuminance of all the wavelength light in the ultraviolet light. The thing which can irradiate the light which is is preferable. By setting the irradiation illuminance of light having a wavelength of 275 nm or less in ultraviolet light to 5% or more, the effect of suppressing color transfer between colored pixels and the upper and lower layers and the effect of improving light resistance can be more effectively enhanced. From this point, it is preferable to use a light source different from a light source such as an i-line or the like used for exposure in the pattern forming step, specifically, a high pressure mercury lamp, a low pressure mercury lamp, or the like. Among these, for the same reason as described above, 7% or more is preferable with respect to the integrated irradiation illuminance of all wavelength light in ultraviolet light. Moreover, the upper limit of the irradiation illuminance of light having a wavelength of 275 nm or less is preferably 25% or less.

The integrated irradiation illuminance is a curve with the illuminance for each spectral wavelength (radiant energy passing through a unit area per unit time; [mW / m ² ]) as the vertical axis and the wavelength [nm] of light as the horizontal axis. When drawn, it means the sum (area) of the illuminance of each wavelength light included in the irradiation light.

Irradiation with UV light is performed as an irradiation light amount [mJ / cm ² ] that is 10 times or more of the exposure amount at the time of exposure in the pattern forming step. If the amount of irradiation light in this step is less than 10 times, color transfer between colored pixels and between upper and lower layers cannot be prevented, and light resistance also deteriorates.
Especially, the irradiation light quantity of UV light is preferably 12 times or more and 200 times or less, more preferably 15 times or more and 100 times or less the exposure amount at the time of exposure in the pattern forming step.

In this case, the integrated irradiation illuminance in the irradiated ultraviolet light is preferably 200 mW / cm ² or more. When the integrated irradiation illuminance is 200 mW / cm ² or more, the effect of suppressing color transfer between colored pixels and the upper and lower layers and the effect of improving light resistance can be more effectively enhanced. Among them, preferred is ^{250~2000mW / cm 2, 300~1000mW / cm} 2 is more preferable.
The post-heating is preferably performed at 100 ° C. to 300 ° C. using a hot plate or an oven, and more preferably 150 ° C. to 250 ° C. The post-heating time is preferably 30 seconds to 30000 seconds, more preferably 60 seconds to 1000 seconds.
On the other hand, the post-exposure can be performed by g-line, h-line, i-line, KrF, ArF, UV light, electron beam, X-ray, etc., but g-line, h-line, i-line, UV light is preferable. UV light is preferred. When performing irradiation with UV light (UV cure), it is preferable to carry out at a low temperature of 20 ° C. or more and 50 ° C. or less (preferably 25 ° C. or more and 40 ° C. or less). The wavelength of the UV light preferably includes a wavelength in the range of 200 nm to 300 nm. As the light source, for example, a high pressure mercury lamp, a low pressure mercury lamp, or the like can be used. The irradiation time is 10 seconds to 180 seconds, preferably 20 seconds to 120 seconds, and more preferably 30 seconds to 60 seconds.
Either post-exposure or post-heating may be performed first, but post-exposure is preferably performed prior to post-heating. This is because curing is promoted by post-exposure, thereby suppressing deformation of the shape due to heat sagging and soaking of the pattern seen in the post-heating process.

The colored pattern thus obtained constitutes a pixel in the color filter.
In the production of a color filter having a plurality of hue pixels, the aforementioned coating process, exposure process, and development process (a curing process as necessary) may be repeated in accordance with the desired number of colors.

Since the color filter obtained by the method for producing a color filter of the present invention (the color filter of the present invention) uses the colored curable composition of the present invention, the color filter has excellent light resistance.
Therefore, the color filter of the present invention can be used for a liquid crystal display element, a solid-state imaging element such as a CCD image sensor or a CMOS image sensor, and a camera system using the same. In addition, it is suitable for use in a solid-state imaging device that requires a good rectangular cross-sectional profile, particularly for a high-resolution CCD device, CMOS, or the like exceeding 1 million pixels.

<Solid-state imaging device>
The solid-state imaging device of the present invention includes the color filter of the present invention. The color filter of the present invention has high light resistance, and a solid-state imaging device provided with this color filter can obtain excellent color reproducibility.

The configuration of the solid-state imaging device is not particularly limited as long as it includes the color filter of the present invention and functions as a solid-state imaging device. For example, the following configuration can be given.
That is, a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of an image sensor (solid-state imaging device) such as a CCD or CMOS is provided on a support, and the color filter of the present invention is further provided thereon. Next, the microlens is laminated.

  In addition, the camera system including the color filter of the present invention includes a cover lens, a microlens, and the like in which a camera lens and an IR cut film are dichroically coated, from the viewpoint of light fading of a color material. It is desirable that the characteristics absorb part or all of UV light of 400 nm or less. Further, the structure of the camera system is preferably such that the oxygen permeability to the color filter is reduced in order to suppress oxidation fading of the color material. For example, a part or the whole of the camera system Is preferably sealed with nitrogen gas.

<Liquid crystal display element>
The color filter of the present invention is used for a color filter for a liquid crystal display device. The liquid crystal display element provided with the color filter of the present invention can display a high-quality image having a good display image color and excellent display characteristics.

  For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issued in the first year). 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 may be used in 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.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a lateral 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 bright and high-definition COA (Color-filter On Array) system. In a COA type liquid crystal display device, the required characteristics for the color filter layer require the required characteristics for the interlayer insulating film in addition to the normal required characteristics as described above, that is, low dielectric constant and peeling liquid resistance. Sometimes. In the color filter of the present invention, since a dye multimer excellent in hue is used, it is considered that the deterioration in display characteristics which is a concern when a dye is used as a colorant is eliminated. As a result, it is excellent in good hues such as color purity, so that it is possible to provide a COA liquid crystal display device with high resolution and excellent long-term durability. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trends in the market (issued by Toray Research Center Research Division 2001)".

The liquid crystal display element of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display element composed of these known members. Regarding these materials, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding backlighting, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Yukiaki Yagi), etc. Are listed.

  When the color filter of the present invention is used for a liquid crystal display element, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, and 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.

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

[Examples 1-1 to 1-29]
(1) Preparation of resist solution A (negative type)
The following components were mixed and dissolved to prepare a resist solution A.
-Propylene glycol monomethyl ether acetate 5.20 parts-Cyclohexanone 52.60 parts-Binder 30.50 parts (benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate copolymer, molar ratio = 60: 20: 20, Average molecular weight 30200 (polystyrene conversion),
41% cyclohexanone solution)
・ Dipentaerythritol hexaacrylate 10.20 parts ・ Polymerization inhibitor (p-methoxyphenol) 0.006 parts ・ Fluorosurfactant (F-475 manufactured by DIC Corporation) 0.80 parts ・ Photopolymerization initiator 0 58 parts [4-Benzoxolane-2,6-bis (trichloromethyl) -s-triazine: TAZ-107 manufactured by Midori Chemical Co., Ltd.]

(2) Production of glass substrate with undercoat layer A glass substrate (Corning 1737) was ultrasonically washed with 0.5% NaOH water, and then washed with water and dehydrated (200 ° C./20 minutes). Next, the resist solution A obtained in the above (1) was applied on a glass substrate washed with a spin coater so that the film thickness after drying was 2 μm, and was dried by heating at 220 ° C. for 1 hour to form an undercoat layer An attached glass substrate was prepared.

(3) Preparation of colored curable composition (3-1) C.I. I. Preparation of Pigment Blue 15: 6 Dispersion I. Pigment Blue 15: 6 dispersion was prepared as follows.
That is, C.I. I. Pigment Blue 15: 6 (11.8 parts by mass (average particle diameter 55 nm)), pigment dispersant BY-161 (manufactured by BYK) 5.9 parts by mass, and PGMEA 82.3 parts by mass were mixed with a bead mill (zirconia). A pigment dispersion was prepared by mixing and dispersing for 3 hours using beads having a diameter of 0.3 mm. Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a pigment dispersion (CI Pigment Blue 15: 6 dispersion). With respect to the obtained pigment dispersion, the particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) and found to be 24 nm.

(3-2) Preparation of colored curable composition The following components were mixed and dispersed and dissolved to obtain a colored curable composition.
Cyclohexanone 1.133 parts Alkali-soluble resin (J1 or J2: compounds described in Table 2) 1.009 parts Solsperse 20000 (1% cyclohexane solution, manufactured by Nippon Lubrizol Co., Ltd.)
0.125 parts-photopolymerization initiator (compound with the following structure: compounds described in Table 2) 0.087 parts-colorant (pigment multimer: exemplary compounds P1 to P21: compounds described in Table 2) 0.183 Part / Pigment Blue 15: 6 dispersion 2.418 parts (solid content concentration 17.70%, pigment concentration 11.80%)
・ Dipentaerythritol hexaacrylate 0.521 parts ・ Glycerol propoxylate (1% cyclohexane solution) 0.048 parts

(4) Exposure and development of colored curable composition (image formation)
Using a spin coater, the colored curable composition obtained in (3) above is dried on the undercoat layer of the glass substrate with an undercoat layer obtained in (2) so that the film thickness after drying is 0.6 μm. It was applied and prebaked at 100 ° C. for 120 seconds.
Next, using an exposure apparatus UX3100-SR (manufactured by USHIO INC.), The coating film was irradiated at a wavelength of 365 nm through a mask having a line width of 2 μm with an exposure amount of 200 mJ / cm ² . After the exposure, development was performed using a developer CD-2000 (manufactured by Fuji Film Electronics Materials Co., Ltd.) at 25 ° C. for 40 seconds. Then, after rinsing with running water for 30 seconds, spray drying was performed. Thereafter, post-baking was performed at 200 ° C. for 15 minutes.

(5) Evaluation The heat resistance, solvent resistance, and light resistance of the coating film coated on the glass substrate using the colored curable composition were evaluated as follows. The evaluation results are shown in Table 2 below.

〔Heat-resistant〕
The glass substrate coated with the colored curable composition obtained in (3) above was placed on a 200 ° C. hot plate so as to be in contact with the substrate surface and heated for 1 hour, and then the chromaticity meter MCPD-1000 ( Otsuka Electronics Co., Ltd.) measured the color difference (ΔE ^* ab value) before and after heating and used it as an index for evaluating heat fastness, and evaluated according to the following criteria. A smaller ΔE ^* ab value indicates better heat resistance. The ΔE ^* ab value is a value obtained from the following color difference formula based on the CIE 1976 (L ^* , a ^* , b ^* ) space color system (Japanese Society for Color Science, New Color Science Handbook (Showa 60)) p. 266).
ΔE ^* ab = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2

[Solvent resistance]
The spectra of the various coating films after post-baking obtained in (4) above were measured (spectrum A). On this coating film, the resist solution A obtained in (1) above was applied so as to have a film thickness of 1 μm and prebaked, followed by CD-2000 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) development. Using the solution, development was performed under the conditions of 23 ° C. and 120 seconds, and the spectrum was measured again (spectrum B). The dye residual ratio (%) was calculated from the difference between the spectra A and B, and this was used as an index for evaluating the solvent resistance. This value indicates that the closer to 100%, the better the solvent resistance.

[Light resistance]
The spectra of the various coating films after post-baking obtained in (4) above were measured (spectrum A). The coating film was irradiated with a xenon lamp at 100,000 lux for 20 hours (equivalent to 2 million lux · h). The color difference (ΔE ^* ab value) of the coating film before and after irradiation with the xenon lamp was measured and used as an index of light resistance. The smaller ΔE ^* ab value is, the better the light resistance is, and the judgment criteria are as follows.

(Comparative Examples 1-1, 1-2)
In the same manner as in Example 1, except that (a) the dye multimer used in Example 1-1 was used as the colorant, B-1 or B-11 exemplified above as a dye monomer was used. The colored curable compositions of Comparative Examples 1 and 2 were prepared and evaluated in the same manner as in Example 1. The results are also shown in Table 2 below.

  From the results in Table 2, the colored curable compositions of Examples 1 to 24 according to the present invention were excellent in all of heat resistance, solvent resistance, and weather resistance. On the other hand, even if it is a colorant having the same squarylium skeleton, when the dye monomer is used as it is, even if it has a polymerizable group in the molecule, all the evaluation items are compared with the examples. It was inferior.

[Examples 2-1 to 2-29, Comparative examples 2-1 to 2-2]
A color filter was prepared by the following procedure using the colored curable compositions used in Examples 1-1 to 1-29 and Comparative Examples 1-1 to 1-2, and Examples 2-1 to 2-29 and Color transfer evaluation was carried out as Comparative Examples 2-1 to 2-2. The evaluation results are shown in Table 3 below.

-Fabrication of single color filter-
On the glass substrate with an undercoat layer (2) produced in Example 1-1, any one of the colored curable compositions used in Examples 1-1 to 1-29 and Comparative Examples 1-1 to 1-2 was used. Then, it was applied using a spin coater so that the dry film thickness was 1 μm, and pre-baked at 100 ° C. for 120 seconds to form a colored film. To this colored film, 7.0 [mu] m square pixels are respectively 200 [mJ] by an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.) through a mask pattern in which 4 mm × 3 mm regions are arranged on the substrate. / cm ^2] of the exposure amount, it was exposed at an intensity 1200 mW / cm ² (integral irradiation illuminance). After exposure, paddle development was performed at 23 ° C. for 60 seconds using a developer (Fuji Film Electronics Materials Co., Ltd. CD-2000, 60%) to form a pattern. Subsequently, it was rinsed with running water for 20 seconds and then spray-dried. Thereafter, as an ultraviolet irradiation step after the development step, the entire glass substrate on which the pattern was formed was irradiated with 10,000 [mJ / cm ² ] ultraviolet rays using a high-pressure mercury lamp (Ushio Electric Co., Ltd. UMA-802-HC552FFAL). . After irradiation, post-baking treatment was performed on a hot plate at 220 ° C. for 300 seconds to form a colored pattern on the glass substrate. In addition, the wavelength light of 275 nm or less contained in the irradiation light from a high pressure mercury lamp is 10%.

-Color transfer evaluation-
Apply the CT-2000L solution (base clearing agent, manufactured by FUJIFILM Electronics Materials Co., Ltd.) to the colored pattern forming surface of the color filter produced as described above so that the dry film thickness is 1 μm, and let it dry. After forming the transparent film, heat treatment was performed at 200 ° C. for 5 minutes. After the heating, the absorbance of the transparent film adjacent to the colored pattern was measured with a microspectrophotometer (LCF-1500M manufactured by Otsuka Electronics Co., Ltd.). The ratio [%] of the absorbance value of the obtained transparent film to the absorbance of the colored pattern similarly measured before heating was calculated and used as an index for evaluating the color transfer.

  From the results of Table 3, in any color filter having a colored pattern formed by using the colored curable compositions of Examples 1 to 24 according to the present invention, the color image on the transparent film adjacent to the colored pattern is well attributed. You can see that

<Example 3>
(Production of solid-state image sensor)
-Preparation of colored curable composition-
The C.I. used as the blue colorant in the above (3-1) “Preparation of CI Pigment Blue 15: 6 Dispersion”. I. A pigment dispersion for red and a pigment dispersion for green were prepared in the same manner except that the following colorant was used instead of Pigment Blue 15: 6.

C. Pigment for forming pixels / pigment for red color used in curable composition for each color of RGB I. Pigment Red 254
Green pigment C.I. I. Pigment Green 36 and C.I. I. 70/30 [mass ratio] mixture with Pigment Yellow 139

(4-1-1) Blue pigment dispersion C.I. prepared in (3-1) above. I. Pigment Blue 15: 6 dispersion was used.
(4-1-2) Preparation of Red Pigment Dispersion and Green Pigment Dispersion 11.8 parts by weight (average particle size 55 nm) of the red pigment or green pigment described above, and pigment dispersant BY-161 (manufactured by BYK) ) And 5.9 parts by mass of PGMEA were mixed and dispersed by a bead mill (zirconia beads 0.3 mm diameter) for 3 hours to prepare a pigment dispersion. Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to prepare a red pigment dispersion and a green pigment dispersion, respectively. With respect to the obtained pigment dispersion, the particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)), and all were 24 nm.

(4-2) Preparation of colored curable composition (4-2-1) Blue colored curable composition As the blue colored curable composition, the one prepared in Example 1-18 was used.

(4-2-2) Red colored curable composition and green colored photosensitive composition In the same manner as the blue colored curable composition prepared in Example 1-18, the following components were mixed and dispersed and dissolved. Thus, a red colored curable composition and a green colored curable composition were obtained.
-Cyclohexanone 1.133 parts-Alkali-soluble resin (J1) 1.009 parts-Solsperse 20000 (1% cyclohexane solution, manufactured by Nippon Lubrizol Co., Ltd.)
0.125 parts-Photopolymerization initiator (I-1) 0.087 parts-Red pigment dispersion or green pigment dispersion 2.418 parts (solid content concentration 17.70%, pigment concentration 11.80%)
・ Dipentaerythritol hexaacrylate 0.521 parts ・ Glycerol propoxylate (1% cyclohexane solution) 0.048 parts

-Fabrication of full-color color filters for solid-state image sensors-
Using the colored curable composition for red, a red pixel is formed with an island pattern of 1.0 × 1.0 μm, and then 1.0 × 1.0 μm is formed using the colored curable composition for green. A green pixel is formed with a Bayer pattern, and a blue pixel with an island pattern of 1.0 × 1.0 μm is formed in the remaining lattice using the colored curable composition for blue, and a light shielding portion solid is formed. A color filter for an image sensor was produced.

-Evaluation-
When the obtained full-color color filter for a solid-state image sensor is incorporated in the solid-state image sensor, the solid-state image sensor has a high light-shielding property, a high resolution, and a good color separation property. It was confirmed.

Claims (13)

(A) a dye multimer comprising a squarylium compound represented by the following general formula (M) as a partial structure of the dye part, (b) a polymerizable compound, (c) a photopolymerization initiator, and (d) an organic solvent. A colored curable composition to be contained.

[In General Formula (M), A and B each independently represents an aryl group or a heterocyclic group. ] The squarylium compound represented by the general formula (M) is one or more compounds selected from a compound represented by the following general formula (M-1) and a compound represented by the general formula (M-2). The colored curable composition according to claim 1.

[In General Formula (M-1), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , and R ⁸ are each independently a hydrogen atom, a halogen atom, a linear or branched alkyl group, a cyclo Alkyl group, linear or branched alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy Group, acyloxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or aryl Sulfonylamino group, mercapto group, alkylthio group, arylthio Group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, It represents a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group or a silyl group. R ¹ and R ² , R ⁵ and R ⁶ may be connected to each other to form a ring. R ³ and R ⁷ each independently represents a hydrogen atom, a chain alkyl group, a cycloalkyl group, a cycloalkenyl group, an alkynyl group, an aryl group or a heterocyclic group. ]

[In the general formula (M-2), R ²¹ , R ²³ , R ²⁴ , R ²⁵ , R ²⁷ and R ²⁸ are the same as R ¹ , R ³ , R ⁴ , R ⁵ in the general formula (M-1), respectively R ⁷ and ^{R 8} are synonymous. ] The (a) dye multimer comprises at least one of structural units represented by the following general formula (A) and general formula (C), or is represented by the general formula (D) The colored curable composition according to claim 1 or 2, which is a multimer.

[In General Formula (A), X ^A1 represents a linking group formed by polymerization, and L ^A1 represents a single bond or a divalent linking group. Dye represents a dye residue obtained by removing one arbitrary hydrogen atom of the squarylium compound represented by the general formula (M). ]
[In the general formula (C), L ^C1 represents a single bond or a divalent linking group, and Dye represents a dye residue obtained by removing two hydrogen atoms of the squarylium compound of the general formula (M). n represents an integer of 1 to 4. ]
[In General Formula (D), L ^D1 represents an m-valent linking group, m represents an integer of 2 to 100, and Dye represents an arbitrary hydrogen atom of the squarylium compound represented by General Formula (M). Represents the pigment residue after removal. ] The colored curable composition according to claim 3, wherein the structural unit represented by the general formula (A) is derived from a dye monomer represented by the following general formula (1).

[In General Formula (1), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. L ¹ is —N (R ² ) C (═O) —, —OC (═O) —, —C (═O) N (R ¹² ) —, —C (═O) O—, The group represented by (2), the group represented by the following general formula (3), or the group represented by the following general formula (4) is represented. L ² represents a divalent linking group. m and n each independently represents 0 or 1. Dye is a dye residue obtained by removing one hydrogen atom from the squarylium compound represented by the general formula (M-1), or any hydrogen atom derived from the squarylium compound represented by the general formula (M-2). Represents a dye residue with one atom removed. R ¹² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. ]


[In General Formula (2) to General Formula (4), R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ³ represents a monovalent substituent. k represents an integer of 0 to 4. In the general formula (2) to the general formula (4), * represents a position bonded to the —C (R ¹ ) ═CH ₂ group in the general formula (1), and ** represents L in the general formula (1). ² or Dye (when n = 0) is represented. ] The colored curable composition according to any one of claims 1 to 4, wherein the (a) dye multimer has an alkali-soluble group. Furthermore, the coloring curable composition of any one of Claims 1-5 containing coloring agents other than (a-2) (a) pigment | dye multimer. A colorant other than the (a-2) (a) dye multimer is C.I. I. The colored curable composition according to claim 6, which is CI Pigment Blue 15: 6. The color filter which uses the colored curable composition as described in any one of Claims 1-7. The process of providing the colored curable composition as described in any one of Claims 1-7 on a board | substrate, and forming a colored curable composition layer, and this colored curable composition layer in a pattern form A method for producing a color filter, comprising: an exposure step; and a step of developing and removing an unexposed portion to form a pattern. The colored curable composition according to any one of claims 1 to 7, which is used for forming a color filter for a solid-state imaging device. A solid-state imaging device comprising the color filter according to claim 8. The colored curable composition according to any one of claims 1 to 7, which is used for forming a color filter for a liquid crystal display element. A liquid crystal display device comprising the color filter according to claim 8.