JP5992486B2 - Colored curable composition, color filter, method for producing the same, solid-state imaging device, and liquid crystal display device - Google Patents

Description

The present invention is suitable colored curable composition in the manufacture of color filters for use in liquid crystal display devices and solid-state imaging device or the like, a color filter, a method of manufacturing a solid-state imaging device, and relates to a liquid crystal display equipment.

One of the methods for producing a color filter used for a liquid crystal display device, a solid-state image sensor, etc. is a pigment dispersion method. As this pigment dispersion method, color curable in which pigments are dispersed in various photosensitive compositions. There is a method of producing a color filter by a photolithography method using a composition. That is, a colored curable composition is applied onto a substrate using a spin coater, a roll coater, or the like, dried to form a colored curable composition coating film, and the coating film is subjected to pattern exposure and development. Get colored pixels. By repeating this operation for a desired hue, a color filter is produced.
The method described above is stable to light and heat because it uses a pigment, and also has a sufficient positional accuracy because it is patterned by photolithography, and is suitable for manufacturing a color filter for a liquid crystal display device. 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 until now 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 definition and high resolution, the use of a dye as a colorant has been studied (for example, see Patent Document 1). However, the dye-containing colored 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 colored 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 colored curable composition The other components must be reduced, and the curability of the colored curable composition, the heat resistance after curing, the developability after exposure, and the like are reduced.

Among these problems of dyes, (4) as dyes that solve the molar extinction coefficient (ε) of dyes, there are xanthenes (see, for example, Patent Document 2). Many compounds are inferior to dyes, and their improvement is strongly desired.
In addition, the colored curable composition containing a dye has a problem of color transfer in addition to the above-described problems.
For example, in order to provide a red pixel on a formed green pixel, a colored curable composition containing a red dye is applied on the green pixel, and an unexposed red curable composition layer on the green pixel is developed. The dye in the green pixel is eluted into the red curable composition, or the dye in the red colored curable composition is transferred to the green pixel, and the green pixel is decolored or discolored, or the green pixel is red. There is a tendency to generate a taste-like phenomenon, so-called “color transfer”, and the improvement thereof is strongly desired.

  Furthermore, the coloring curable composition containing the dye has a heat resistance of the dye when the colored pixel is subjected to heat in the manufacturing process of the color filter for forming the colored pixel, the process of incorporating the color filter into the solid-state imaging device, etc. In addition to the above problems, dyes tend to sublimate, and there are also problems such as the color pixels being decolored and discolored by sublimation of the dye, and the desired hue cannot be obtained, and the manufacturing process is contaminated by the sublimated dye. There are also some problems. As a technique for preventing this, it has been proposed to use a dye provided with a polymerizable group in a colored curable composition (see, for example, Patent Document 3), but it is sufficient for the above-described color transfer and the like. No effect was obtained, and further improvement in heat resistance has been awaited.

JP-A-6-75375 JP 2010-32999 A JP 2000-162429 A

Colored curable compositions containing xanthenes as dyes have 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 components in the cured part are not eluted into the solvent and are retained in the colored pixels. When an RGB color filter is produced by a photolithography method, colored curable compositions having different hues are covered on the colored pattern in order to sequentially form patterns of each color. 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, the cured portion is required to have high solvent resistance. 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.

This invention is made | formed in view of said problem, and makes it a subject to achieve the following objectives.
That is, the first object of the present invention is a colored curing containing a dye multimer 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. It is to provide a sex composition.
In addition, the second object of the present invention is to provide a color filter having a colored pattern excellent in color purity, heat resistance and light resistance even when thinned, a method for producing the color filter, and a solid provided in the color filter. An image sensor and a liquid crystal display device are provided.
Furthermore, the third object of the present invention is to provide a dye multimer that can form a colored curable composition having excellent color purity, light resistance, heat resistance, solvent resistance, little color transfer, and good pattern moldability. It is to provide.

  As a result of detailed examination of various dyes, the present inventors have found that a xanthene compound having a specific structure has a good hue and a high extinction coefficient, and that the xanthene skeleton is introduced into the dye multimer. By introducing a polymerizable group into the skeleton and forming a dye multimer as a polymerization component, a colored curable composition having high solvent resistance and capable of reducing color transfer can be provided, and the dye multimer is necessary if necessary. By introducing an alkali-soluble group, the inventors have obtained knowledge that a colored curable composition having excellent pattern-forming properties (low concentration dependency of an alkali developer) can be provided, and the present invention has been achieved based on such knowledge. .

  Specific means for solving the above problems are as follows.

<1> (a) a dye multimer containing a xanthene skeleton as a partial structure of the dye moiety and having a weight average molecular weight in the range of 5000 to 30000, (b) a polymerizable compound, (c) a photopolymerization initiator, and , containing organic solvent (d), the xanthene skeleton, dye skeleton der from xanthene compound represented by the following general formula (M) is, the (a) dye multimer has the general formula described below (a ), the general formula (B) and the general formula (C) comprise or consists of at least one of structural units represented by, or the colored curable composition dye Ru multimer der represented by the general formula (D) object.

[In General Formula (M), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or a monovalent substituent; R ⁵ each independently represents a monovalent substituent; Represents an integer of 0 to 5. ]

[In General Formula (A), X ¹ represents a linking group formed by polymerization, L ¹ represents a single bond or a divalent linking group, and Dye represents an arbitrary hydrogen atom from the general formula (M). Represents the pigment residue after removal. ]

[In General Formula (B), X ² represents a linking group formed by polymerization, L ² represents a single bond or a divalent linking group, A represents a * —COO ^— group, and Dye represents the above general formula. It is a dye skeleton represented by (M) and represents a dye cation structure capable of ionic bonding with A. ]

[In General Formula (C), L ³ represents a single bond or a divalent linking group, and when a plurality of L ³ are present , the structures of L ³ may be the same or different. Dye represents a dye residue obtained by removing two arbitrary hydrogen atoms from the general formula (M). n3 represents an integer of 1 to 4. ]

[In General Formula (D), L ⁴ represents an n4-valent linking group, n4 represents an integer of 2 to 100, and a plurality of Dye each independently represents one arbitrary hydrogen atom from General Formula (M). Represents the removed pigment residue. ]

<2> The colored curable composition according to <1>, wherein the (c) photopolymerization initiator is an oxime compound.
<3> (a) a dye multimer containing a xanthene skeleton as a partial structure of the dye moiety and having a weight average molecular weight in the range of 5000 to 30000, (b) a polymerizable compound, (c) a photopolymerization initiator, and , (d) contain an organic solvent, wherein (c) a photopolymerization initiator Ri oxime compounds der, wherein (a) dye multimer has the general formula of the aforementioned (a), formula (B) and the general or comprising at least one of structural units represented by the formula (C), or the general formula (D) dye polymer der represented by Ru colored curable composition.
<4> The colored curable composition according to any one of <1> to <3>, wherein the (a) dye multimer further has an alkali-soluble group.
<5> The (a) a dye multimer, or comprise at least one structural unit represented by the following general formula (A), contact and the general formula (C), and or, in general formula (D) The colored curable composition according to any one of <1> to <4>, which is a dye multimer represented.

[In General Formula (A), X ¹ represents a linking group formed by polymerization, L ¹ represents a single bond or a divalent linking group, and Dye represents an arbitrary hydrogen atom from the general formula (M). Represents the pigment residue after removal. ]

[In General Formula (C), L ³ represents a single bond or a divalent linking group, and when a plurality of L ³ are present, the structures of L ³ may be the same or different. Dye represents a dye residue obtained by removing two arbitrary hydrogen atoms from the general formula (M). n3 represents an integer of 1 to 4. ]

[In General Formula (D), L ⁴ represents an n4-valent linking group, n4 represents an integer of 2 to 100, and a plurality of Dye each independently represents one arbitrary hydrogen atom from General Formula (M). Represents the removed pigment residue. ]

<6> The colored curable composition according to any one of <1> to <5>, further including a phthalocyanine pigment.
<7> A color filter using the colored curable composition according to any one of <1> to <6>.
<8> A method for producing a color filter, wherein the colored curable composition according to any one of <1> to <6> is applied onto a substrate, exposed through a mask, and developed to form a pattern image. .

<9> A solid-state imaging device comprising the color filter according to <7>.
<10> A liquid crystal display device comprising the color filter according to <7>.

  In the present invention, the pixel pattern is formed in a thin film (for example, 1 μm or less in thickness), and the fineness is as small as 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). This is particularly effective for forming a color filter for a solid-state imaging device that is required and requires a good rectangular cross-sectional profile.

According to the present invention, there is provided a colored curable composition comprising a dye multimer 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. can do.
Also provided are a color filter having a coloring pattern excellent in color purity, heat resistance and light resistance even when it is thinned, a method for producing the color filter, a solid-state imaging device including the color filter, and a liquid crystal display device it is Ru can be.

  The colored curable composition, the color filter, the method for producing the color filter, the solid-state imaging device, the liquid crystal display device, and the dye multimer of the present invention will be described in detail below. 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 comprises (a) a dye multimer containing a xanthene skeleton as a partial structure of a dye moiety and having a weight average molecular weight in the range of 5000 to 30000, (b) a polymerizable compound, (c) ) a photopolymerization initiator, and, (d) contain an organic solvent, wherein the xanthene skeleton, Ri dye skeleton der from xanthene compounds represented by the general formula below (M), wherein (a) dye polymer Contains at least one of structural units represented by general formula (A), general formula (B) and general formula (C) described later, or a large amount of dye represented by general formula (D) and wherein the Karadadea Rukoto.
In addition, the colored curable composition of the present invention includes (a) a dye multimer containing a xanthene skeleton as a partial structure of the dye part and having a weight average molecular weight in the range of 5000 to 30000, (b) a polymerizable compound, (c) a photopolymerization initiator, and, (d) contain an organic solvent, wherein the photopolymerization initiator (c) is an oxime-based compound der is, the (a) dye multimer has the general formula described below (a ), the general formula (B) and the general formula (C) in or represented by comprising at least one constitutional unit, or a feature of the dye multimer der Rukoto represented by the general formula (D) To do.
The dye multimer containing (a) the xanthene skeleton used as the partial structure of the dye part for use in the colored curable composition of the present invention will be described.

<< (a) Dye Multimer Containing Xanthene Skeleton as Partial Structure of Dye Part >>
The dye multimer in the present invention is a dye multimer containing a xanthene skeleton described in detail below as a partial structure of the dye moiety. The method of introducing the xanthene skeleton into the dye multimer of the present invention is arbitrary, and a polymer obtained by introducing a xanthene skeleton into a polymerizable monomer may be polymerized or copolymerized to obtain a multimer. After forming the body, a xanthene skeleton may be introduced by a polymer reaction or the like.
As a preferred embodiment, a multimer comprising at least one structural unit represented by the above general formula (A), general formula (B), and general formula (C), or the above general formula (D) And a dye multimer represented.

<Preferred physical properties of the dye multimer in the present invention>
The dye multimer in 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 moldability. It can be used in suitable colored curable compositions. From such a viewpoint, if the preferable physical properties of the dye multimer in the present invention are mentioned, when the dye multimer in the present invention is applied to a colored curable composition, the dye in the present invention is improved from the viewpoint of improving the color pattern forming property. The multimer preferably has an alkali-soluble group.

The method for introducing an alkali-soluble group into the dye multimer in the present invention is not particularly limited, but can be introduced by synthesizing a dye multimer using a monomer having an alkali-soluble group, An 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, at least one of the structural units represented by the general formula (A), the general formula (B), and the general formula (C) is used. It is sufficient that at least one of the dye multimer comprising or the dye multimer represented by the general formula (D) has an alkali-soluble group. When the structural unit represented by the general formula (A), the general formula (B), or the general formula (C) is a monomer having an alkali-soluble group, it is alkali-soluble in the Dye portion (dye residue). It may have a group. From the viewpoint of synthetic compatibility, at least one of the other ethylenically unsaturated bond-containing monomers contained as a copolymerization component is included rather than a monomer that forms a structural unit having a Dye moiety (dye residue). A monomer having an alkali-soluble group is preferable.

Preferred alkali-soluble groups possessed by the dye multimer in the present invention are a carboxyl group, a sulfonic acid group, a phosphonic acid group, a hydroxyl group, and a sulfonimide group, and preferably a carboxyl group and a sulfonic acid group.
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, methacryloxyethylphosphonic acid, styrenesulfonic acid, p-hydroxystyrene, acrylic acid, methacrylic acid Is preferred.

The dye multimer in 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. More preferably, the acid value is more preferably 50 to 200 mgKOH / g.
In the present invention, the acid value is determined by the method described in JIS standard (JIS K 0070: 1992).

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

  The dye multimer in the present invention is preferably dissolved 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 1% by mass or more and 50% by mass or less is preferable, more preferably 5% by mass or more and 40% by mass or less, and still more preferably 10% by mass or more and 30% by mass or less. By being in this region, when applying the dye multimer in the present invention to a colored curable composition, etc., it is possible to reduce a decrease in concentration due to a suitable coating surface shape and elution after coating a colored curable composition of another color. You can do it.

  The Tg of the dye multimer in the present invention is preferably 50 ° C. or higher, and more preferably 100 ° C. or higher. Further, the 5% mass reduction temperature by thermal mass spectrometry (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 becomes possible to reduce the concentration change caused by the heating process when the dye multimer of the present invention is applied to a colored curable composition or the like.

  The maximum absorption wavelength (λmax) of the dye multimer in the present invention is preferably from 510 nm to 590 nm, preferably from 530 nm to 570 nm, and more preferably from 540 nm to 555 nm. By being in this region, a color filter with good color reproducibility can be produced when applied to a colored curable composition 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, more preferably 100,000 times the absorbance at 450 nm of the dye multimer of the present invention. More preferably, it is twice or more. When this ratio is in this range, when applying the dye multimer of the present invention to a colored curable composition or the like, it is possible to form a color filter with higher transmittance, particularly when producing a blue color filter. it can.

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

  Moreover, it is more preferable that the dye multimer in the present invention satisfies the preferable ranges of the maximum absorption wavelength (λmax) and the extinction coefficient per unit weight of the dye multimer at the same time.

  The molecular weight of the dye multimer in the present invention is 5,000 to 30,000, more preferably 5,000 to 25,000, and still more preferably 5,000 to 20,000. By being in this range, the effects of the present invention can be fully exhibited, the solubility in a solvent is good, and the film (colored pixel) of the colored curable composition obtained by curing is light-resistant. Good heat resistance and solvent resistance.

<Structure of Dye Multimer in the Present Invention>
Details of the structure of the dye multimer in the present invention will be described below.
The dye multimer in the present invention includes a xanthene skeleton as a partial structure of the dye part.
In the dye multimer in the present invention, the xanthene skeleton is preferably a dye skeleton derived from a xanthene compound represented by the following general formula (M).

<Xanthene skeleton represented by general formula (M)>
A preferred embodiment of the dye multimer in the present invention is a dye multimer containing a dye skeleton derived from a xanthene compound represented by the following general formula (M) as a partial structure of the dye part.

In general formula (M), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or a monovalent substituent, R ⁵ each independently represents a monovalent substituent, and m is Represents an integer from 0 to 5.

Examples of the monovalent substituent when R ^{1 to} R ⁴ and R ⁵ in the general formula (M) represent a monovalent substituent include, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom) An alkyl group (preferably a linear, branched, or cyclic alkyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group. , T-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), An alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as vinyl group, allyl group, 3-butene 1-yl group), an aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably an aryl group having 6 to 24 carbon atoms, such as a phenyl group or a naphthyl group), a heterocyclic group (preferably having 1 to 32 carbon atoms). More preferably a heterocyclic group having 1 to 18 carbon atoms, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl. Group, 1-pyrazolyl group, benzotriazol-1-yl group) group, silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, such as trimethylsilyl group, triethylsilyl group, Tributylsilyl group, t-butyldimethylsilyl group, t-hexyldimethylsilyl group), hydroxyl group, cyano group, nitro group, alkoxy group (preferably An alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, an isopropoxy group, a t-butoxy group, a dodecyloxy group, A cycloalkyloxy group such as a cyclopentyloxy group or a cyclohexyloxy group; an aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as a phenoxy group, 1- A naphthoxy group), a heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group) Group),

A silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, a trimethylsilyloxy group, a t-butyldimethylsilyloxy group, a diphenylmethylsilyloxy group), an acyloxy group (preferably An acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an acetoxy group, pivaloyloxy group, benzoyloxy group, dodecanoyloxy group), an alkoxycarbonyloxy group (preferably having 2 to 48 carbon atoms, More preferably, it is an alkoxycarbonyloxy group having 2 to 24 carbon atoms, for example, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, a cycloalkyloxycarbonyloxy group, such as cyclohexyloxycarbonyloxy), an aryloxycarbonoyl. An oxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxycarbonyloxy), a carbamoyloxy group (preferably having 1 to 48 carbon atoms, more preferably carbon 1 to 24 carbamoyloxy groups, for example, N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group, N-ethyl-N-phenylcarbamoyloxy group), sulfamoyl An oxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group), Alkylsulfonyloxy group (preferably having 1 to 38 carbon atoms, more preferably carbon In alkylsulfonyloxy group having 1 to 24, for example, methylsulfonyl group, hexadecyl sulfonyloxy group, cyclohexyl sulfonyloxy group),

An arylsulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, such as a phenylsulfonyloxy group), an acyl group (preferably having 1 to 48 carbon atoms, more preferably C1-C24 acyl group, for example, formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group), alkoxycarbonyl group (preferably C2-C48, more preferably An alkoxycarbonyl group having 2 to 24 carbon atoms, for example, a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group), Aryloxycarbonyl group (preferred Or an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as a phenoxycarbonyl group, and a carbamoyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms). Carbamoyl group such as carbamoyl group, N, N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methyl N-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group), amino group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as amino group, methylamino group, N, N-dibutylamino group, tetradecylamino group, 2-ethylhexylamino group, cyclohexyl Shiruamino group),

Anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as an anilino group or N-methylanilino group), a heterocyclic amino group (preferably having 1 to 32 carbon atoms, more preferably 1 A heterocyclic amino group having ˜18, for example, 4-pyridylamino group), a carbonamido group (preferably a carbonamide group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, an acetamide group, a benzamide group, tetradecane Amide group, pivaloylamide group, cyclohexaneamide group), ureido group (preferably ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as ureido group, N, N-dimethylureido group, N- Phenylureido group) and imide group (preferably having 36 or less carbon atoms, more preferably having 24 or less carbon atoms) An N-succinimide group, an N-phthalimido group, an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as a methoxycarbonylamino group, ethoxy A carbonylamino group, a t-butoxycarbonylamino group, an octadecyloxycarbonylamino group, a cyclohexyloxycarbonylamino group), an aryloxycarbonylamino group (preferably having 7 to 32 carbon atoms, more preferably having 7 to 24 carbon atoms) An amino group, for example, a phenoxycarbonylamino group), a sulfonamide group (preferably a sulfonamide group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methanesulfonamide group, a butanesulfonamide group, Benzenesulfonamide group, hexadecanesulfonamide group, cyclohexanesulfonamide group), sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N-dipropylsulfamoylamino group, N-ethyl-N-dodecylsulfamoylamino), azo group (preferably an azo group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, phenylazo group , 3-pyrazolylazo group),

An alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms, for example, a methylthio group, an ethylthio group, an octylthio group, a cyclohexylthio) group, an arylthio group (preferably 6 to 48 carbon atoms). More preferably, it is an arylthio group having 6 to 24 carbon atoms, such as a phenylthio group, and a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, Dodecanesulfinyl group), arylsulfinyl group (preferably having 6 to 32 carbon atoms, more preferably An arylsulfinyl group having 6 to 24 prime atoms, such as a phenylsulfinyl group, an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably an alkylsulfonyl group having 1 to 24 carbon atoms, such as a methylsulfonyl group, ethyl Sulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably having 6 to 48 carbon atoms, more preferably An arylsulfonyl group having 6 to 24 carbon atoms, for example, a phenylsulfonyl group, 1-naphthylsulfonyl group), a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, Rufamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group), sulfo group, phosphonyl A group (preferably a phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl), phosphinoylamino group (preferably carbon A phosphinoylamino group having 1 to 32, more preferably 1 to 24 carbon atoms, such as a diethoxyphosphinoylamino group or a dioctyloxyphosphinoylamino group).

In the case where the monovalent substituents represented by R ^{1 to} R ⁵ in the general formula (M) are further substitutable groups, they may further have the substituents described for R ^{1 to} R ^5. In the case of having two or more substituents, these substituents may be the same or different.

R ¹ and R ² , R ³ and R ^{4 in} the general formula (M), and R ^{5 in} the case where m is 2 or more are independently bonded to each other to form a 5-, 6-, or 7-member. A saturated ring or an unsaturated ring may be formed. When the 5-membered, 6-membered, and 7-membered rings formed are further substitutable groups, they may be substituted with the substituents described for R ^{1 to} R ⁵ above. When substituted with a substituent, these substituents may be the same or different.
R ¹ and R ² in the general formula (M), R ³ and R ⁴ , and R ^{5 in} the case where m is 2 or more are each independently bonded to each other, and are 5 members having no substituent, When a 6-membered or 7-membered saturated ring or unsaturated ring is formed, examples of the 5-membered, 6-membered, or 7-membered saturated ring or unsaturated ring having no substituent include, for example, a pyrrole ring, furan Ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexene ring, benzene ring, pyridine ring, pyrazine ring, pyridazine ring, preferably Examples thereof include a benzene ring and a pyridine ring.

The molar extinction coefficient of the compound having a xanthene skeleton represented by the general formula (M) is preferably as large 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 compound having a xanthene skeleton represented by the general formula (M) is preferably not too high from the viewpoint of solubility.

  The compound having a xanthene skeleton represented by the general formula (M) can be synthesized by a method described in the literature. Specifically, Tetrahedron Letters, 2003, vol. 44, No. 23, pages 4355-4360, Tetrahedron, 2005, vol. 61, No. 12, pages 3097-3106, etc. Can be applied.

Further preferred dye multimers in the present invention will be described.
Does the dye multimer containing a xanthene skeleton as a partial structure of the dye part, contains at least one of the structural units represented by the following general formula (A), general formula (B), and general formula (C)? Or a dye multimer represented by the general formula (D). These will be described sequentially.

<Structural Unit Represented by General Formula (A)>

In the general formula (A), X ¹ represents a linking group formed by polymerization, L ¹ represents a single bond or a divalent linking group, and Dye represents one arbitrary hydrogen atom from the general formula (M). Represents the removed pigment residue.

In the general formula (A), X ¹ 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 ¹ 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 the like. Preferably, an unsaturated ethylene group is polymerized. A linking group formed as described above. Specific examples include the following linking groups, but the linking groups formed by polymerization in the present invention are not limited to these.
Incidentally, indicating that it is linked to ^{L 1} at a site indicated by * in the following (X-1) ~ (X -15).

In general formula (A), L ¹ represents a single bond or a divalent linking group. In the case where L ¹ 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-, where R represents 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 (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 hydrogen atom or a substituent. k represents an integer of 0 to 4. When k is 2 or more, R ³ may be the same or different. In the general formulas (2) to (4), * represents a position bonded to the X ¹ group in the general formula (A), and ** represents a position bonded to Dye in the general formula (A). ]

  In the general formula (A), Dye represents a dye residue obtained by removing one arbitrary hydrogen atom from the general formula (M).

  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 (B)>
Next, details of the structural unit represented by the general formula (B) will be described.

In general formula (B), X ² represents a linking group formed by polymerization, L ² represents a single bond or a divalent linking group, A represents a group capable of ionic bonding or coordination bonding with Dye, Dye represents a dye residue capable of ionic bond or coordinate bond with A by removing one hydrogen atom from the general formula (M).
In the present invention, A * -COO ^- represents a group, Dye is a dye skeleton represented by the general formula (M), representing the A and ion-linkable dye cation structure.

In the general formula (B), the group represented by X ² and L ² each represent a group having the same meaning as X ¹ and L ¹ in the general formula (A), and the preferred range is also the same.
The group represented by A in the general formula (B) may be any group capable of ionic bonding or coordination bonding with Dye, and the group capable of ionic bonding may be either an anionic group or a cationic group. . The anionic group is preferably an anionic group having a pKa of 12 or less, such as a carboxyl group, a phospho group, a sulfo group, an acylsulfonamide group, or a sulfonimide group, more preferably a pKa of 7 or less, still more preferably 5 or less.
Specific examples of preferred anionic groups are shown below, but the present invention is not limited thereto. In the anionic groups shown below, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

As the cationic group represented by A in the general formula (B), a substituted or unsubstituted onium cation (for example, a substituted or unsubstituted ammonium group, pyridinium group, imidazolium group, sulfonium group, phosphonium group, etc.) Are preferable, and a substituted ammonium group is particularly preferable.
Specific examples of preferable cationic groups are shown below, but the present invention is not limited thereto. In the cationic groups shown below, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

  Although the specific example of the structural unit represented by general formula (B) 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 General Formula (C), L ³ represents a single bond or a divalent linking group, and when a plurality of L ³ are present, the structures of L ³ may be the same or different. Dye represents a dye residue obtained by removing two arbitrary hydrogen atoms from the general formula (M). n3 represents an integer of 1 to 4.

In the general formula (C), the divalent linking group represented by L ³ 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, etc.), substituted or unsubstituted arylene group having 6 to 30 carbon atoms (eg, 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)-etc.) are preferred. Here, R in each said formula represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.

It describes a specific example which is suitably used as the divalent linking group represented by L ³ in the general formula (C) below, but not limited to as L ³ of the present invention.

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

<Copolymerization component>
The dye multimer in the present invention may be formed of only the structural units represented by the general formula (A), the general formula (B), and the general formula (C), but may be formed together with other structural units. It may be quantified. The other structural units are preferably the structural units shown below, and specific examples thereof are shown, but the present invention is not limited thereto.

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

In General Formula (D), L ⁴ represents an n4-valent linking group, n4 represents an integer of 2 to 100, and a plurality of Dye each independently removes one arbitrary hydrogen atom from General Formula (M). Represents a pigment residue.

In the general formula (D), n4 is preferably 2 to 80, more preferably 2 to 40, and particularly preferably 2 to 10.
In the general formula (D), when n4 is 2, the divalent linking group represented by L ⁴ 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.

An n4 valent linking group having n4 of 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.

  Hereinafter, preferred examples of the dye multimer in the present invention are shown in the following Table 1 including the structural unit (the structural unit), the copolymer mass ratio, the weight average molecular weight, and the degree of dispersion.

  The dye multimer in the present invention preferably contains the structural unit represented by the general formula (A), the general formula (B), or the general formula (C) as a part thereof. Among these, It is preferably contained as a structural unit represented by the general formula (A).

The dye multimer in the present invention includes 100 mass% of the structural units represented by the general formula (A), the general formula (B), and the general formula (C) in a mass ratio (mass%), that is, A multimer obtained by polymerizing only the structural units represented by the general formula (A), the general formula (B), and the general formula (C) may be used.
From the viewpoint of coloring power, the structural units represented by the general formula (A), the general formula (B), and the general formula (C) are expressed in a mass ratio (% by mass) and 10% by mass to 10% by mass in the dye multimer. The content is preferably 100% by mass, more preferably 20% by mass to 100% by mass, and still more preferably 30% by mass to 100% by mass.

The method for synthesizing the dye multimer in the present invention will be described by taking S-4 exemplified above as an example.
<Synthesis of Exemplary Compound S-4>
23 g (0.034 mol) of a commercially available xanthene dye (Acid Red 289: Tokyo Chemical) was added to sulfolane (150 ml), and 40 g (0.34 mol) of chlorosulfonic acid was added dropwise while stirring at 5 ° C. . This solution was heated to an internal temperature of 80 ° C. and stirred at that temperature for 4 hours. After lowering the reaction solution to about 30 ° C., 40 g (0.34 mol) of thionyl chloride was slowly added dropwise, heated again to 80 ° C. and stirred for 4 hours. The reaction solution was poured into ice water, and the precipitated acid chloride was filtered off and dried.
Separately, 2-aminoethanol (1.2 g, 0.02 mol) dissolved in acetonitrile was cooled to an internal temperature of 5 ° C., and the acid chloride obtained previously was gradually added. The reaction liquid was raised to 40 ° C., stirred for 4 hours, poured into ice water, and the precipitated crystals were separated by filtration and dried to obtain an alcohol form (5.7 g, 0.008 mol).
The alcohol was dissolved in N, N-dimethylacetamide (50 ml), methacrylic acid chloride was added at 5 ° C., and the mixture was stirred as it was for 3 hours. The reaction solution was poured into water, and the precipitated crystals were separated by filtration and dried to obtain Q-1 form (4.7 g, 0.0072 mol).

The obtained Q-1 (4 g), methacrylic acid (0.54 g) and dodecanethiol (0.1 g) were dissolved in 10.0 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) and stirred at 85 ° C. Then, a solution of dimethyl 2,2′-azobis (2-methylpropionate) (0.2 g) dissolved in 1 g of PGMEA was added dropwise over 3 hours. Four hours after the start of dropping, dimethyl 2,2′-azobis (2-methylpropionate) (0.2 g) was added, and stirring was continued at 85 ° C. for another 2 hours. To the reaction solution, 200 ml of PGMEA and 200 ml of methanol were added, and the reaction solution was added dropwise while stirring. The precipitated crystals were filtered, and the obtained crystals were dried under reduced pressure to obtain 3.9 g of Example Compound S-4.
As for the structure of S-4, the disappearance of the peak of 5.56-6.12 which is the polymerizable group site of Q-1 and the introduction of methacrylic acid by acid value measurement were confirmed by ¹ H-NMR.

The molecular weight of the dye multimer in the present invention is preferably in the range of 5000 to 30000 in terms of weight average molecular weight (Mw) and in the range of 3000 to 20000 in terms of number average molecular weight (Mn). More preferably, the weight average molecular weight (Mw) is in the range of 5000 to 25000, and the number average molecular weight (Mn) is in the range of 3000 to 17000. Particularly preferably, the weight average molecular weight (Mw) is in the range of 5000 to 20000, and the number average molecular weight (Mn) is in the range of 3000 to 15000.
The weight average molecular weight (Mw) of the specific polymer is preferably 20000 or less from the viewpoint of developability when the dye multimer in the present invention is applied to a colored curable composition to produce a color filter.

≪Colored curable composition≫
The colored curable composition of the present invention contains, as a colorant, at least one dye multimer described above in the present invention, and (b) a polymerizable compound, (c) a photopolymerization initiator, and (d). Contains organic solvents. The colored curable composition of the present invention is characterized by being cured by heat, light or both, and can be constituted by using other components such as a binder and a crosslinking agent, if necessary.

  The colored curable composition of the present invention has a thin pixel pattern (for example, a thickness of 1 μm or less) due to the characteristics of the compound containing the xanthene skeleton as a partial structure of the dye portion, which is included in the structure of the dye multimer in the present invention. 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, the said pigment | dye multimer may be used individually by 1 type, and may be used together 2 or more types.
The content of the dye multimer in the colored curable composition of the present invention varies depending on the molecular weight and molar extinction coefficient of the dye multimer, but is 10% by mass with respect to the total solid content component of the colored curable composition. -70 mass% is preferable, 10 mass%-50 mass% is more preferable, 15 mass%-30 mass% is the most preferable.

  In the colored curable composition of the present invention and the color filter using the colored curable composition, a colorant other than the dye multimer can be used in combination as long as the effects of the present invention are not impaired. 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.

  The content of the triarylmethane-based colorant can be used within a range that does not impair the effects of the present invention, and is 0.5% by mass to 50% by mass with respect to the total solid content of the colored curable composition of the present invention. It is preferable that

  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, 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.
Further, the content ratio of the dye multimer having the xanthene skeleton as a partial structure of the dye portion and the phthalocyanine pigment is expressed as a ratio of the dye multimer having the xanthene skeleton as the partial structure of the dye portion. Dye multimer = 100: 5 to 100: 100 is preferable, 100: 15 to 100: 75 is more preferable, and 100: 25 to 100: 50 is still more preferable.

(Dispersant)
When the colored curable composition of this invention contains a pigment, it can contain a dispersing agent.
Examples of pigment dispersants that can be used in the present invention include polymer dispersants [for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified poly (meth) acrylates. , (Meth) acrylic copolymers, naphthalenesulfonic acid formalin condensates], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, pigment derivatives, and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures.
On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  Examples of the terminal-modified polymer having an anchor site to the pigment surface include polymers having a phosphate group at the terminal described in JP-A-3-112992, JP-T2003-533455, and the like. Examples thereof include a polymer having a sulfonic acid group at the terminal end described in JP-A-273191, and a polymer having a partial skeleton of an organic dye or a heterocyclic ring described in JP-A-9-77994. In addition, a polymer in which two or more anchor sites (acid group, basic group, partial skeleton of organic dye, heterocycle, etc.) to the surface of the pigment described in JP-A-2007-277514 are introduced. It is preferable because of excellent dispersion stability.

  Examples of the graft polymer having an anchor site to the pigment surface include poly (lower alkyleneimine) described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, and the like. ) And a polyester reaction product, a reaction product of polyallylamine and polyester described in JP-A-9-169821, etc., a macromonomer described in JP-A-10-339949, JP-A-2004-37986, and the like, Copolymers with nitrogen atom monomers, graft-type polymers having partial skeletons or heterocyclic rings of organic dyes described in JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, etc. And a copolymer of a macromonomer and an acid group-containing monomer described in JP2010-106268A. It is. In particular, the amphoteric dispersion resin having a basic group and an acidic group described in JP-A-2009-203462 exhibits dispersibility of the pigment dispersion, dispersion stability, and a colored curable composition using the pigment dispersion. Particularly preferred from the viewpoint of developability.

  As the macromonomer used when the graft polymer having an anchor site to the pigment surface is produced by radical polymerization, a known macromonomer can be used. Macromonomer AA-6 (terminal) manufactured by Toa Gosei Co., Ltd. Polymethyl methacrylate whose group is a methacryloyl group), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (a copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 ( Polybutyl acrylate whose end group is a methacryloyl group), PLACEL FM5 manufactured by Daicel Chemical Industries, Ltd. (5 molar equivalent addition product of ε-caprolactone of 2-hydroxyethyl methacrylate), FA10L (2-hydroxyethyl acrylate) ε-caprolactone 10 molar equivalent addition product), and JP-A-2-2720 Polyester macromonomer described in No. 09 publication. Among these, polyester-based macromonomers that are particularly flexible and have good solvophilic properties are particularly preferred from the viewpoint of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the colored curable composition using the pigment dispersion. The polyester macromonomer represented by the polyester macromonomer described in JP-A-2-272009 is most preferable.

  As the block polymer having an anchor site to the pigment surface, block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.

  The pigment dispersant that can be used in the present invention is also available as a commercial product, and specific examples thereof include “Disperbyk-101 (polyamideamine phosphate), 107 (carboxylic acid ester)”, 110 (by BYK Chemie). Copolymer containing acid groups), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ) "EFKA 4047, 4050-4010-4165 (polyurethane)", EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylic acid) Salt), 6220 (fatty acid polyester), 6745 Phthalocyanine derivatives), 6750 (azo pigment derivatives) ”,“ Ajisper PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fine Techno Co.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co.,“ Polyflow No. 50E, No. .300 (acrylic copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester), DA-703-50, manufactured by Enomoto Kasei Co., Ltd. DA-705, DA-725 "," Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "manufactured by Kao Corporation," Homogenol L- 18 (polymer polycarboxylic acid) "," Emulgen 920, 930, 935 " 985 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, manufactured by Nippon Lubrizol Corporation. , 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate) ”, MYS-IEX (poly) Oxyethylene monostearate), Hinoact T-8000E manufactured by Kawaken Fine Chemical Co., Ltd., Sanyo Chemical Industries Ionette S-20, and the like.

These pigment dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant.
The pigment dispersant of the present invention may be used in combination with an alkali-soluble resin together with a terminal-modified polymer, a graft polymer, or a block polymer having an anchor site to the pigment surface. Alkali-soluble resins include (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and carboxylic acid in the side chain. Examples of the acid cellulose derivative include a resin having a hydroxyl group modified with an acid anhydride, and a (meth) acrylic acid copolymer is particularly preferable. Further, N-substituted maleimide monomer copolymers described in JP-A-10-300902, ether dimer copolymers described in JP-A-2004-300204, and polymerizable groups described in JP-A-7-319161. An alkali-soluble resin containing is also preferred.

As content of the pigment dispersant in a polymeric composition, it is preferable that it is 1-80 mass parts with respect to 100 mass parts of pigments which are colorants, 5-70 mass parts is more preferable, 10-60 mass parts More preferably, it is part.
Specifically, if a polymer dispersant is used, the amount used is preferably in the range of 5 to 100 parts in terms of mass, and in the range of 10 to 80 parts, with respect to 100 parts by mass of the pigment. It is more preferable.
Moreover, when using together a pigment derivative, it is preferable that it is in the range of 1-30 parts in conversion of mass as a usage-amount of a pigment derivative, and is in the range of 3-20 parts with respect to 100 mass parts of pigments. A range of 5 to 15 parts is particularly preferable.

  In the polymerizable composition, when a pigment as a colorant is used and a pigment dispersant is further used, the total content of the colorant and the dispersant constitutes the polymerizable composition from the viewpoint of curing sensitivity and color density. It is preferably 30% by mass or more and 90% by mass or less, more preferably 40% by mass or more and 85% by mass or less, and further preferably 50% by mass or more and 80% by mass or less with respect to the total solid content.

<(B) Polymerizable compound>
The colored curable composition of this invention can be comprised suitably by containing at least 1 type of (b) polymeric compound. The polymerizable compound is mainly contained when the colored curable composition is configured as a negative type.
In addition, a polymeric compound can be contained with the below-mentioned photoinitiator in the positive type | system | group containing a naphthoquinone diazide compound, and can further promote the hardening degree of the pattern formed in this case. Hereinafter, the polymerizable compound will be described.

  Specifically, the polymerizable compound 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. The polymeric compound in this invention may be used individually by 1 type, and may use 2 or more types together.

Examples of monomers and their (co) polymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and these (Co) polymers, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and their (co) It is a polymer. 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 numbers 0248 to 0251 of JP2007-26979A. Can also be suitably used in the present invention.

Moreover, it is preferable to contain the polyfunctional monomer which has a caprolactone structure as a polymerizable monomer.
The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta Ε-caprolactone modified polyfunctionality obtained by esterifying polyhydric alcohol such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone ( Mention may be made of (meth) acrylates. Among these, a polyfunctional monomer having a caprolactone structure represented by the following formula (i) is preferable.

  (In the formula (i), all six Rs are groups represented by the following formula (ii), or 1 to 5 of the six Rs are groups represented by the following formula (ii) And the remainder is a group represented by the following formula (iii).)

(In formula (ii), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.)

(In formula (iii), R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.)

Such a polyfunctional monomer having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (i) to (iii)). , Number of groups represented by formula (ii) = 2, compound in which R ¹ is all hydrogen atoms, DPCA-30 (same formula, m = 1, number of groups represented by formula (ii) = 3 , Compounds in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (ii) = 6, compounds in which R ¹ is all hydrogen atoms), DPCA- 120 (a compound in which m = 2 in the formula, the number of groups represented by formula (ii) = 6, and R ¹ is all hydrogen atoms).
In this invention, the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.

  As for content of the polymeric compound in the colored curable composition of this invention, 0.1 mass%-90 mass% are preferable with respect to solid content in a colored curable composition, 1.0 mass%-80 mass. % Is more preferable, and 2.0% by mass to 70% by mass is particularly preferable.

  In the colored curable composition of the present invention, the content mass ratio of the dye multimer to the polymerizable compound in the present invention (the dye multimer in the present invention: the polymerizable compound) is 1: 2 from the viewpoint of thinning. It is preferably 20: 1, more preferably 1: 1 to 10: 1.

<(C) Photopolymerization initiator>
The colored curable composition of the present invention contains (c) a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound described above, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.

  Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyloxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, and an acetophenone compound. And derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, oxime compounds, and the like. Specific examples of the photopolymerization initiator include those described in paragraphs 0070 to 0077 of JP-A No. 2004-295116. Among these, an oxime compound is preferable from the viewpoint of rapid polymerization reaction.

The oxime compound (hereinafter also referred to as “oxime photopolymerization initiator”) is not particularly limited, and is described in, for example, JP-A No. 2000-80068, WO 02 / 100903A1, and JP-A No. 2001-233842. These oxime compounds are mentioned.
Specific examples include 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (o-benzoyloxime) -1- [4- (phenylthio). Phenyl] -1,2-pentanedione, 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (o-benzoyloxime) -1- [4 -(Phenylthio) phenyl] -1,2-heptanedione, 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (o-benzoyloxime)- 1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (o-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1, -Butanedione, 2- (o-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (o-acetyloxime) -1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (o-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (o-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (o-acetyloxime) -1- [9- Ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (o-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) Such as 9H- carbazol-3-yl] ethanone and the like. However, it is not limited to these.

  Among these, 2- (o-benzoyloxime) -1- [4- (phenylthio) is obtained in that a good pattern (particularly, the rectangularity of the pattern in the case of a solid-state imaging device) can be obtained with a smaller exposure amount. Oxime-o such as phenyl] -1,2-octanedione, 1- (o-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone -Acyl compounds are particularly preferable, and specific examples include OXE-01 and OXE-02 (manufactured by BASF).

  In the present invention, compounds represented by the following formulas (E) and (F) are more preferable as oxime compounds from the viewpoints of sensitivity, stability over time, and coloring during post-heating.

  In the above formulas (E) and (F), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 1-5.

  R is preferably an acyl group from the viewpoint of increasing sensitivity, and specifically, an acetyl group, a propionyl group, a benzoyl group, and a toluyl group are preferable.

  A is an alkylene group 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 heat aging, An alkylene group substituted with an alkenyl group (for example, vinyl group, allyl group), an aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) A substituted alkylene group is preferred.

  Ar is preferably a substituted or unsubstituted phenyl group from the viewpoint of increasing sensitivity and suppressing coloring due to heating. In the case of a substituted phenyl group, the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

X is an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkenyl that may have a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. Group, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy group which may have a substituent, a substituent An arylthioxy group which may have an amino group and an amino group which may have a substituent are preferable.
Further, n in the formulas (E) and (F) is preferably an integer of 1 to 2.

  Specific examples of the compounds represented by formulas (E) and (F) are shown below, but the present invention is not limited thereto.

  In addition to the above photopolymerization initiator, other known photopolymerization initiators described in paragraph 0079 of JP-A No. 2004-295116 may be used in the colored curable composition of the present invention. .

A photoinitiator can be contained individually by 1 type or in combination of 2 or more types.
The content of the photopolymerization initiator in the total solid content of the colored curable composition (total content in the case of two or more) is 3% by mass to 20% by mass from the viewpoint of more effectively obtaining the effects of the present invention. % Is preferable, 4% by mass to 19% by mass is more preferable, and 5% by mass to 18% by mass is particularly preferable.

<(D) Organic solvent>
The colored curable composition of the present invention contains (d) 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.

-Alkali-soluble binder-
The alkali-soluble binder is not particularly limited except that it has alkali solubility, and can be preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

  The alkali-soluble binder is preferably a linear organic high molecular polymer that is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful. In addition, a polymer obtained by polymerizing a compound having a specific structure which is an ether dimer of 2- (hydroxyalkyl) acrylic acid ester (for example, a compound described in JP-A-2004-300203) is also useful.

  Another preferred example of the binder in the present invention includes a polymer containing a structure derived from a compound represented by the following general formula (ED) (hereinafter appropriately referred to as “ether dimer”) as a polymerization component.

In the general formula (ED), R ²¹ and R ²² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
By using a binder containing a structural unit derived from an ether dimer, the polymerizable composition of the present invention has an advantage that a cured coating film having excellent heat resistance and transparency can be formed.
In the general formula (ED) showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ²¹ and R ²² 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, a primary or secondary carbon substituent which is difficult to be removed by an acid or heat such as methyl, ethyl, cyclohexyl, benzyl and the like is particularly preferable from the viewpoint of heat resistance.

  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-propeno , 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- Tilcyclohexyl) -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. One type of these structural units derived from the ether dimer may be contained in the binder, or two or more types may be contained.
The binder comprising the monomer derived from the compound represented by the general formula (ED) is a copolymer comprising other monomers other than the structure derived from the compound represented by the general formula (ED). Also good. As other monomers that can be used in combination, the monomers listed above as the constituent components of the binder can be used in the same manner, and they can be used in combination as long as the properties of the ether dimer are not impaired.

  In addition to the above, the alkali-soluble binder in the present invention includes a polymer having a hydroxyl group added with an acid anhydride, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth)), and the like. Acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful. Further, the linear organic high molecular polymer may be a copolymer of hydrophilic monomers. Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth). Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight Examples include butyl (meth) acrylate of a chain, phenoxyhydroxypropyl (meth) acrylate, and the like. Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group and groups derived from salts thereof, morpholinoethyl group, etc. Monomers comprising it are also useful.

  The alkali-soluble binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Polymers and the like are also useful. Examples of the above-mentioned polymer containing a polymerizable group include: Dynal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd., manufactured by), 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 Corporation), Ebecryl 3800 (manufactured by Daicel UC Corporation), and the like. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Among these various alkali-soluble binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.

  Examples of the acrylic resin include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, the Photomer 6173, and the KS resist-106. Cyclomer P series and the like are preferable.

Alkali-soluble binder, developability, from the viewpoint of liquid viscosity, weight average molecular weight (measured in terms of polystyrene by GPC method) is preferably a polymer of 1,000 to 2 × 10 ^5, the weight of the 2000-1 × 10 ⁵ A coalescence is more preferable, and a polymer of 5000 to 5 × 10 ⁴ is particularly preferable.

-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 that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6- t-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
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-
A surfactant may be added to the colored curable composition of the present invention. As the surfactant, various surfactants such as a fluorosurfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.
In particular, by containing a fluorosurfactant, the liquid properties (particularly fluidity) when used as a coating liquid can be further improved, and the uniformity of coating thickness and liquid saving can be further improved.
That is, in the polymerizable composition containing a fluorosurfactant, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid, and the coating property to the coated surface is improved. Will improve. For this reason, even when a thin film having a thickness of about several μm to several tens of μm is formed with a small amount of liquid, it is effective in that a uniform film with small thickness unevenness can be formed more suitably.

  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. When the fluorine content is within this range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.

  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, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (manufactured by Asahi Glass Co., Ltd.), and the like.

Specific examples of cationic surfactants include phthalocyanine derivatives (commercially available product EFKA-745 (manufactured by Morishita Sangyo)), 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 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.) Rusupasu 20000 (manufactured by Nippon Lubrizol Corporation), 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-based surfactant include “Toray Silicone DC3PA”, “Same SH7PA”, “Same DC11PA”, “Short SH21PA”, “Short SH28PA”, “Short SH29PA”, “Short SH30PA” manufactured by Torre Silicone Co., Ltd. “Same SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-444 (4) (5) (6) (7) 6” manufactured by Momentive Performance Materials, “TSF-44 60”, “TSF-4452”, “KP341” manufactured by Shin-Etsu Chemical Co., Ltd., “BYK307”, “BYK323”, “BYK330” manufactured by Big Chemie, and the like.
Two or more surfactants may be combined.

-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.
The colored curable composition of the present invention can contain 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. .

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 filter having a pore size of 0.01 μm to 3.0 μm, more preferably a pore size of 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 (LCD) or a solid-state imaging device (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 of the present invention described above is applied onto a support by a coating method such as spin coating, cast coating, roll coating, and the like. A composition layer is formed, and then pre-curing (pre-baking) is performed as necessary, and the colored curable composition is dried (application step).

  Examples of the support used in the method for producing a color filter of the present invention include alkali-free glass, soda glass, borosilicate glass (Pyrex (registered trademark) glass), quartz glass, and quartz glass used for liquid crystal display elements and the like. Examples include a substrate to which a transparent conductive film is attached and a photoelectric conversion element substrate used for a solid-state imaging element such as a CCD or CMOS. 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, for example, even when the colored curable composition adheres to the nozzle of the coating apparatus discharge section, the piping section of the coating apparatus, the inside of the coating apparatus, etc., a known cleaning liquid is used. Can be easily washed away. 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.

Subsequently, in the method for producing a color filter of the present invention, the colored curable composition layer formed on the support is exposed through a mask (exposure step).
As light or radiation applicable to this exposure, 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 a nitrogen gas in the chamber in order to suppress oxidation fading of the colorant 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 developing solution dissolves the uncured portion (non-exposed portion) of the colored curable composition layer and does not dissolve the cured portion (exposed portion), a combination of various organic solvents, sodium hydroxide, hydroxide Potassium, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8- An aqueous solution of an organic or inorganic alkaline compound such as diazabicyclo- [5,4,0] -7-undecene can be used.
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). By irradiating the developed pattern (colored curable composition) with UV light for a predetermined time between the development process in the pattern formation step and the heat treatment described later, the color shifts when heated later. Can be effectively prevented, 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 with an irradiation light amount [mJ / cm 2] that is 10 times or more of the exposure amount during 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 device, a solid-state imaging device 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 or CMOS device 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 a CCD image sensor (solid-state imaging device) is provided on a support, and the color filter of the present invention is provided on the transfer electrode. The microlenses are stacked.

  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 device, organic EL display device>
The color filter of the present invention is used for a color filter for a liquid crystal display device and an organic EL display device. The liquid crystal display device and the organic EL display device provided with the color filter of the present invention can display a high-quality image with 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)”. There are no particular limitations on the liquid crystal display device and the organic EL display device to which the present invention can be applied. For example, the liquid crystal display device and the organic EL display device of various systems described in the “next-generation liquid crystal display technology” described above. Applicable.

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. Since the color filter of the present invention uses a dye multimer excellent in hue, it has excellent hue such as color purity, so that it provides a COA type liquid crystal display device with high resolution and excellent long-term durability. it can. 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 device 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 compensation 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 device 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. Have been described.

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

  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.

[Example 1-1]
(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 (hereinafter referred to as PGMEA) 5.20 parts Cyclohexanone (hereinafter referred to as CyH) 52.60 parts Binder 30.50 parts (benzyl methacrylate / methacrylic acid / methacrylic acid-2) -Hydroxyethyl 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: 4-Benzoxolane-2,6-bis (trichloromethyl) -s-triazine (manufactured by Midori Chemical Co., Ltd. TAZ-107) 0.58 parts

(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 (average particle size 55 nm)), pigment dispersant BYK-161 (manufactured by BYK) 5.9 parts, and PGMEA 82.3 parts were mixed with a bead mill (zirconia beads 0. 3 mm diameter), and mixed and dispersed 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 obtain a pigment dispersion (CI Pigment Blue 15: 6 dispersion). With respect to the obtained pigment dispersion, the average primary 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 each component was mixed and the colored curable composition was obtained.
Solvent: 1.133 parts of CyH Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (20% CyH solution) 1.009 parts (molar ratio = 70: 30, weight average molecular weight 30000)
・ Polymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) 0.225 part ・ Surfactant: Solsperse 20000 (1% cyclohexane solution, manufactured by Zeneca) 0.125 part ・ Start of oxime photopolymerization Agent (compound having the following structure) 0.087 parts · Dye multimer (Exemplary Compound S-1) 0.183 parts · Pigment Blue 15: 6 dispersion 2.418 parts (solid content concentration 13.57%, pigment concentration 11) .80%)
Surfactant: 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
-Criteria-
A: ΔE ^* ab value <3
○: 3 ≦ ΔE ^* ab value <5
Δ: 5 ≦ ΔE ^* ab value ≦ 15
×: ΔE ^* ab value> 15

[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.
-Criteria-
○: Dye remaining rate> 90%
Δ: 70% ≦ dye residual rate ≦ 90%
X: Dye residual ratio <70%

[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.
-Criteria-
A: ΔE ^* ab value <3
○: 3 ≦ ΔE ^* ab value <5
Δ: 5 ≦ ΔE ^* ab value ≦ 15
×: ΔE ^* ab value> 15

[Examples 1-2 to 1-17, Comparative Examples 1-1 to 1-2]
In the preparation of the colored curable composition of Example 1-1 (3), the same procedure as in Example 1-1 was carried out except that the exemplified compound S-1 was changed to the colorant described in Table 2 below (however, with equal mass). Then, a pattern was formed, and the same evaluation was performed. The evaluation results are shown in Table 2. The structures of Comparative Dye 1 and Comparative Dye 2 (CI Acid Red 87) in Table 2 are shown below.

[Examples 2-1 to 2-17, Comparative examples 2-1 to 2-2]
Color filters were prepared by the following procedures using the colored curable compositions used in Examples 1-1 to 1-17 and Comparative Examples 1-1 to 1-2, and Examples 2-1 to 2-17 were produced. And color transfer evaluation was implemented as Comparative Examples 2-1 to 2-2. The evaluation results are shown in Table 3 below.

-Fabrication of single color filter-
Using the colored curable compositions used in Examples 1-1 to 1-17 and Comparative Examples 1-1 to 1-2 on the glass substrate with an undercoat layer (2) prepared in Example 1-1, respectively. The film 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. With respect to this colored film, 200 [mJ / m] is obtained by an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.) through a mask pattern in which 7.0 μm square pixels are arranged in a 4 mm × 3 mm region on the substrate. exposure of cm ^2], 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 was calculated with respect to the absorbance of the colored pattern measured before heating, and used as an index for evaluating the color transfer.
-Criteria-
Color transfer to adjacent pixels (%)
A: Color transfer to adjacent pixels <1%
○: 1% <color transfer to adjacent pixels ≦ 10%
Δ: 10% ≦ color transfer to adjacent pixel ≦ 30%
×: Color transfer to adjacent pixels> 30%

  As shown in Table 2 and Table 3, Examples 1-1 to 1-17 using the dye multimer of the present invention all exhibited excellent heat resistance, solvent resistance, and light resistance. Moreover, it turns out that all of Examples 2-1 to 2-17 using the dye multimer of the present invention are those in which the color transfer to the adjacent pattern is suppressed.

In addition, as for the colored curable composition which changed the photoinitiator in Example 1-1 into the compounds OXE-01 and OXE-02 having the following structures, the same results as in Example 1-1 were obtained. It was found that a colored curable composition using an oxime-based initiator has good heat resistance, solvent resistance, and light resistance.
Both OXE-01 and OXE-02 are commercially available initiators from BASF.

Claims (10)

(A) a dye multimer comprising a xanthene skeleton as a partial structure of the dye moiety and having a weight average molecular weight in the range of 5000 to 30000, (b) a polymerizable compound, (c) a photopolymerization initiator, and (d ) contain an organic solvent, wherein the xanthene skeleton, dye skeleton der from xanthene compound represented by the following general formula (M) is, the (a) dye polymer is represented by the following general formula (a), the general formula (B) and the general formula (C) comprise or consists of at least one of structural units represented by, or the general formula (D) dye polymer der represented by Ru colored curable composition.

[In General Formula (M), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or a monovalent substituent; R ⁵ each independently represents a monovalent substituent; Represents an integer of 0 to 5. ]

[In General Formula (A), X ¹ represents a linking group formed by polymerization, L ¹ represents a single bond or a divalent linking group, and Dye represents an arbitrary hydrogen atom from the general formula (M). Represents the pigment residue after removal. ]

[In General Formula (B), X ² represents a linking group formed by polymerization, L ² represents a single bond or a divalent linking group, A represents a * —COO ^— group, and Dye represents the above general formula. It is a dye skeleton represented by (M) and represents a dye cation structure capable of ionic bonding with A. ]

[In General Formula (C), L ³ represents a single bond or a divalent linking group, and when a plurality of L ³ are present , the structures of L ³ may be the same or different. Dye represents a dye residue obtained by removing two arbitrary hydrogen atoms from the general formula (M). n3 represents an integer of 1 to 4. ]

[In General Formula (D), L ⁴ represents an n4-valent linking group, n4 represents an integer of 2 to 100, and a plurality of Dye each independently represents one arbitrary hydrogen atom from General Formula (M). Represents the removed pigment residue. ]   The colored curable composition according to claim 1, wherein the photopolymerization initiator (c) is an oxime compound. (A) a dye multimer comprising a xanthene skeleton as a partial structure of the dye moiety and having a weight average molecular weight in the range of 5000 to 30000, (b) a polymerizable compound, (c) a photopolymerization initiator, and (d ) contain an organic solvent, wherein (c) a photopolymerization initiator Ri oxime compounds der, wherein (a) the dye polymer is represented by the following general formula (a), formula (B) and the general formula (C) in comprise happens at least one of structural units represented by or the general formula (D) dye polymer der represented by Ru colored curable composition.

[In General Formula (M), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or a monovalent substituent; R ⁵ each independently represents a monovalent substituent; Represents an integer of 0 to 5. ]

[In General Formula (A), X ¹ represents a linking group formed by polymerization, L ¹ represents a single bond or a divalent linking group, and Dye represents an arbitrary hydrogen atom from the general formula (M). Represents the pigment residue after removal. ]

[In General Formula (B), X ² represents a linking group formed by polymerization, L ² represents a single bond or a divalent linking group, A represents a * —COO ^— group, and Dye represents the above general formula. It is a dye skeleton represented by (M) and represents a dye cation structure capable of ionic bonding with A. ]

[In General Formula (C), L ³ represents a single bond or a divalent linking group, and when a plurality of L ³ are present , the structures of L ³ may be the same or different. Dye represents a dye residue obtained by removing two arbitrary hydrogen atoms from the general formula (M). n3 represents an integer of 1 to 4. ]

[In General Formula (D), L ⁴ represents an n4-valent linking group, n4 represents an integer of 2 to 100, and a plurality of Dye each independently represents one arbitrary hydrogen atom from General Formula (M). Represents the removed pigment residue. ]   The colored curable composition according to any one of claims 1 to 3, wherein the (a) dye multimer further has an alkali-soluble group. Wherein (a) a dye multimer, before following general formula (A), or comprising at least one of structural units represented by the Contact and the general formula (C), and or, is represented by the general formula (D) The colored curable composition according to any one of claims 1 to 4, which is a dye multimer.   The colored curable composition according to any one of claims 1 to 5, further comprising a phthalocyanine pigment.   The color filter which uses the colored curable composition of any one of Claims 1-6.   The manufacturing method of the color filter which apply | coats the coloring curable composition of any one of Claims 1-6 on a board | substrate, exposes it through a mask, and develops and forms a pattern image.   A solid-state imaging device comprising the color filter according to claim 7.   A liquid crystal display device comprising the color filter according to claim 7.