TWI632202B - Colored composition, cured film, method for manufacturing color filter, color filter, solid-state image sensing device, and image display device - Google Patents

Abstract

The present invention provides a colored composition which does not cause spectroscopic fluctuation during development, and which can obtain a cured film having excellent heat resistance, a cured film using the colored composition, a method for producing a color filter, a color filter, Solid-state imaging device and image display device. The coloring composition includes a dye multimer including a repeating unit represented by the following formula, and a curable compound; R ¹ and R ³ are each independently an aliphatic hydrocarbon group, and R ² and R ⁴ are each independently The aromatic hydrocarbon group, R ⁵ to R ¹⁰ each independently represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and R ¹¹ to R ¹⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a carbonyl group. Nitro, amine, alkylamino, arylamine, or sulfonyl.

Description

Coloring composition, cured film, method for producing color filter, color Color filter, solid-state imaging element, and image display device

The present invention relates to a coloring composition, a cured film, a method of producing a color filter, a color filter, a solid-state image sensor, and an image display device.

Previously, a color filter was produced by using a coloring composition containing a dye compound, a curable compound, and other components as needed, and forming a colored pattern by photolithography or dry etching. Such a coloring composition can be used to form a solid color imaging element or a color filter layer of an image display device.

Here, the xanthene compound is described, for example, in Patent Document 1 and Patent Document 2. Further, Patent Document 3 discloses a coloring curable composition containing a dye multimer, which contains a dye moiety derived from a xanthene compound as a partial structure.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] International Publication WO2013/089197

[Patent Document 2] International Publication WO2013/146218

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2012-32754

Here, the dye multimer has an advantage that the pigment concentration in the colored composition can be increased and the pigment is formed when the cured film is formed, as compared with the low molecular compound described in Patent Document 1 and Patent Document 2. The compound is not easily detached. However, as a result of investigations by the inventors of the present invention, it has been found that a xanthene dye compound having a specific structure tends to cause spectroscopic fluctuation during development or poor light resistance. The present invention has an object of solving the above problems, and an object of the invention is to provide a colored composition which does not cause spectroscopic fluctuation during development, and which can obtain a cured film having excellent light resistance, and a cured film using the colored composition. A method of manufacturing a color filter, a color filter, a solid-state image sensor, and an image display device.

The inventors of the present invention have conducted intensive studies based on the above-mentioned conditions, and as a result, it has been found that a predetermined xanthene dye structure is used in a dye multimer having a repeating unit having a xanthene dye structure, whereby the above problem can be solved. Specifically, the above problem is preferably solved by means <2> to <16> by the following means <1>.

<1> A coloring composition comprising: a dye multimer comprising a repeating unit represented by the formula (A1-1) and/or a repeating unit represented by the formula (A1-2); and hardenability Compound; general formula (A1-1)

In the general formula (A1-1), one of R ¹ to R ¹⁵ is a main chain structure represented by the following general formula (A1-1-1), and at least one of R ¹ to R ¹⁵ is an anion. a substituent or an anion group-containing substituent, R ¹ and R ³ are each independently an aliphatic hydrocarbon group, R ² and R ⁴ are each independently an aromatic hydrocarbon group, and R ⁵ to R ¹⁰ each independently represent a hydrogen atom or a halogen. An atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and R ¹¹ to R ¹⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carbonyl group, a nitro group, an amine group, an alkylamino group, an arylamino group, or Sulfhydryl group; general formula (A1-1-1) [Chemical 2]

In the formula (A1-1-1), L ¹¹ represents a single bond or a divalent linking group, and R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group; and the formula (A1-2)

In the general formula (A1-2), one of R ¹ to R ¹⁵ includes a main chain structure represented by the above formula (A1-1-1), and R ¹ and R ³ are each independently an aliphatic hydrocarbon group. R ² and R ⁴ are each independently an aromatic hydrocarbon group, and R ⁵ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and R ¹¹ to R ¹⁵ each independently represent a hydrogen atom or a halogen. Atom, alkyl, aryl, carbonyl, nitro, amine, alkylamino, arylamine, or sulfonyl; X represents an anion forming an anti-salt with a cation of xanthene.

<2> The colored composition according to <1>, wherein the yin in the formula (A1-1) The ionic group includes a carboxylate anion, a sulfonate anion, an anion represented by the formula (A1-1-2) or an anion represented by the formula (A1-1-3), or a formula (A1-2) X in the group is a carboxylate anion, a sulfonate anion, a quinone imine anion, a methide anion, and a borate anion;

General formula (A1-1-2)

In the formula (A1-1-2), L ¹ represents a single bond or a divalent linking group, L ² represents -SO ₂ - or -CO-, and G represents a carbon atom or a nitrogen atom, and when G is a carbon atom, N1 represents 2, when G is a nitrogen atom, n1 represents 1, R ⁶ represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom, and when n1 is 2, two R ^{6 's} may be the same or different;

General formula (A1-1-3)

In the formula (A1-1-3), L ¹ represents a single bond or a divalent linking group, L ² represents -SO ₂ - or -CO-, L ³ represents a divalent linking group, and G represents a carbon atom or nitrogen. An atom, when G is a carbon atom, n2 represents 1, and when G is a nitrogen atom, n2 represents 0, and R ^7A and R ^7B each independently represent an alkylene group containing a fluorine atom or an extended aryl group containing a fluorine atom, R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group.

<3> The colored composition according to <1> or <2>, wherein the dye multimer further has an alkali-soluble group.

The colored composition according to any one of <1> to <3> wherein the dye multimer further has a polymerizable group.

The colored composition according to any one of <1> to <4> wherein the curable compound is a polymerizable compound and further contains a photopolymerization initiator.

<6> The coloring composition according to any one of <1> to <5> which further comprises a pigment having an indigo skeleton.

<7> The <1> to <6> The coloring composition according to any one of the general formula wherein R R to (A1-1) and ¹¹ ~ R 1 th formula (A1-2) ^{15 11} One of ~R ¹⁵ is a main chain structure represented by the general formula (A1-1-1).

<8> The <1> to <7> The coloring composition according to any one of wherein R and R of the general formula R ² (A1-1) is ^4, and the formula (A1-2) is ² and R ⁴ is a phenyl group.

<9> The <1> to the coloring composition of <8> to any preceding claim, wherein R and R of the general formula R ² (A1-1) is ^4, and the formula (A1-2) is ² and R At least one of ⁴ is represented by the following general formula (A1-1-2);

In the formula (A1-1-2), R ²³ to R ²⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group having 1 to 12 carbon atoms, a carbonyl group, a carbonyl guanamine group, or a sulfonate. a mercapto group, a sulfonylamino group, a nitro group, an amine group, an aminocarbonyl group, an aminosulfonyl group, a sulfonyl quinone imine group or a carbonyl fluorenylene group, and R ²² and R ²⁶ each independently represent a carbon The number is 1 to 5 alkyl groups.

<10> The <1> to <9> The coloring composition according to any one of the general formula wherein R R (A1-1) ¹ and R ^3, and the formula (A1-2) is ¹ and R ^{3 is} independently an alkyl group having 1 to 5 carbon atoms.

<11> The coloring composition according to any one of <1> to <10> which is used for forming a coloring layer of a color filter.

<12> A cured film obtained by curing the colored composition according to any one of <1> to <11>.

<13> A method of producing a color filter, comprising: a step of forming a colored composition layer on a support using the colored composition according to any one of <1> to <11>; a step of exposing the layer to a pattern; and developing the unexposed portion of the exposed colored composition layer.

<14> A color filter comprising the cured film according to <12>, or It is obtained by the method of producing a color filter as described in <13>.

<15> A solid-state image pickup element comprising the color filter according to <14>.

<16> An image display device comprising the color filter of <14>.

According to the present invention, it is possible to provide a colored composition which does not cause spectroscopic fluctuation during development, and which can obtain a cured film having excellent light resistance, a cured film using the colored composition, a method for producing a color filter, and a color filter. Light sheet, solid-state imaging element, and image display device.

Hereinafter, the coloring composition, the cured film, the pattern forming method, the method of producing the color filter, the color filter, the solid-state image sensor, and the image display device of the present invention will be described in detail.

The description of the constituent elements of the present invention described below may be carried out based on representative embodiments of the present invention, but the present invention is not limited to such an embodiment.

In the expression of the group (atomic group) in the present specification, the substituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and also a group having a substituent (atomic group). For example, the so-called "alkyl" not only contains no The alkyl group having an substituent (unsubstituted alkyl group) also includes an alkyl group having a substituent (substituted alkyl group).

In addition, the term "radiation" in the present specification means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (Extreme Ultraviolet (EUV) light), an X-ray, an electron beam, or the like. Further, in the present invention, light means actinic rays or radiation. The "exposure" in the present specification includes exposure using a mercury lamp, a far-ultraviolet light represented by a pseudo-molecular laser, X-rays, EUV light, or the like, and is performed by a particle beam such as an electron beam or an ion beam, unless otherwise specified. The depiction is also included in the exposure.

In the present specification, the numerical range expressed by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit.

In the present specification, the total solid content refers to the total mass of the components after the solvent is removed from the total composition of the coloring composition.

The solid content concentration in the present specification means the concentration of a solid component at 25 °C.

In the present specification, "(meth)acrylate" means either or both of acrylate and methacrylate, and "(meth)acrylic acid" means both of acrylic acid and methacrylic acid, or Either "(meth)acryloyl group" means either or both of an acryloyl group and a methacryloyl group.

In addition, in this specification, "single quantity" and "monomer" have the same meaning. The monomer in the present specification is different from the oligomer and the polymer, and means a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. So-called The polymerizable functional group means a group which participates in a polymerization reaction.

In the present specification, the term "step" means not only an independent step, but even if it cannot be clearly distinguished from other steps, it is included in the term as long as the intended effect of the step is achieved.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a coloring composition excellent in color characteristics.

In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene-converted values obtained by gel permeation chromatography (GPC). In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, by using HLC-8220 (manufactured by Tosoh Co., Ltd.) and TSKgel Super AWM- H (manufactured by Tosoh Co., Ltd., 6.0 mm inner diameter (Inner Diameter, ID) × 15.0 cm) was used as a column, and 10 mmol/L of lithium bromide N-methylpyrrolidine (NMP) solution was used. As a solution.

In the present specification, a methyl group is sometimes represented by Me, an ethyl group is represented by Et, a propyl group is represented by Pr, a butyl group is represented by Bu, and a phenyl group is represented by PH or Ph.

The colored composition of the present invention (hereinafter sometimes simply referred to as "the composition of the present invention") includes a dye multimer, and contains a repeating unit represented by the formula (A1-1) and/or a formula (A1). -2) a repeating unit represented; and a curable compound.

General formula (A1-1) [Chemical 7]

In the general formula (A1-1), one of R ¹ to R ¹⁵ is a main chain structure represented by the following general formula (A1-1-1), and at least one of R ¹ to R ¹⁵ is an anion. a substituent or an anion group-containing substituent, R ¹ and R ³ are each independently an aliphatic hydrocarbon group, R ² and R ⁴ are each independently an aromatic hydrocarbon group, and R ⁵ to R ¹⁰ each independently represent a hydrogen atom or a halogen. An atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and R ¹¹ to R ¹⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carbonyl group, a nitro group, an amine group, an alkylamino group, an arylamino group, or Sulfonyl

General formula (A1-1-1)

In the formula (A1-1-1), L ¹¹ represents a single bond or a divalent linking group, and R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group; and the formula (A1-2)

In the general formula (A1-2), one of R ¹ to R ¹⁵ includes a main chain structure represented by the above formula (A1-1-1), and R ¹ and R ³ are each independently an aliphatic hydrocarbon group. R ² and R ⁴ are each independently an aromatic hydrocarbon group, and R ⁵ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and R ¹¹ to R ¹⁵ each independently represent a hydrogen atom or a halogen. An atom, an alkyl group, an aryl group, a carbonyl group, a nitro group, an amine group, an alkylamino group, an arylamino group, or a sulfonyl group; and X represents an anion which forms a relative salt with a cation of xanthene.

According to this configuration, it is possible to obtain a colored composition of a cured film which does not cause spectroscopic fluctuation during alkali development and which is excellent in heat resistance.

Although the mechanism is inferred, it can be considered as follows.

There are many ways in which the light fading of dyes is known, but under the light resistance test conditions, the chemical species are often exposed to light. There are the following ways: Under such conditions, an electrophilic species typified by singlet oxygen is generated, which reacts with the dye to thereby fade. Regarding the reactivity with electrophilic species, the oxidation potential of the dye dominates, and the higher the oxidation potential, the easier it is to take away electrons and fade. However, in dyes There is an electron distribution, and a portion having a relatively high potential such as a Highest Occupied Molecular Orbital (HOMO) is a portion that easily reacts with an electrophilic species, but if there is a factor such as a large volume which is three-dimensionally large and reduces reactivity, Sometimes it is not easy to produce fading.

In the case of the xanthene structure used in the present invention, the nitrogen atom is considered to be a portion which easily reacts with the electrophilic species. Here, when the substituent of the nitrogen atom is an electron-donating group such as an alkyl group, the oxidation potential is further increased, and thus the color is easily discolored. When the electron-donating group such as a phenyl group is used, the oxidation potential is lowered and fading is difficult. In the present invention, it is estimated that the light resistance can be improved by setting the group bonded to the nitrogen atom of the xanthene structure to an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

Further, the coloring composition of the present invention is usually subjected to an alkali development treatment in order to remove unexposed portions. At this time, a part of the alkaline developing solution also penetrates into the pattern of the exposed portion, so that the dye is exposed to alkaline conditions. When a proton having a high acidity is present in the xanthene structure, the spectroscopic changes under alkaline conditions, and the original spectroscopic characteristics are impaired. In the case of the xanthene structure, it is considered that protons on the nitrogen atom are easily affected by pH, and if the acidity is high, there is a case where spectroscopic fluctuation occurs during alkali development.

In the present invention, it is estimated that the group bonded to the nitrogen atom of the xanthene structure is an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the spectral variation during alkali development can be suppressed.

In the present invention, the dye multimer comprises one or both of a repeating unit represented by the formula (A1-1) and a repeating unit represented by the formula (A1-2), preferably at least Contains the formula (A1-1).

<Pigment polymer>

<<Repeating unit represented by the general formula (A1-1)>>

The repeating unit represented by the formula (A1-1) in the present invention is as follows.

General formula (A1-1)

In the general formula (A1-1), one of R ¹ to R ¹⁵ contains a main chain structure represented by the above formula (A1-1-1), and R ¹ and R ³ are each independently an aliphatic hydrocarbon group. R ² and R ⁴ are each independently an aromatic hydrocarbon group, and R ⁵ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and R ¹¹ to R ¹⁵ each independently represent a hydrogen atom or a halogen. Atom, alkyl, aryl, carbonyl, nitro, amine, alkylamino, arylamine, or sulfonyl.

In the formula (A1-1), R ¹ and R ³ are each independently an aliphatic hydrocarbon group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and further more. It is preferably a methyl group, an ethyl group, a propyl group or a butyl group, and particularly preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group or an n-butyl group. R ¹ and R ³ may be different, but are preferably the same. The alkyl group as R ¹ and R ³ may have a substituent, but preferably has no substituent.

In the formula (A1-1), R ² and R ⁴ each independently represent an aromatic hydrocarbon group, and more preferably a phenyl group. The aromatic hydrocarbon group of R ² and R ⁴ may have a substituent and is selected from the group of substituents described later, more preferably an alkyl group having 1 to 5 carbon atoms, and still more preferably a methyl group, an ethyl group or a C group. Base, butyl, particularly preferably methyl, ethyl, n-propyl, n-butyl.

More preferably, at least one of R ² and R ⁴ of the formula (A1-1) and R ² and R ⁴ of the formula (A1-2) is represented by the following formula (A1-1-2).

In the formula (A1-1-2), R ²³ to R ²⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group having 1 to 12 carbon atoms, a carbonyl group, a carbonyl guanamine group, or a sulfonate. a mercapto group, a sulfonylamino group, a nitro group, an amine group, an aminocarbonyl group, an aminosulfonyl group, a sulfonyl quinone imine group or a carbonyl fluorenylene group, and R ²² and R ²⁶ each independently represent a carbon The number is 1 to 5 alkyl groups.

In the formula (A1-1-2), R ²³ to R ^{25 are} preferably a hydrogen atom or a halogen atom, and more preferably a hydrogen atom.

In the formula (A1-1-2), R ²² and R ²⁶ are each independently an alkyl group having 1 to 5 carbon atoms (more preferably an alkyl group having 3 to 5 carbon atoms). The alkyl group having 1 to 5 carbon atoms is more preferably a methyl group, an ethyl group, a propyl group or a butyl group, and more preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group or a n-butyl group, and particularly preferably different. Propyl.

In the formula (A1-1), R ⁵ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and preferably a hydrogen atom. The halogen atom may, for example, be a fluorine atom, a chlorine atom or a bromine atom, and is preferably a fluorine atom or a chlorine atom. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms. Further, examples of the aliphatic hydrocarbon group include an alkyl group and an alkenyl group, and an alkyl group is preferred. The aromatic hydrocarbon group is preferably an aryl group, more preferably a phenyl group.

In the formula (A1-1), R ¹¹ to R ¹⁴ are each independently a hydrogen atom or a halogen atom, and more preferably a hydrogen atom.

In the formula (A1-1), R ^{15 is} preferably a carbonyl group or a sulfonyl group.

Substituent group A: Examples of the substituent which the dye may have include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, and an alkoxy group. , aryloxy, decyloxy, heterocyclooxy, decyloxy, amine methoxycarbonyl, amine (including alkylamino, anilino), mercaptoamine, aminocarbonylamino, alkane Oxycarbonylamino, aryloxycarbonylamino, aminesulfonylamino, alkylsulfonylamino or arylsulfonylamino, fluorenyl, alkylthio, arylthio, heterocyclic thio Aminesulfonyl, sulfo, alkylsulfinyl or arylsulfinyl, alkylsulfonyl or arylsulfonyl, fluorenyl, aryloxycarbonyl, alkoxycarbonyl, amine Mercapto, arylazo or heterocyclic azo, quinone imine, phosphino, phosphinyl, phosphinyloxy, phosphinylamino, decyl and the like. The details will be described below.

A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine) Atom), a straight or branched alkyl group (linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, Isopropyl, tert-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), cycloalkyl (preferably substituted with a carbon number of 3 to 30 or Examples of the unsubstituted cycloalkyl group include a cyclohexyl group, a cyclopentyl group, and a polycycloalkyl group, and examples thereof include a bicycloalkyl group (preferably a substituted or unsubstituted dicycloalkyl group having a carbon number of 5 to 30). a polycyclic structure group such as bicyclo[1,2,2]heptan-2-yl, bicyclo[2,2,2]oct-3-yl) or tricycloalkyl. Preferably monocyclic a cycloalkyl group, a bicycloalkyl group, particularly preferably a monocyclic cycloalkyl group),

a linear or branched alkenyl group (linear or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as a vinyl group, an allyl group, an isoprenyl group, A geranyl group, an oleyl group, a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having a carbon number of 3 to 30, for example, 2-cyclopenten-1-yl group, 2-ring ring Hexen-1-yl, polycycloalkenyl, such as bicycloalkenyl (preferably substituted or unsubstituted bicycloalkenyl having 5 to 30 carbon atoms, such as bicyclo[2,2,1]hept-2 -alken-1-yl, bicyclo[2,2,2]oct-2-en-4-yl) or tricycloalkenyl, particularly preferably monocyclic cycloalkenyl), alkynyl (preferably carbon number) a substituted or unsubstituted alkynyl group of 2 to 30, such as an ethynyl group, a propargyl group, a trimethyldecyl ethynyl group,

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

Alkoxy (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy (preferably substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 2, 4-di-p-pentylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecylaminophenoxy), decyloxy (preferably a decyloxy group having 3 to 20 carbon atoms, such as trimethylnonyloxy group, butylene dimethyl decyloxy group, a heterocyclic oxy group (preferably a substituted or unsubstituted carbon number of 2 to 30) The substituted heterocyclic oxy group preferably has a heterocyclic moiety as described in the heterocyclic group, for example, 1-phenyltetrazole-5-oxyl, 2-tetrahydropyranyloxy),

a decyloxy group (preferably a methyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having a carbon number of 6 to 30) a group such as methyl methoxy, ethoxycarbonyl, trimethyl ethoxy methoxy, stearyl oxime, benzhydryloxy, p-methoxyphenylcarbonyloxy), amine methyl methoxy ( Preferred is a substituted or unsubstituted amine methyl methoxy group having a carbon number of 1 to 30, such as N,N-dimethylamine methyl methoxy group, N,N-diethylamine methyl methoxy group, Morpholinylcarbonyloxy, N,N-di-n-octylaminocarbonyl, N-n-octylaminemethyloxy), alkoxycarbonyloxy (preferably having a carbon number of 2 to 30) Substituted or unsubstituted alkoxycarbonyloxy group, such as methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxy a carbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having a carbon number of 7 to 30, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, aligned Hexadecyloxyphenoxycarbonyloxy), An amine group (preferably an amine group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a carbon number of 0 to 30 heterocyclic amino groups, such as amine, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazine- a 2-ylamino group, a mercaptoamine group (preferably a mercaptoamine group, a substituted or unsubstituted alkylcarbonylamino group having a carbon number of 1 to 30, and a substituted carbon number of 6 to 30) Or unsubstituted arylcarbonylamino group, such as formazanylamine, ethionylamino, trimethylethenylamine, laurylamine, benzhydrylamine, 3,4, 5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having a carbon number of 1 to 30, such as an amine formamidine Base, N,N-dimethylaminocarbonylamino group, N,N-diethylaminocarbonylamino group, morpholinylcarbonylamino group), alkoxycarbonylamino group (preferably having a carbon number of 2 to 30) Substituted or unsubstituted alkoxycarbonylamino group, such as methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamine Base, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group, An aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having a carbon number of 7 to 30, such as a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, and a An octyloxyphenoxycarbonylamino group, an aminesulfonylamino group (preferably a substituted or unsubstituted sulfonylamino group having a carbon number of 0 to 30, such as an aminesulfonylamino group, N,N-dimethylaminosulfonylamino, N-n-octylaminosulfonylamino), alkyl sulfonate a mercaptoamino group or an arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having a carbon number of 1 to 30, substituted or not having a carbon number of 6 to 30) Substituted arylsulfonylamino group, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino , p-methylphenylsulfonylamino), mercapto, An alkylthio group (preferably a substituted or unsubstituted alkylthio group having a carbon number of 1 to 30, such as a methylthio group, an ethylthio group, an n-hexadecylthio group), an arylthio group (preferably a carbon) a substituted or unsubstituted arylthio group of 6 to 30, such as a phenylthio group, a p-chlorophenylthio group, a m-methoxyphenylthio group, or a heterocyclic thio group (preferably having a carbon number of 2~) a substituted or unsubstituted heterocyclic thio group of 30, preferably a heterocyclic moiety as described in the heterocyclic group, for example, 2-benzothiazolylthio, 1-phenyltetrazole-5 -ylthio), aminsulfonyl (preferably substituted or unsubstituted sulfonyl group having a carbon number of 0 to 30, such as N-ethylamine sulfonyl, N-(3-12 Alkoxypropyl)amine sulfonyl, N,N-dimethylamine sulfonyl, N-acetamimidoxime, N-benzamidesulfonyl, N-(N'- Phenylamine, mercapto) sulfonyl, sulfo, An alkylsulfinyl group or an arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having a carbon number of 1 to 30, a substituted or unsubstituted carbon number of 6 to 30) Substituted arylsulfinylene, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkylsulfonyl or aryl a sulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as a methyl group Sulfosyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), mercapto (preferably formazan, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as an ethylidene group, a trimethylethenyl group, or a 2- a chloroethyl group, a stearyl group, a benzhydryl group, a p-octyloxyphenylcarbonyl group, an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxy group having a carbon number of 7 to 30) a carbonyl group such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p-tert-butylphenoxycarbonyl, Alkoxycarbonyl (preferably substituted or unsubstituted alkoxycarbonyl having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxy) Alkylcarbonyl), an amine carbenyl group (preferably a substituted or unsubstituted amine carbenyl group having a carbon number of 1 to 30, such as an amine carbenyl group, an N-methylamine carbenyl group, N,N- Dimethylamine methyl sulfhydryl, N,N-di-n-octylamine carbhydryl, N-(methylsulfonyl)amine carbaryl, arylazo or heterocyclic azo a substituted or unsubstituted arylazo group having a carbon number of 6 to 30, a substituted or unsubstituted heterocyclic azo group having a carbon number of 3 to 30 (the heterocyclic ring is preferably as described above) a heterocyclic moiety described in the heterocyclic group), for example, phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo a quinone imine group (preferably a substituted or unsubstituted quinone group having a carbon number of 2 to 30, such as N-succinimide group, N-phthalimido group), phosphine a base (preferably a substituted or unsubstituted phosphino group having a carbon number of 2 to 30, such as a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group) or a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having a carbon number of 2 to 30, such as a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group), a phosphinyloxy group (preferably substituted or unsubstituted having a carbon number of 2 to 30) a phosphinyloxy group, such as a diphenoxyphosphinyloxy group, a dioctyloxyphosphinyloxy group, a phosphinylamino group (preferably a substituted or unsubstituted carbon number of 2 to 30) Substituted phosphinylamino group, such as dimethoxyphosphinylamino group, dimethylaminophosphinylamino group, decyl group (preferably substituted or unsubstituted having a carbon number of 3 to 30) A decyl group, such as a trimethyl decyl group, a tert-butyl dimethyl decyl group, a phenyl dimethyl decyl group.

Among the functional groups, a functional group having a hydrogen atom may be substituted for a portion of a hydrogen atom in the functional group by any of the functional groups. Examples of the functional group which can be introduced as a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, an arylsulfonylaminocarbonyl group, and specifically In other words, a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an ethyl fluorenylsulfonyl group, and a benzhydrylaminosulfonyl group can be mentioned.

<<Main chain structure represented by the general formula (A1-1-1)>>

The dye multimer used in the present invention is preferably a compound of the formula (A1-1), and one of R ¹ to R ¹⁵ contains a main chain structure represented by the formula (A1-1-1). One of R ¹¹ to R ¹⁵ of the formula (A1-1) is a main chain structure represented by the formula (A1-1-1), or R ¹ , R ² , R of the formula (A1-1) At least one of ³ and R ⁴ contains a main chain structure represented by the general formula (A1-1-1), and more preferably one of R ¹¹ to R ¹⁵ of the general formula (A1-1) is a general formula ( The main chain structure represented by A1-1-1), and more preferably R ¹⁵ is a main chain structure represented by the formula (A1-1-1).

When one of R ¹ , R ² , R ³ and R ⁴ of the formula (A1-1) contains a main chain structure, it is preferred that R ² or R ⁴ is represented by the formula (A1-1-1). The main chain structure, more preferably one of R ²² to R ²⁶ of the formula (A1-1-2) is a main chain structure represented by the formula (A1-1-1), and more preferably R ^{22 .} It is a main chain structure represented by the general formula (A1-1-1).

General formula (A1-1-1)

In the formula (A1-1-1), L ¹¹ represents a single bond or a divalent linking group, and R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group.

L ¹¹ represents a single bond or a divalent linking group, and is preferably a divalent linking group. The divalent linking group represents a substituted or unsubstituted alkylene group having a carbon number of 1 to 30 (e.g., methylene, ethyl, methylene, propyl, butyl, etc.), carbon a substituted or unsubstituted extended aryl group of 6 to 30 (e.g., a phenylene group, a naphthyl group, etc.), a substituted or unsubstituted heterocyclic linkage group, -CH=CH-, -O-, -S-, -C(=O)-, -CO ₂ -, -NR-, -CONR-, -O ₂ C-, -SO-, -SO ₂ - and two or more of these are linked to form Linkage. Further, it is also preferable that L ¹¹ is a composition containing an anion.

L ^{11 is} preferably -CO ₂ - and a phenyl group, more preferably -CO ₂ -.

R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group, preferably a hydrogen atom or a methyl group.

In one molecule of the dye multimer, represented by the formula (A1-1-1) The main chain structure may be one type or two or more types.

The main chain structure which can be preferably used in the present invention is exemplified below, but the present invention is of course not limited to the main chain structures.

In particular, the linking group represented by the following (XX-1) to the following (XX-24) is more preferable, and the (meth)acrylic acid represented by the free (XX-1) and (XX-2) is more preferable. a styrene-based linking chain represented by (XX-10) to (XX-17), a vinyl chain represented by (XX-18), (XX-19), and (XX-24) The chain is selected, and the (meth)acrylic linkage chain represented by (XX-1) and (XX-2), and the styrene linkage represented by (XX-10) to (XX-17) are preferred. The chain is selected from the vinyl-based linking chain represented by (XX-24), and more preferably the (meth)acrylic linking chain represented by (XX-1) and (XX-2), and The styrene-based linking chain represented by XX-11).

In (XX-1) to (X X-24), it is shown that the portion indicated by * is connected to L ¹¹ . Me represents a methyl group. Further, R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group.

[Chemistry 13]

[Chemistry 14]

<<Anionic base>>

The general formula (A1-1) contains an anionic group. An anionic group is contained in accordance with the valence of the cation contained in the dye multimer.

In the general formula (A1-1), the anionic group is a group of any of R ¹ to R ¹⁵ or a substituent which is a substituent of any of R ¹ to R ¹⁵ , preferably R ¹¹ and R ^{15 .} Any one or a group contained as a substituent of any of R ¹¹ and R ¹⁵ .

Further, when the formula (A1-1) contains a structure represented by the formula (A1-1-2), it is also preferred that R ²² or R ²⁶ is an anionic group or an anionic group.

The anionic group contained in the dye multimer of the present invention may be one type or two or more types.

The anionic group in the formula (A1-1) preferably contains a carboxylate anion, a sulfonate anion, an anion represented by the formula (A1-1-2) or a formula (A1-1-3) Expressed anion.

General formula (A1-1-2)

In the formula (A1-1-2), L ¹ represents a single bond or a divalent linking group, L ² represents -SO ₂ - or -CO-, and G represents a carbon atom or a nitrogen atom, and when G is a carbon atom, n1 represents 2, when G is a nitrogen atom, n1 represents. 1, R ⁶ represents an alkyl group or an aryl group containing a fluorine atom containing fluorine atoms, when n1 is 2, two R ⁶ may be identical to each other, or different.

In the formula (A1-1-2), R ⁶ represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom.

The alkyl group having a fluorine atom preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably 1 to 3 carbon atoms. Further, the alkyl group containing a fluorine atom may be linear, branched or cyclic, and more preferably linear.

The aryl group having a fluorine atom preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, still more preferably 6 carbon atoms.

The alkyl group containing a fluorine atom or the aryl group containing a fluorine atom preferably has a fluorine atom content More than 50%, more preferably perfluoro group. The fluorine atom content is represented by the following.

Fluorine atom content = [(atom atom of fluorine atom) × (number of fluorine atoms) / (molecular weight of alkyl group containing fluorine atom or aryl group containing fluorine atom)] × 100

In the formula (A1-1-2), * represents a bonding site with R ¹ to R ¹⁵ or a substituent of the groups.

The example of the general formula (A1-1-2) is shown below, but the present invention is of course not limited to these examples.

General formula (A1-1-3)

In the formula (A1-1-3), L ¹ represents a single bond or a divalent linking group, L ² represents -SO ₂ - or -CO-, L ³ represents a divalent linking group, and G represents a carbon atom or nitrogen. An atom, when G is a carbon atom, n2 represents 1, and when G is a nitrogen atom, n2 represents 0, and R ^7A and R ^7B each independently represent an alkylene group containing a fluorine atom or an extended aryl group containing a fluorine atom, R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group.

In the formula (A1-1-3), L ¹ represents a single bond or a divalent linking group, and is preferably a single bond. Examples of the divalent linking group include an alkylene group having 1 to 6 carbon atoms, an extended aryl group having 6 to 12 carbon atoms, -O-, -S-, or a group containing a combination of these.

In the formula (A1-1-3), L ³ represents a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 6 carbon atoms, an extended aryl group having 6 to 18 carbon atoms, -O-, -CO-, -S-, -SO ₂ -, - NR ^A R ^B - or a group or the like containing the combination of these. The alkylene group having 1 to 6 carbon atoms may be linear, branched or cyclic. The exoaryl group having a carbon number of 6 to 18 may be a single ring or a polycyclic ring. In -NR ^A R ^B -, R ^A and R ^B each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ^A and R ^B may be bonded to each other to form a ring.

In the formula (A1-1-3), R ^7A and R ^7B each independently represent an alkylene group containing a fluorine atom or an extended aryl group containing a fluorine atom, and the alkyl group having a fluorine atom preferably has a carbon number of 1~. 6, more preferably 1 to 4, and even more preferably 1 to 3. Further, the alkyl group containing a fluorine atom may be linear, branched or cyclic, and more preferably linear.

The aryl group having a fluorine atom preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, still more preferably 6 carbon atoms.

The alkyl group containing a fluorine atom or the aryl group containing a fluorine atom preferably has a fluorine atom content More than 50%, more preferably perfluoro group.

In the formula (A1-1-3), R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group, preferably a hydrogen atom or a methyl group. When R ^X represents an alkoxymethyl group, the alkoxymethyl group preferably has 1 to 3 carbon atoms.

The example of the general formula (A1-1-3) is shown below, but the present invention is of course not limited to these examples. R ^X represents a hydrogen atom or a methyl group.

<<Repeating unit represented by the general formula (A1-2)>>

The repeating unit represented by the formula (A1-2) in the present invention is as follows.

General formula (A1-2)

In the general formula (A1-2), one of R ¹ to R ¹⁵ includes a main chain structure represented by the above formula (A1-1-1), and R ¹ and R ³ are each independently an aliphatic hydrocarbon group. R ² and R ⁴ are each independently an aromatic hydrocarbon group, and R ⁵ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and R ¹¹ to R ¹⁵ each independently represent a hydrogen atom or a halogen. An atom, an alkyl group, an aryl group, a carbonyl group, a nitro group, an amine group, an alkylamino group, an arylamino group, or a sulfonyl group; and X represents an anion which forms a relative salt with a cation of xanthene.

In the general formula (A1-2), R ¹ and R ³ are each independently an aliphatic hydrocarbon group, and R ² and R ⁴ are each independently an aromatic hydrocarbon group, and R ⁵ to R ¹⁰ each independently represent a hydrogen atom. , R R the same as in the case of a halogen atom, an aliphatic or aromatic hydrocarbon group of ¹ ~ R ¹⁵ in the meaning of general formula (A1-1) is ¹ ~ R ^15, preferred ranges are also the same.

The dye multimer used in the present invention is preferably a compound of the formula (A1-2), and one of R ¹ to R ¹⁵ contains a main chain structure represented by the formula (A1-1-1). One of R ¹¹ to R ¹⁵ of the formula (A1-2) is a main chain structure represented by the formula (A1-1-1), or R ¹ , R ² , R of the formula (A1-2) At least one of ³ and R ⁴ contains a main chain structure represented by the general formula (A1-1-1), and more preferably one of R ¹¹ to R ¹⁵ of the general formula (A1-2) is a general formula ( The main chain structure represented by A1-1-1), and more preferably R ¹⁵ is a main chain structure represented by the formula (A1-1-1).

When one of R ¹ , R ² , R ³ and R ⁴ of the formula (A1-2) contains a main chain structure, it is preferred that R ² or R ⁴ is represented by the formula (A1-1-1). The main chain structure, more preferably one of R ²² to R ²⁶ of the formula (A1-1-2) is a main chain structure represented by the formula (A1-1-1), and more preferably R ^{22 .} It is a main chain structure represented by the general formula (A1-1-1).

<<Anion X in the general formula (A1-2)>>

In the general formula (A1-2), X represents an anion which forms a relative salt with a cation of xanthene. child. The anion is contained in correspondence with the valence of the cation contained in the dye multimer.

The dye multimer used in the present invention may contain only one type of anion X, or may contain two or more types.

X is preferably a carboxylate anion, a sulfonate anion, a quinone imine anion, a methide anion, and an anion of any of the borate anions, more preferably a bis(sulfonyl) quinone imine anion, a tris(sulfonate) Methyl anion, tetraaryl borate anion.

The bis(sulfonyl) quinone imine anion is preferably a structure represented by the following formula (AN-1).

(In the formula (AN-1), X ¹ and X ² each independently represent a fluorine atom or an alkyl group having a fluorine atom and having 1 to 10 carbon atoms. X ¹ and X ² may be bonded to each other to form a ring)

X ¹ and X ² each independently represent a fluorine atom or an alkyl group having a fluorine atom of 1 to 10, preferably a fluorine atom or an alkyl group having a fluorine atom of 1 to 10, more preferably carbon. The number is 1 to 10 perfluoroalkyl groups, more preferably a perfluoroalkyl group having 1 to 4 carbon atoms, particularly preferably a trifluoromethyl group.

The tris(sulfonyl)methyl anion is preferably a structure of the following formula (AN-2).

(In the formula (AN-2), X ³ , X ⁴ and X ⁵ each independently represent a fluorine atom or an alkyl group having a fluorine atom of 1 to 10)

X ³ , X ⁴ and X ⁵ are each independent, and have the same meanings as X ¹ and X ² , and the preferred ranges are also the same.

The tetraaryl borate anion is preferably a compound represented by the following formula (AN-5).

(In the formula (AN-5), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an aryl group)

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each preferably an aryl group having a carbon number of 6 to 20, more preferably an aryl group having a carbon number of 6 to 14, and more preferably a carbon number of 6 to 6. 10 aryl groups.

The aryl group represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may have a substituent. When it has a substituent, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbonyloxy group, an amine mercapto group, a sulfo group, a sulfonylamino group, a nitro group, etc. are mentioned, and a halogen atom is preferable. The alkyl group is more preferably a fluorine atom or an alkyl group, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.

Ar ¹ , Ar ² , Ar ³ and Ar ^{4 are more} preferably phenyl groups each independently having a halogen atom and/or an alkyl group containing a halogen atom, and more preferably an alkyl group having a fluorine atom and/or a fluorine atom. Phenyl.

Specific examples of the non-nucleophilic counter anion used in the present invention are shown below, but the present invention is not limited thereto.

[Chem. 24]

[Chem. 26]

Hereinafter, examples of the repeating unit represented by the formula (A1-1) or the repeating unit represented by the formula (A1-2) used in the present invention are shown. The invention is of course not limited to these examples.

[化27]

The dye multimer used in the present invention contains, in all repeating units, a total of 1 mol% to 100 mol% of a repeating unit represented by the formula (A1-1) and a formula (A1-2) The repeating unit represented is preferably from 5 mol% to 40 mol%, more preferably from 10 mol% to 30 mol%. The repeating unit represented by the formula (A1-1) and the repeating unit represented by the formula (A1-2) may be contained alone or in combination of two or more.

<<Other functional groups and repeating units>>

The dye multimer of the present invention may have other functional groups in a repeating unit containing the dye structure. As another functional group, a polymerizable group, an alkali-soluble group, etc. are illustrated.

Further, the dye multimer of the present invention contains a repeating unit containing the dye structure In addition, other repeating units may also be included. Other repeating units may also have a functional group.

In addition, as another repeating unit, at least one type of repeating unit containing a polymerizable group or an alkali-soluble group (preferably an acid group) can be exemplified.

<<<Polymerizable groups of pigment multimers>>>

The dye multimer of the present invention preferably contains a polymerizable group. It may contain only one type of polymerizable group, and may contain two or more types.

Regarding the polymerizable group, the dye structure may contain a polymerizable group, and other portions may contain a polymerizable group. In the present invention, it is preferred that the dye structure contains a polymerizable group. With such a configuration, heat resistance tends to increase.

Further, in the present invention, a form in which a polymerizable group is contained in a portion other than the dye structure is also preferable.

As the polymerizable group, a known polymerizable group which can be crosslinked by a radical, an acid or a heat can be used, and examples thereof include a group containing an ethylenically unsaturated bond, and a cyclic ether group (epoxy group, oxa group). A cyclobutane group, a methylol group or the like is particularly preferably a group containing an ethylenically unsaturated bond, more preferably a (meth)acrylonitrile group, and still more preferably a glycidyl (meth)acrylate and (Meth)acrylonitrile group of 3,4-epoxy-cyclohexylmethyl (meth)acrylate.

The polymerizable group is preferably contained in the dye multimer as a repeating unit having a polymerizable group, and more preferably contained as a repeating unit having an ethylenically unsaturated bond in the dye multimer. That is, an example of a preferred embodiment of the dye multimer of the present invention is a form in which the dye multimer contains a repeating unit containing a dye unit and a repeating unit having a polymerizable group, and more preferably contains a dye-containing unit. Repetitive unit of the volume, And a repeating unit having an ethylenically unsaturated bond.

The method of introducing a polymerizable group includes (1) a method of modifying a dye polymer by a compound containing a polymerizable group, and (2) copolymerizing a dye unit and a compound containing a polymerizable group. Import method, etc. Hereinafter, a detailed description will be made.

(1) A method of modifying a pigment multimer by a compound containing a polymerizable group and introducing it:

A method of introducing and modifying a dye multimer by a compound containing a polymerizable group can be carried out by a known method without particular limitation. From the viewpoint of production, for example, (a) a method of reacting a carboxylic acid having a dye multimer with an epoxy compound containing an unsaturated bond, and (b) a dye multimer A method of reacting a hydroxyl group or an amine group with an isocyanate compound containing an unsaturated bond, and (c) a method of reacting an epoxy compound of the dye multimer with a carboxylic acid compound containing an unsaturated bond.

Examples of the (a) epoxy compound containing an unsaturated bond in the method of reacting a carboxylic acid having a dye multimer with an epoxy compound containing an unsaturated bond include glycidyl methacrylate and acrylic acid. Glycidyl ester, allyl glycidyl ether, 3,4-epoxy-cyclohexyl methyl acrylate, 3,4-epoxy-cyclohexyl methyl methacrylate, etc., especially glycidyl methacrylate and The 3,4-epoxy-cyclohexylmethyl methacrylate is excellent in crosslinkability and storage stability, and is preferable. Well-known conditions can be used for reaction conditions.

As the (b) the hydroxyl group or the amine group possessed by the dye multimer

Examples of the isocyanate compound containing an unsaturated bond in the method of reacting an isocyanate compound having an unsaturated bond include 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, and isocyanic acid 1. 1-bis(acryloxymethyl)ethyl ester or the like, but 2-isocyanatoethyl methacrylate is excellent in crosslinkability and storage stability, and is preferable. Well-known conditions can be used for reaction conditions.

The (c) unsaturated compound-containing carboxylic acid compound in the method of reacting the epoxy compound of the dye multimer with the carboxylic acid compound containing an unsaturated bond, as long as it is known to have (meth) The acryloyloxy group-containing carboxylic acid compound can be used without particular limitation, but it is preferably methacrylic acid and acrylic acid, particularly methacrylic acid, which is excellent in crosslinkability and storage stability. Well-known conditions can be used for reaction conditions.

(2) A method of introducing a pigment monomer and a polymerizable group-containing compound after copolymerization: (2) A method in which a monomer and a polymerizable group-containing compound are copolymerized and introduced, and a known method can be used without particular limitation, but (d) a single amount of a pigment capable of radical polymerization is preferred. Method for copolymerizing a body with a polymerizable group-containing compound capable of undergoing radical polymerization, and (e) a method for copolymerizing a polymerizable monomer capable of undergoing polyaddition and a polymerizable group-containing compound capable of undergoing polyaddition .

(d) a polymerizable group-containing compound capable of undergoing radical polymerization in a method of copolymerizing a monomer monomer capable of radical polymerization and a polymerizable group-containing compound capable of undergoing radical polymerization, and particularly, a polymerizable group-containing compound An allyl group-containing compound (for example, allyl (meth) acrylate) or an epoxy group-containing compound (for example) Such as glycidyl (meth)acrylate, 3,4-epoxy-cyclohexylmethyl (meth)acrylate, etc.), oxetane-containing compounds (eg 3-methyl (meth)acrylate A hydroxymethyl group-containing compound (for example, N-(hydroxymethyl) acrylamide or the like) is particularly preferably an epoxy compound or an oxetane compound. Well-known conditions can be used for reaction conditions.

(e) a polymerizable group-containing compound which can be subjected to polyaddition in a method of copolymerizing a monomeric substance capable of undergoing polyaddition and a polymerizable group-containing compound which can be subjected to polyaddition, and examples thereof include A diol compound having an unsaturated bond (for example, 2,3-dihydroxypropyl (meth)acrylate, etc.). Well-known conditions can be used for reaction conditions.

As a method of introducing the polymerizable group, a method of reacting a carboxylic acid having a dye multimer with an epoxy compound containing an unsaturated bond is particularly preferable.

The amount of the polymerizable group of the dye multimer is preferably 0.1 mmol to 2.0 mmol, more preferably 0.2 mmol to 1.5 mmol, and particularly preferably 0.3 mmol to 1.0 mmol, based on 1 g of the dye multimer.

Further, when the dye multimer contains a repeating unit having a polymerizable group, the ratio of the repeating unit is preferably from 1 mol% to 60 mol%, more preferably from 10 mol% to 50 mol% of all repeating units. The ear, and more preferably 15% to 40% by mole.

Specific examples of the repeating unit having a polymerizable group include the following. However, the invention is not limited to the specific examples.

[化30]

[化31]

In the above specific examples, from the viewpoint of substrate adhesion and surface roughness, a dye monomer having an ethylenically unsaturated bond is preferable, and among them, a methacryl fluorenyl group or an acryl fluorenyl group is preferred. Further, a styryl group or a vinyloxy group is more preferably a methacryl fluorenyl group, an acryl fluorenyl group, and even more preferably a methacryl fluorenyl group.

<<<Alkali soluble groups of pigment multimers>>>

An example of the alkali-soluble group which the dye multimer in the present invention has may be an acid group, and examples of the acid group include a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. It may contain only one type of alkali-soluble group, and may contain two or more types.

In the present invention, the alkali-soluble group (preferably an acid group) is preferably contained in the dye multimer as a repeating unit having an alkali-soluble group (acid group).

In the present invention, the acid value of the dye multimer can be calculated, for example, from the average content of the acid groups in the dye multimer. Further, by changing the content of the monomer unit containing the acid group constituting the dye multimer, a resin having a desired acid value can be obtained.

As a method of introducing an alkali-soluble group into a dye multimer, a method of introducing an alkali-soluble group into a dye monomer in advance and an alkali-soluble group are mentioned. Monomers other than pigment monomers ((meth)acrylic acid, caprolactone modification of acrylic acid, succinic anhydride modification of 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate Ester phthalic anhydride modified material, 1,2-cyclohexane dicarboxylic anhydride modified product of 2-hydroxyethyl (meth)acrylate, styrene carboxylic acid, itaconic acid, maleic acid, lower a monomer containing a carboxylic acid such as bornene carboxylic acid, a monomer containing phosphoric acid such as acidic phosphonium oxyethyl methacrylate or vinylphosphonic acid, vinyl sulfonic acid, 2-propenylamine-2-methylsulfonate The method of copolymerizing a sulfonic acid-containing monomer such as an acid is more preferably used.

The amount of the alkali-soluble group of the dye multimer is preferably from 0.3 mmol to 2.0 mmol, more preferably from 0.4 mmol to 1.5 mmol, particularly preferably from 0.5 mmol to 1.0 mmol, based on 1 g of the dye multimer.

Further, when the dye multimer contains a repeating unit containing a single substance of a dye and a repeating unit having an acid group, the ratio of the repeating unit having an acid group is preferably 5 with respect to all the repeating units in the single unit of the dye. Mohr%~70% by mole, more preferably 10% by mole to 60% by mole, and even more preferably 10% by mole to 50% by mole.

Examples of other functional groups of the dye multimer include a lactone group, an acid anhydride group, a guanamine group, a -COCH ₂ CO-, a cyano group, and the like, and a long-chain alkyl group, a cyclic alkyl group, and an aralkyl group. A hydrophilic or hydrophobicity adjusting group such as a aryl group, an aryl group, a polyalkylene oxide group, a hydroxyl group, a maleimide group, or an amine group can be appropriately introduced.

As a method of introduction, a method of introducing into a single substance of a dye in advance and a method of copolymerizing a monomer having the functional group are mentioned.

The dye multimer used in the present invention may contain the following repeating unit (hereinafter, sometimes referred to as "(b) repeating unit") as a repeat containing an alkali-soluble group And a repeating unit having a group comprising from 2 to 20 unsubstituted repeating alkoxy chains in the side chain. By containing such an alkali-soluble group, a coloring composition having more excellent discoloration resistance can be obtained.

(b) The number of repetitions of the alkoxy chain of the repeating unit is preferably from 2 to 10, more preferably from 2 to 15, and still more preferably from 2 to 10.

The one alkoxy chain is represented by -(CH ₂ ) _n O-, n is an integer, and n is preferably from 1 to 10, more preferably from 1 to 5, still more preferably 2 or 3.

The group containing 2 to 20 unsubstituted repeating alkylene oxide chains in the present invention may contain only one kind of alkylene oxide chain, or may contain two or more types.

In the present invention, the (b) repeating unit is preferably represented by the following formula (P).

General formula (P)

(In the formula (P), X ¹ represents a linking group formed by polymerization, and L ¹ represents a single bond or a divalent linking group. P represents a group containing a group containing a repeating alkoxy chain)

The meanings of X ¹ and L ¹ in the formula (P) are the same as those of R ^x and L ¹¹ in the formula (A1-1-1), and the preferred ranges are also the same.

P represents a group containing a group containing a repeating alkoxy chain, and more preferably a group-containing terminal group or terminal group containing a repeating alkoxy chain.

The terminal atom or the terminal group is preferably a hydrogen atom, an alkyl group, an aryl group or a hydroxyl group, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, a hydroxyl group, and more preferably a hydrogen atom. A base, a phenyl group and a hydroxyl group are particularly preferably a hydrogen atom.

(b) the proportion of repeating units having a group containing 2 to 20 unsubstituted repeating alkoxy groups in the side chain is preferably 2 moles constituting all repeating units of the dye multimer %~20% by mole, more preferably 5% by mole to 15% by mole.

Hereinafter, examples of the (b) repeating unit which can be used in the present invention are shown, but the present invention is of course not limited to the examples.

[化33]

Examples of other functional groups of the dye multimer include a lactone group, an acid anhydride group, a guanamine group, a -COCH ₂ CO-, a cyano group, and the like, and a long-chain alkyl group, a cyclic alkyl group, and an aralkyl group. A hydrophilic or hydrophobicity adjusting group such as a aryl group, an aryl group, a polyalkylene oxide group, a hydroxyl group, a maleimide group, or an amine group can be appropriately introduced.

Examples of the introduction method include a method of introducing into a single color body in advance, and A method of copolymerizing a monomer having the functional group.

Representing other functional groups such as alkali-soluble groups which the pigment multimer can have Specific examples of the repeating unit of the group, but the present invention is not limited thereto.

<<<A constituent unit having at least one type of the structure represented by the formula (1) to the formula (5)>>>

The dye multimer used in the present invention may have at least one of the structures represented by the formulae (1) to (5) in the same molecule. With such a configuration, when the cured film is formed, the exposure sensitivity and the light resistance can be improved. Here, the structure represented by the formulas (1) to (5) functions as a light stabilizer, thereby contributing to an improvement in exposure sensitivity and light resistance. In addition, the adhesion can be improved. Further, generation of development residue can be suppressed. Although the mechanism is inferred, by using the same intramolecular color The pigment structure and the dye multimer of at least one of the structures represented by the formulas (1) to (5), and the distance between the dye structure and the structures represented by the formulas (1) to (5) become more near. As a result, it can be considered that the exposure sensitivity and the light resistance can be improved more effectively.

The structure represented by the formula (1) is generally referred to as a hindered amine group. The structure represented by the formula (2) is generally referred to as a hindered phenol system. The structure represented by the formula (3) is generally referred to as a benzotriazole system. The structure represented by the formula (4) is generally referred to as a hydroxybenzophenone system. The structure represented by the formula (5) is generally referred to as a triazine system.

In the formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group or an oxy radical. R ² and R ³ each independently represent an alkyl group having 1 to 18 carbon atoms. R ² and R ³ may be bonded to each other to represent an aliphatic ring having 4 to 12 carbon atoms. "*" represents a bond between the structure represented by the formula (1) and the polymer skeleton.

In the formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group or an oxy radical, and preferably an alkyl group having 1 to 18 carbon atoms.

The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, but is preferably linear. The number of carbon atoms of the alkyl group having 1 to 18 carbon atoms is preferably 1 to 12, more preferably 1 to 8, more preferably 1 to 3, particularly preferably 1 or 2. In particular, the alkyl group having 1 to 18 carbon atoms is preferably a methyl group or an ethyl group, more preferably a methyl group.

The aryl group may have a carbon number of 6 to 18, a range of 6 to 12, or a carbon number of 6. Specifically, a phenyl group is mentioned.

When R ¹ in the formula (1) represents an alkyl group or an aryl group having 1 to 18 carbon atoms, the alkyl group having 1 to 18 carbon atoms and the aryl group may have a substituent or may be unsubstituted. As the substituent which may be possessed, a substituent selected from the substituent group A may be mentioned.

In the formula (1), R ² and R ³ each independently represent a methyl group or an ethyl group, preferably a methyl group. R ² and R ³ may be bonded to each other to represent an aliphatic ring having 4 to 12 carbon atoms.

In the formula (1), "*" represents a bond between the structure represented by the formula (1) and the polymer skeleton. The bonding bond may be bonded to the polymer backbone directly or via a linking group, or may be bonded to the dye structure directly or via a linking group. In particular, "*" in the formula (1) is preferably bonded to the polymer skeleton directly or via a linking group.

Specific examples of the structure represented by the formula (1) are shown below, but are not limited to these specific examples. In the following structure, "*" represents a bond between the structure represented by the formula (2) and the polymer skeleton.

[化43]

In the formula (2), R ⁴ represents an alkyl group or an aryl group having the following formula (2A) and having a carbon number of 1 to 18. R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. "*" indicates a bond of a structure represented by the formula (2) to a polymer skeleton.

In the formula (2), R ⁴ represents an alkyl group or an aryl group having the following formula (2A) and having 1 to 18 carbon atoms, and is preferably represented by the formula (2A). The alkyl group and the aryl group having 1 to 18 carbon atoms have the same meanings as the alkyl group and the aryl group having 1 to 18 carbon atoms as described for R ¹ in the formula (1). In addition, the meaning of "*" is the same as the binding key described in the formula (1).

In the formula (2A), R ⁶ each independently represents an alkyl group having 1 to 18 carbon atoms.

"*" indicates a bond of the structure represented by the formula (2A) and the structure represented by the formula (2).

In the formula (2A), R ^{6 has} the same meaning as the alkyl group having 1 to 18 carbon atoms described in R ¹ in the formula (1). In addition, the meaning of "*" is the same as the binding key described in the formula (1).

Specific examples of the structure represented by the formula (2) are shown below, but are not limited to these specific examples. In the following structure, "*" indicates the structure and aggregation represented by the formula (2) The binding bond of the backbone of the compound.

In the formula (3), R ⁷ represents an alkyl group having 1 to 18 carbon atoms; and n1 represents an integer of 0 to 3. When n1 is 2 or 3, each R ⁷ may be the same or different. "*" indicates a bond of a structure represented by the formula (3) to a polymer skeleton.

In the formula (3), R ^{7 has} the same meaning as the alkyl group having 1 to 18 carbon atoms described in R ¹ in the formula (1).

In the formula (3), n1 represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1.

In the formula (3), the meaning of "*" is the same as the bond described in the formula (1).

Specific examples of the structure represented by the formula (3) are shown below, but are not limited to these specific examples. In the following structure, "*" represents a bond between the structure represented by the formula (3) and the polymer skeleton.

[化47]

In the formula (4), R ⁸ and R ⁹ each independently represent an alkyl group having 1 to 18 carbon atoms. N2 represents an integer from 0 to 3. N3 represents an integer from 0 to 4. When n2 is 2 or 3, each R ⁸ may be the same or different. When n3 represents an integer of 2 to 4, each of R ⁹ may be the same or different. "*" indicates a bond of a structure represented by the formula (4) to a polymer skeleton.

In the formula (4), R ⁸ and R ^{9 have} the same meanings as the alkyl group having 1 to 18 carbon atoms as described for R ¹ in the formula (1).

In the formula (4), n2 represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1.

In the formula (4), n3 represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1.

In the formula (4), the meaning of "*" is the same as the bond described in the formula (1).

Specific examples of the structure represented by the formula (4) are shown below, but are not limited to these specific examples. In the following structure, "*" represents a bond between the structure represented by the formula (4) and the polymer skeleton.

In the formula (5), R ¹⁰ to R ¹² each independently represent an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. N4 to n6 each independently represent an integer of 0 to 5. N7 to n9 each independently represent 0 or 1, and at least one of n7 to n9 represents 1. "*" indicates a bond of a structure represented by the formula (5) to a polymer skeleton.

When R ¹⁰ in the formula (5) represents an alkyl group having 1 to 18 carbon atoms, the meaning is the same as the alkyl group having 1 to 18 carbon atoms as illustrated in R ¹ in the formula (1), and preferably The alkyl group having 1 to 3 carbon atoms is more preferably a methyl group. When R ¹⁰ represents an alkoxy group having 1 to 8 carbon atoms, the alkoxy group preferably has 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 4 carbon atoms.

R ¹⁰ in the formula (5) may further have a substituent. The substituent which may be further included may be a substituent selected from the substituent group A.

N4 in the formula (5) represents an integer of 0 to 5, preferably an integer of 1 to 4, preferably 2 or 3. When n4 represents an integer of 2 to 5, each R ¹⁰ may be the same or different.

R ¹¹ in the formula (5) has the same meaning as R ¹⁰ in the formula (5), and the preferred range is also the same.

N5 in the formula (5) represents an integer of 0 to 5, preferably an integer of 1 to 3, more preferably 1 or 2. When n5 represents an integer of 2 to 5, each of R ¹¹ may be the same or different.

R ¹² in the formula (5) has the same meaning as R ¹⁰ in the formula (5), and the preferred range is also the same.

N6 in the formula (5) represents an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 0 or 1. When n6 represents an integer of 2 to 5, each R ¹² may be the same or different.

In the formula (5), n7 to n9 each independently represent 0 or 1, and at least one of n7 to n9 represents 1. In particular, it is preferable that only n7 indicates 1, or only n8 and n9 indicate 1, or only n7 and n8 and n9 indicate one.

In the formula (5), the meaning of "*" is the same as the bond described in the formula (1).

Hereinafter, a specific example of the structure represented by the formula (5) is shown, but the invention is not limited thereto. These specific examples. In the following structure, "*" represents a bond between the structure represented by the formula (5) and the polymer skeleton.

The constituent unit having at least one of the structures represented by the formulas (1) to (5) contained in the dye-polymer of the present invention is preferably represented by the following formula (E).

Formula (E)

In the formula (E), X ^{3 has} the same meaning as R ^x in the formula (A1-1-1). The meaning of L ^{4 is} the same as L ¹¹ in the formula (A1-1-1). Z ¹ represents a structure represented by the above formulas (1) to (5).

Specific examples of the constituent units having at least one of the structures represented by the formulas (1) to (5) are shown below, but the present invention is not limited to the specific examples.

The dye multimer may not contain at least one constituent unit having a structure represented by the formulas (1) to (5), but in the case where the constituent unit is contained, all the constituents in the dye multimer are included. When the unit is 100% by mass, the content of at least one structural unit having a structure represented by the formulas (1) to (5) is preferably 0.5% by mass to 20% by mass, and more preferably 1% by mass. 10% by mass, particularly preferably 1% by mass to 5% by mass.

<<<Specific end base>>>

The dye multimer used in the present invention preferably has a group represented by the formula (I) or a group represented by the formula (II) (hereinafter sometimes referred to as "specific terminal group"). By adopting such a configuration, solvent resistance and light resistance can be imparted. Further, for example, since it is synthesized by living radical polymerization, the degree of dispersion (Mw/Mn) of the dye multimer can be reduced. In other words, by making the pigment multimer and reducing the ratio of the high molecular weight component, the light resistance can be further improved, and the solvent resistance can be improved by reducing the ratio of the low molecular weight component. Further, heat resistance, coatability, and developability can be further improved.

General formula (I)

In the formula (I), Z represents a hydrogen atom or a monovalent substituent. * indicates the bonding position with the end of the main chain.

In the formula (I), Z represents a monovalent substituent. Z is preferably a hydrogen atom, a halogen atom, a carboxyl group, a cyano group, an alkyl group having 1 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, and a total of 3 atomic atoms of a carbon atom and a hetero atom. Monovalent heterocyclic groups of ~30, -OR ¹ , -SR ¹ , -OC(=O)R ¹ , -N(R ¹ )(R ² ), -C(=O)OR ¹ , -C( =O)N(R ¹ )(R ² ), -P(=O)(OR ¹ ) ₂ , -P(=O)(R ¹ ) ² or a monovalent group having a polymer chain, preferably Selected from -SR ¹ , aryl, heteroaryl, alkyl and/or aryl substituted amine, alkoxy, and aryloxy, more preferably from -SR ¹ (preferably alkylthio) It is selected from an arylthio group and an aryl group, and more preferably an alkylthio group or an aryl group, particularly preferably an alkylthio group.

The aryl group as Z is preferably a phenyl group or a naphthyl group. The heteroaryl group as Z is preferably a nitrogen-containing 5-membered ring or a 6-membered ring compound. The amine group substituted with an alkyl group and/or an aryl group of Z is preferably an amine group substituted with an alkyl group having 1 to 5 carbon atoms or a phenyl group. The alkoxy group as Z is preferably an alkoxy group having 2 to 5 carbon atoms. The aryloxy group as Z is preferably a phenoxy group.

R ¹ and R ² each independently represent an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, or a carbon atom and a hetero atom. a monovalent heterocyclic group having 3 to 30 atoms in total, an alkyl group having 1 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, and a total number of atoms of a carbon atom and a hetero atom The monovalent heterocyclic group of 3 to 30, R ¹ and R ² may be substituted or unsubstituted. As a substituent at the time of substitution, an alkyl group, an aryl group, etc. are illustrated.

R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms or benzene. base.

General formula (II)

In the formula (II), A and B each independently represent a monovalent substituent. A and B They can be joined to each other to form a ring. * indicates the bonding position with the end of the main chain.

The monovalent substituent represented by A and B is preferably an alkyl group having 1 to 30 carbon atoms and an aryl group having 6 to 30 carbon atoms, respectively. The alkyl group having 1 to 30 carbon atoms is more preferably 3 to 10 carbon atoms.

In particular, it is preferred that one of A and B is a secondary or tertiary alkyl group having a carbon number of 1 to 30, and the other is an alkyl group having a carbon number of 1 to 30 or a carbon number of 6 to 30. More preferably, one of A and B is a tertiary alkyl group having a carbon number of 1 to 30, and the other of A and B is an alkyl group having 1 to 30 carbon atoms, particularly preferably one of A and B. The one is a tertiary alkyl group having a carbon number of 1 to 30, and the other is a secondary or tertiary alkyl group having a carbon number of 1 to 30 (more preferably a secondary alkyl group having 1 to 30 carbon atoms).

The substituent which the alkyl group having 1 to 30 carbon atoms may have is preferably an aryl group, more preferably a phenyl group. As the substituent which the aryl group may have, an aryl group is preferred. Further, the groups may be substituted by other substituents. A and B may be bonded to each other to form a ring.

In the present invention, it is particularly preferred that Z in the formula (I) is -SR ¹ or an aryl group, and A and B in the formula (II) are a secondary alkyl group or a tertiary group having a carbon number of 1 to 30, respectively. An alkyl group (wherein A and B may be bonded to each other to form a ring).

A specific example of the terminal group is shown, but the present invention is not limited thereto.

[化56]

[化58]

As a method of introducing a terminal group represented by the general formula (I) or the general formula (II) into a polymer main chain, a method represented by the compound represented by the general formula (Ia) and a general formula ( The polymerizable compound having a dye structure is subjected to radical polymerization in the presence of at least one of the compound represented by IIa) and the radical represented by the formula (IIb).

General formula (Ia)

In the formula (Ia), Z has the same meaning as in the formula (I). C represents a monovalent organic group.

General formula (IIa)

In the formula (IIa), Z has the same meaning as in the formula (II). D represents a monovalent organic group.

General formula (IIb)

In the formula (IIb), A and B have the same meanings as in the formula (II).

By blending such an additive, the active passivation of the terminal at the time of radical polymerization becomes a state of equilibrium, and it appears that the radical is not deactivated. By polymerizing by such living radical polymerization, a polymer having a small dispersion can be obtained.

The weight average molecular weight (Mw) of the dye multimer is preferably from 2,000 to 50,000, more preferably from 3,000 to 30,000, particularly preferably from 6,000 to 20,000.

Further, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the dye multimer [(Mw) / (Mn)] is preferably from 1.0 to 2.0, more preferably from 1.1 to 1.8, particularly preferably from 1.1 to 1. 1.5.

The glass transition temperature (Tg) of the dye multimer of the present invention is preferably 50 ° C or higher, more preferably 100 ° C or higher. In addition, using thermogravimetric analysis (thermogravimetric analysis) The 5% weight loss temperature obtained by (Thermogravimetric Analysis, TGA) measurement is preferably 120 ° C or more, more preferably 150 ° C or more, and still more preferably 200 ° C or more. By being in this region, when the colored composition of the present invention is applied to the production of a color filter or the like, the concentration change caused by the heating process can be reduced.

When the dye multimer used in the present invention contains a repeating unit having a dye structure and other repeating units, a random polymer containing a polymerizable compound of a dye and another polymerizable compound is preferable. By using a random polymer, the dye structure is randomly present in the dye multimer, and the effects of the present invention are more effectively exhibited.

Further, the light absorption coefficient per unit weight of the dye multimer of the present invention (hereinafter referred to as ε'. ε' = ε / average molecular weight, unit: L / g. cm) is preferably 30 or more, more preferably 60 or more. More preferably, it is 100 or more. By being in this range, when the color filter of the present invention is applied to produce a color filter, a color filter having good color reproducibility can be produced.

From the viewpoint of the coloring power, the molar absorption coefficient of the dye multimer used in the colored composition of the present invention is preferably as high as possible.

The reduction viscosity of the dye multimer used in the coloring composition of the present invention is preferably from 4.0 to 10.0, more preferably from 5.0 to 9.0, still more preferably from 6.0 to 7.0, from the viewpoint of color shift. The reducing viscosity can be measured, for example, using a Ubbelohde viscometer.

The dye multimer of the present invention is preferably a compound dissolved in the following organic solvent.

As the organic solvent, esters (for example, methyl 3-ethoxypropionate, 3-ethyl b) Ethyl oxypropionate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, etc., 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 (eg toluene, xylene, etc.) The amount of the solvent is preferably 1% by mass or more and 50% by mass or less, 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 based on the solvent. By applying the coloring composition of the present invention to the production of a color filter or the like in this region, it is possible to form a suitable coating surface or to reduce the concentration caused by dissolution after coating other colors. decline.

In the colored composition of the present invention, one type of dye multimer may be used alone or two or more types may be used in combination. When two or more types are used, it is preferable that the total amount thereof corresponds to the content described later.

The content of the dye multimer in the colored composition of the present invention is set in consideration of the content ratio of the pigment to be described later.

The mass ratio (pigment polymer/pigment) of the dye multimer to the pigment is preferably from 0.1 to 5, more preferably from 0.2 to 2, still more preferably from 0.3 to 1.

The coloring agent component (the pigment multimer, the total of the pigments and other dyes described later) in the coloring composition of the present invention is preferably 10% by mass to 80% by mass, and more preferably 15% by mass of the total solid content of the coloring composition. %~60% by mass.

The colored composition of the present invention contains a curable compound in addition to the dye multimer. Further, the colored composition of the present invention may contain other components. For example, for the purpose of adjusting the color value, etc., it is preferred to include, in addition to the dye multimer, There are other colorants (preferably pigments) or pigment dispersants.

Further, the coloring composition of the present invention can be used for the formation of a coloring layer of a color filter. In the case of forming a color filter, a curable compound is usually contained in addition to the dye multimer, a pigment, and a pigment dispersant. The polymerizable compound or the alkali-soluble resin (including an alkali-soluble resin containing a polymerizable group) is exemplified as the curable compound, and is appropriately selected depending on the use or the production method. The curable compound is preferably a polymerizable compound. Further, the colored composition of the present invention preferably contains a photopolymerization initiator.

For example, when the coloring layer is formed by a photoresist, the coloring composition of the present invention preferably contains the dye multimer of the present invention, an alkali-soluble resin as a curable compound, a pigment, a pigment dispersing agent, and photopolymerization. The composition of the starter. Further, a component such as a surfactant or a solvent may be contained.

Further, when the colored layer is formed by dry etching, it is preferably a composition containing the dye multimer of the present invention, a polymerizable compound as a curable compound, a pigment, a pigment dispersant, and a photopolymerization initiator. Further, a component such as a surfactant or a solvent may be contained.

Hereinafter, the details will be described.

<Polymerizable compound>

The colored composition of the present invention preferably contains a polymerizable compound.

A known polymerizable compound which can be crosslinked by a radical, an acid or a heat can be used, and examples thereof include an ethylenically unsaturated bond, a cyclic ether (epoxy group, oxetane), and a methylol group. A polymerizable compound. Polymerization from the viewpoint of sensitivity The compound can be suitably selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Among them, a tetrafunctional or higher polyfunctional polymerizable compound is preferred, and a pentafunctional or higher polyfunctional polymerizable compound is more preferred.

Such a compound group is widely known in the industrial field of the present invention, and these compounds can be used without particular limitation in the present invention. These compounds may be, for example, any of the chemical forms such as monomers, prepolymers, i.e., dimers, trimers, and oligomers, or mixtures thereof, and multimers thereof. The polymerizable compound in the present invention may be used alone or in combination of two or more.

More specifically, examples of the monomer and the prepolymer thereof include an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or Esters, guanamines, and multimers thereof, preferably esters of an unsaturated carboxylic acid and an aliphatic polyol compound, and guanamines of an unsaturated carboxylic acid and an aliphatic polyamine compound, and Multimer. Further, an unsaturated carboxylic acid ester or a guanamine having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group, an addition reaction with a monofunctional or polyfunctional isocyanate or an epoxy group, or A dehydration condensation reaction with a monofunctional or polyfunctional carboxylic acid or the like. Further, an addition reaction product of an unsaturated carboxylic acid ester or an oxime amine having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol group, Further, a substituted carboxylic acid ester having a detachable substituent such as a halogen group or a tosyloxy group or a decylamine and a substituted reactant of a monofunctional or polyfunctional alcohol, an amine or a thiol are also suitable. Further, as another example, a group of compounds substituted with a vinylbenzene derivative such as an unsaturated phosphonic acid or styrene, a vinyl ether or an allyl ether may be used instead. The unsaturated carboxylic acid.

As the specific compound, in the present invention, the compound described in Paragraph No. [0095] to Paragraph No. [0108] of JP-A-2009-288705 can also be suitably used.

Further, as the polymerizable compound, an ethylenically unsaturated group-containing compound having at least one ethyl group which can undergo addition polymerization and having a boiling point of 100 ° C or higher at normal pressure is also preferable. Examples of the compound include monofunctional acrylates or methyl groups such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate. Acrylate; polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexane diol (meth) acrylate, trimethylolpropane tri (propylene oxy group) Propyl)ether, tris(propyleneoxyethyl)isocyanurate, addition of ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylolethane (methyl) The (meth)acrylic acid amide is described in Japanese Patent Publication No. Sho-48-41708, Japanese Patent Publication No. SHO-50-6034, and JP-A-51-37193. Ester, Japanese Patent Laid-Open No. Sho 48-64183, Japanese Patent Publication No. Sho 49-43191, Japanese Patent The polyester acrylate described in the publication No. 52-30490, a polyfunctional acrylate or methacrylate such as an epoxy acrylate which is a reaction product of an epoxy resin and (meth)acrylic acid, and the like mixture.

A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated group such as glycidyl (meth)acrylate may, for example, be mentioned.

In addition, as the other preferable polymerizable compound, an anthracene ring described in the specification of Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, and Japanese Patent No. 4364216, and the like can be used. A compound having a difunctional or higher ethylenically unsaturated group, a cardo resin.

In addition, as a compound having a boiling point of 100 ° C or higher and having at least one ethylenically unsaturated group capable of undergoing addition polymerization under normal pressure, paragraph number [0254] of the Japanese Patent Laid-Open Publication No. 2008-292970 The compound described in No. [0257] is also suitable.

In addition to the above, a radical polymerizable monomer represented by the following formula (MO-1) to formula (MO-5) can be suitably used. Further, in the formula, when T is an alkyloxy group, the terminal on the carbon atom side is bonded to R.

[化62]

In the above formula, n is 0 to 14, and m is 1 to 8. R and T in a plurality of molecules may be the same or different from each other.

In each of the polymerizable compounds represented by the above formula (MO-1) to formula (MO-5), at least one of R is represented by -OC(=O)CH=CH ₂ , Or a group represented by -OC(=O)C(CH ₃ )=CH ₂ .

In the present invention, as a specific example of the polymerizable compound represented by the above formula (MO-1) to (MO-5), a paragraph of JP-A-2007-269779 may be suitably used. The compound described in No. 0248 to Paragraph No. 0251.

The following compounds which are described in the general formula (1) and the general formula (2) together with the specific examples thereof can also be used as a polymerizable compound, which is a polyfunctional compound, in the above-mentioned Japanese Patent Publication No. Hei 10-62986. A compound obtained by adding (meth)acrylic acid after adding ethylene oxide or propylene oxide to an alcohol.

Among them, as the polymerizable compound, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available product are preferred). KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercial product is KAYARAD D-310; Nippon Chemical Co., Ltd. Manufactured by the company), dipentaerythritol hexa(meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), ethoxylated dipentaerythritol hexaacrylate (commercially available) The product is A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and the (meth)acrylonitrile group is in the B The structure between the diol and propylene glycol residues. These oligomer types can also be used.

The polymerizable compound may be a polyfunctional monomer and has an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. As described above, when the ethylenic compound is a compound having an unreacted carboxyl group as in the case of a mixture, the ethylenic compound can be directly used, and if necessary, the hydroxyl group and the non-aromatic carboxyl group of the ethylenic compound can also be used. The acid anhydride is reacted to introduce an acid group. In this case, specific examples of the non-aromatic carboxylic anhydride to be used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and alkylation. Hexahydrophthalic anhydride, succinic anhydride, maleic anhydride.

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and it is preferred to react an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to have an acid. The polyfunctional monomer is particularly preferred in the ester, and the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. As a commercial item, M-510, M-520, etc. which are polyacid-acid-modified acrylic oligomer manufactured by the East Asia Synthetic Co., Ltd. are mentioned, for example.

One type of these monomers may be used alone. However, since it is difficult to use a single compound in terms of production, two or more types may be used in combination. Further, as the monomer, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as needed.

A preferred acid value of the polyfunctional monomer having an acid group is from 0.1 mgKOH/g to 40 mgKOH/g, particularly preferably from 5 mgKOH/g to 30 mgKOH/g. If the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are lowered, and if it is too high, manufacturing or handling becomes difficult. Further, the photopolymerization performance is lowered, and the surface smoothness of the pixel is poor. Therefore, when two or more kinds of polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is preferred that the acid value of all the polyfunctional monomers is within the range The way to adjust.

Further, as the polymerizable compound, a polyfunctional monomeric body having a caprolactone structure is also preferable.

The polyfunctional monolith having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trishydroxymethylethane and di-trimethylol B. Polyols such as alkane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylol melamine and (meth)acrylic acid and The ε-caprolactone obtained by esterification of ε-caprolactone is modified with a polyfunctional (meth) acrylate. Among them, a polyfunctional mono-weight having a caprolactone structure represented by the following formula (Z-1) is preferred.

In the general formula (Z-1), all of the six R groups are represented by the following formula (Z-2), or one to five of the six R groups are represented by the following formula (Z-2). The remaining group is a group represented by the following formula (Z-3).

[化65]

In the formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents an integer of 1 or 2, and "*" represents a bond.

In the formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bond.

Such a polyfunctional single body having a caprolactone structure is commercially available, for example, as a KAYARAD DPCA series from Nippon Kayaku Co., Ltd., and may be exemplified by DPCA-20 (the formula (Z-1) to the formula (Z- 3), m = 1, the number of groups represented by the formula (Z-2) = 2, R ¹ is a compound of a hydrogen atom), DPCA-30 (the formula (Z-1) ~ formula (Z In -3), m = 1, the number of groups represented by the formula (Z-2) = 3, a compound in which R ¹ is a hydrogen atom), DPCA-60 (the formula (Z-1) - formula ( Z-3) in, m = 1, the number of groups represented by the formula (Z-2) represented by = 6, R ¹ of the compound are hydrogen atoms), DPCA-120 (of the formula (Z-1) ~ formula In (Z-3), m = 2, the number of groups represented by the formula (Z-2) = 6, a compound in which R ¹ is a hydrogen atom, and the like.

In the present invention, a polyfunctional monothomer having a caprolactone structure can be used alone Use or mix two or more types.

In addition, as the specific monomer in the present invention, at least one selected from the group consisting of compounds represented by the following formula (Z-4) or (Z-5) is also preferable.

In the general formula (Z-4) and the general formula (Z-5), E independently represents -((CH ₂ ) _y CH ₂ O)-, or -((CH ₂ ) _y CH(CH ₃ ) O)-, y each independently represent an integer of 0 to 10, and X each independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.

In the above formula (Z-4), the total of the acrylonitrile group and the methacryl group is 3 or 4, and m each independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. . However, when the total of each m is 0, any one of X is a carboxyl group.

In the above formula (Z-5), the total of the acryloyl group and the methacryl fluorenyl group is 5 or 6, and n each independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. . However, when the total of each n is 0, any one of X is a carboxyl group.

In the above formula (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the total of each m is preferably an integer of 2 to 40, more preferably 2 An integer of ~16, particularly preferably an integer from 4 to 8.

In the above formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

Further, -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- in the formula (Z-4) or the formula (Z-5) is preferably It is a form in which the end of the oxygen atom side is bonded to X.

The compound represented by the above formula (Z-4) or (Z-5) may be used alone or in combination of two or more. In particular, in the general formula (Z-5), it is preferred that all of the six X groups are acrylonitrile groups.

In addition, the total content of the compound represented by the formula (Z-4) or the formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.

The compound represented by the above formula (Z-4) or formula (Z-5) can be synthesized by the following steps as a previously known step: by making pentaerythritol or dipentaerythritol with ethylene oxide or propylene oxide The step of performing a ring-opening addition reaction to bond the ring-opening skeleton and a step of introducing a (meth)acryl fluorenyl group by reacting a terminal hydroxyl group of the ring-opening skeleton with, for example, (meth)acryloyl chloride. Each step is a well-known step, and a compound represented by the formula (Z-4) or the formula (Z-5) can be easily synthesized by a person skilled in the art.

Among the compounds represented by the above formula (Z-4) or formula (Z-5), a pentaerythritol derivative and/or a dipentaerythritol derivative are more preferred.

Specifically, a compound represented by the following formula (a) to formula (f) (hereinafter also referred to as "exemplary compound (a) to exemplary compound (f)")), preferably an exemplified compound (a), exemplified compound (b), exemplified compound (e), and exemplified compound (f).

[化69]

As a commercial item of the polymerizable compound represented by the general formula (Z-4) and the general formula (Z-5), for example, Sartomer Co., Ltd. can be used as the ethoxylated chain. Tetrafunctional acrylate-based SR-494, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having 6 pentyloxy chains, as a trifunctional having 3 out-of-strand butoxy chains Acrylate TPA-330 and the like.

In addition, as a polymerizable compound, for example, Japanese Patent Publication No. Sho 48-41708, Japanese Patent Laid-Open No. Sho 51-37193, Japanese Patent Publication No. Hei 2-32293, and Japanese Patent Publication No. Hei 2-16765 Recorded propylene The acid urethanes are described in Japanese Patent Publication No. Sho 58-49860, Japanese Patent Publication No. SHO 56-17654, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. SHO 62-39418. A urethane compound having an ethylene oxide skeleton is also suitable. In addition, an amine-based structure or a sulfide structure is described in the molecule as described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. As the polymerizable compound, an addition polymerizable compound can obtain a curable composition having a very excellent photospeed.

As a commercial product of a polymerizable compound, urethane oligomer UAS-10, UAB-140 (made by Sanyo Kokusaku Pulp company), UA-7200 (made by Shin-Nakamura Chemical Co., Ltd.) , DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-3061, AH-600, T-600, AI-600 (manufactured by Kyoeisha Co., Ltd.).

Examples of the cyclic ether (epoxy group or oxetane) include, for example, JER-827, JER-828, JER-834, and JER-1001 which are bisphenol A type epoxy resins. , JER-1002, JER-1003, JER-1055, JER-1007, JER-1009, JER-1010 (above, Japan Epoxy Resins (share)), Abilon (EPICLON) 860, EPICLON1050, EPICLON1051, EPICLON1055 (above, DIC (manufactured by DIC)), JER-806, JER-807, JER-4004, JER-4005, JER-4007, JER as bisphenol F-type epoxy resin -4010 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 (above, manufactured by Di Ai Sheng (share)), LCE-21, RE-602S (above, manufactured by Nippon Kayaku Co., Ltd.), etc., JER-152, JER-154, JER-157S70, JER-157S65 as phenol novolac type epoxy resin (above, Japan Epoxy Resin (manufactured by Resin), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by Di Aisheng (share)), etc., EPICLON N-660, EPICLON N as cresol novolac type epoxy resin -665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by Di Aisheng (share)), EOCN-1020 (above, Nippon Chemical Co., Ltd.) Manufactured as an aliphatic epoxy resin, ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (above, manufactured by ADEKA (share)), Cerro Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE-3150 (2,2-bis(hydroxymethyl)-1-butanol 1,2-epoxy-4-(2-oxirane) Base) cyclohexane adduct), EPOLEAD PB 3600, EPOLEAD PB 4700 (above, manufactured by Daicel Chemical Industry Co., Ltd.), Denacol EX-211L, EX -212L, EX-214L EX-216L, EX-321L, EX-850L (above, manufactured by Nagase chemteX (share)), ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (above, manufactured by Aidike (share)), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by Eddie Co., Ltd.), JER-1031S (made by Japan Epoxy Co., Ltd.). Such a polymerizable compound is suitable for the case where a pattern is formed by a dry etching method.

The details of the method of using the polymerizable compound, the use alone or in combination, and the amount of addition can be arbitrarily set depending on the final performance design of the coloring composition. For example, from the viewpoint of sensitivity, a structure having a large content of an unsaturated group per molecule is preferable, and in many cases, a difunctional or higher is preferable. Further, from the viewpoint of improving the strength of the cured film formed by the colored composition, a trifunctional or higher polymerizable compound is preferable, and further, the number of functional groups is different by the combination. A polymerizable compound having different polymerizable groups (for example, an acrylate, a methacrylate, a styrene compound, or a vinyl ether compound) is effective in adjusting both sensitivity and strength. Further, it is preferable to use a polymerizable compound having a trifunctional or higher functional group and a different ethylene oxide chain length in order to adjust the developability of the colored composition and obtain excellent pattern forming ability.

Further, the compatibility and dispersibility of other components (for example, a photopolymerization initiator, a dispersion, an alkali-soluble resin, and the like) contained in the colored composition are selected as the polymerizable compound. The use method is also an important factor. For example, it is sometimes possible to use a low-purity compound or a combination of two or more types to improve compatibility. Moreover, a specific structure can also be selected from the viewpoint of improving the adhesion to a hard surface such as a support.

When the polymerizable compound is blended, the content of the polymerizable compound in the coloring composition of the present invention is preferably from 0.1% by mass to 90% by mass, more preferably from 1.0% by mass to 60%, based on the total solid content of the coloring composition. The mass% is particularly preferably 2.0% by mass to 40% by mass.

The composition of the present invention may contain only one type of polymerizable compound, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is in the above range.

<Multifunctional thiol compound>

The colored composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in the molecule for the purpose of promoting the reaction of the polymerizable compound. The polyfunctional thiol compound is preferably a secondary alkanethiol, and particularly preferably a compound having a structure represented by the following formula (I).

General formula (I)

(wherein, n represents an integer from 2 to 4, and L represents a divalent to tetravalent linkage)

In the above formula (I), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2, and L is an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound include a compound represented by the following structural formula (II) to structural formula (IV), and particularly preferably a compound represented by (II). These polyfunctional thiol compounds may be used alone or in combination of two or more.

[71]

The compounding amount of the polyfunctional thiol compound in the composition of the present invention is desirably from 0.3% by weight to 8.9% by weight, more preferably from 0.8% by weight to 6.4%, based on the total solid content other than the solvent. Added in the range of %. Further, the polyfunctional thiol compound can also be added for the purpose of improving stability, odor, resolution, developability, adhesion, and the like.

<Photopolymerization initiator>

The coloring composition of the present invention preferably contains a photopolymerization initiator in terms of further enhancing the sensitivity.

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferred that the ultraviolet region has a sensitivity to visible light. Further, it may be an active agent which generates a living radical with a photo-excited sensitizer, and may also be an initiator which starts cationic polymerization corresponding to the type of the monomer.

Further, the photopolymerization initiator preferably contains at least one compound having a molecular absorption coefficient of at least about 50 in a range of from about 300 nm to 800 nm, more preferably from 330 nm to 500 nm.

Examples of the photopolymerization initiator include a halogenated hydrocarbon derivative (for example, a triazine skeleton, a oxadiazole skeleton, etc.), a mercaptophosphine compound such as a mercaptophosphine oxide, or a hexaarylbiimidazole. An anthracene compound such as an anthracene derivative, an organic peroxide, a sulfur compound, a ketone compound, an aromatic onium salt, a ketoxime ether, an aminoacetophenone compound, or a hydroxyacetophenone is preferably an anthracene compound.

Further, from the viewpoint of exposure sensitivity, it is preferably selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, a mercaptophosphine compound, Phosphine oxide compound, metallocene compound, hydrazine compound, triallyl imidazole dimer, hydrazine compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene- A compound of the group consisting of an iron complex and a salt thereof, a halomethyl oxadiazole compound, and a 3-aryl-substituted coumarin compound.

More preferably a trihalomethyltriazine compound, an α-amino ketone compound, or a decyl phosphine a compound, a phosphine oxide compound, an anthracene compound, a triallyl imidazole dimer, a triarylimidazole compound, a benzimidazole compound, an anthraquinone compound, a benzophenone compound, an acetophenone compound, particularly preferably selected from the group consisting of trihalide At least one compound selected from the group consisting of a triazine compound, an α-amino ketone compound, an anthraquinone compound, a triallyl imidazole compound, a benzophenone compound, a triarylimidazole compound, and a benzimidazole compound. Further, the triarylimidazole compound may also be a mixture with benzimidazole.

Specifically, the following compounds can be exemplified as the trihalomethyltriazine compound. Further, Ph is a phenyl group.

The following compounds can be exemplified as the triaryl imidazole compound and the benzimidazole compound.

A commercially available product can also be used as the trihalomethyltriazine compound, and for example, TAZ-107 (manufactured by Midori Kagaku Co., Ltd.) can also be used.

In particular, when the colored composition of the present invention is used for the production of a color filter provided in a solid-state image sensor, it is necessary to form a fine pattern in a sharp shape. Therefore, it is important that the color is not exposed to the hardenability and residue. The part is developed. From this point of view, it is particularly preferred to use a ruthenium compound as a polymerization initiator. In particular, when a fine pattern is formed in a solid-state image sensor, a stepper is used for exposure for hardening, but the exposure machine may be damaged by halogen, and it is necessary to suppress the addition amount of the polymerization initiator. In view of the above, when a fine pattern is formed as in a solid-state image sensor, it is particularly preferable to use a ruthenium compound as a photopolymerization initiator.

Examples of the halogenated hydrocarbon compound having a triazine skeleton include, for example, a compound described in "Bull. Chem. Soc. Japan", 42, 2924 (1969), and a British patent. The compound described in the specification of Japanese Patent Laid-Open No. Sho 53-133428, the compound described in the specification of German Patent No. 3337024, and the "Journal of Organic Chemistry" by FC Schaefer et al. A compound described in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The compound described in JP-A No. 5-34920, and the compound described in the specification of U.S. Patent No. 4,212,976, and the like, are, for example, the compounds described in paragraph No. 0075 of JP-A-2013-077009.

Further, as the photopolymerization initiator other than the above, acridine derivative can be exemplified Things. Specifically, a compound or the like described in Paragraph No. 0076 of JP-A-2013-077009 can be incorporated into the specification of the present application.

Examples of the ketone compound include a compound described in Paragraph No. 0077 of JP-A-2013-077009, and the contents of these can be incorporated into the specification of the present application.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can also be suitably used. More specifically, for example, an amino acetophenone-based initiator as described in JP-A-10-291969, and a sulfhydryl phosphine oxide-based initiator described in Japanese Patent No. 42258899 can be used. .

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 can be used (trade name: all are BASF (BASF) )))) As the aminoacetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Corporation) which are commercially available products can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179, which is a wavelength of a long-wavelength source such as 365 nm or 405 nm, can be used. Further, as the mercaptophosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade name: all manufactured by BASF Corporation) which is a commercially available product can be used.

As a photopolymerization initiator, a ruthenium compound is more preferable. As a change Specific examples of the compound include a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, and a compound described in JP-A-2006-342166.

As the hydrazine compound such as an anthracene derivative which can be suitably used as the photopolymerization initiator in the present invention, for example, 3-benzylideneoxyimidobutan-2-one and 3-ethyloxy group can be mentioned. Iminobutan-2-one, 3-propenyloxyimidobutan-2-one, 2-ethyloxyiminopentan-3-one, 2-ethyloxyimide 1-phenylpropan-1-one, 2-benzylideneoxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutane- 2-ketone, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

As the ruthenium compound, "British Chemical Society, JC Perkin II" (1979) pp. 1653-1660, "British Chemical Society, Berkin Journal II" (1979) Pp. 156-162, "Journal of Photopolymer Science and Technology" (1995) pp. 202-232, Japanese Patent Laid-Open Publication No. 2000-66385, Japan A compound or the like described in each of the publications of Japanese Laid-Open Patent Publication No. JP-A-2006-342166.

Commercially available products such as IRGACURE-OXE01 (manufactured by BASF Corporation), IRGACURE-OXE02 (manufactured by BASF Corporation), and TR-PBG-304 (manufactured by Changzhou Power Electronic New Materials Co., Ltd.) can be suitably used.

In addition, as the ruthenium compound other than the above-mentioned, it is possible to use the ninth aspect of the carbazole, which is described in Japanese Patent Laid-Open Publication No. 2009-519904. The compound described in the U.S. Patent No. 7,626,957 to which a compound or a benzophenone moiety is introduced, and a nitro group, and a nitro group, are disclosed in Japanese Patent Laid-Open Publication No. 2010-15025, and U.S. Patent Publication No. 2009-292039 The compound described in the Japanese Patent Laid-Open Publication No. 2009-131189, the compound described in U.S. Patent No. 7,556,910, which contains a triazine skeleton and an anthracene skeleton in the same molecule, has a maximum absorption at 405 nm. Further, the compound described in JP-A-2009-221114, which has a good sensitivity to a g-ray source, is used.

The cyclic ruthenium compound described in JP-A-2007-2320, and JP-A-2007-322744 is preferably used. Among the cyclic ruthenium compounds, the cyclic ruthenium compound which is condensed in the carbazole dye described in Japanese Patent Laid-Open Publication No. 2010-185072, and the like, has high light absorption. It is preferable from the viewpoint of high sensitivity.

In addition, the compound described in JP-A-2009-242469, which has an unsaturated bond at a specific site of the ruthenium compound, can be further improved by regenerating the living radical from the polymerization inert radical, and is suitable. Use.

The ruthenium compound having a specific substituent as shown in Japanese Laid-Open Patent Publication No. 2007-269779, or the ruthenium compound having a thioaryl group as shown in JP-A-2009-191061.

Specifically, the ruthenium compound as a photopolymerization initiator is preferably a compound represented by the following formula (OX-1). Furthermore, the N-O bond of 肟 can be the E of the (E) body The compound may also be a bismuth compound of the (Z) body or a mixture of the (E) body and the (Z) body.

In the formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

In the general formula (OX-1), as the monovalent substituent represented by R, a monovalent non-metal atomic group is preferred.

The monovalent non-metal atomic group may, for example, be an alkyl group, an aryl group, a fluorenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group or an arylthiocarbonyl group. Further, these groups may have one or more substituents. Further, the substituent may be further substituted with other substituents.

The substituent may, for example, be a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, a decyloxy group, a decyl group, an alkyl group or an aryl group.

Specific examples of the general formula (OX-1) are shown below, but the present invention is of course not limited to these specific examples.

[化75]

The ruthenium compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has a maximum absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably a ruthenium compound having a high absorbance at 365 nm and 405 nm.

From the viewpoint of sensitivity, the molar absorption coefficient of the cerium compound at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000. Good is 5,000~200,000.

The molar absorption coefficient of the compound can be measured by a known method. Specifically, for example, an ultraviolet-visible spectrophotometer (Carry-5 spectrophotometer manufactured by Varian) is preferably used. The measurement was carried out at a concentration of 0.01 g/L using an ethyl acetate solvent.

When the photopolymerization initiator is contained in the coloring composition of the present invention, the content of the photopolymerization initiator is preferably 0.1% by mass or more and 50% by mass or less, more preferably 0.5% based on the total solid content of the coloring composition. The mass% or more is 30% by mass or less, and more preferably 1% by mass or more and 20% by mass or less. Within this range, more excellent sensitivity and pattern formation can be obtained.

The composition of the present invention may contain only one type of photopolymerization initiator, and may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is in the above range.

<pigment>

The colored composition of the present invention may further contain a coloring agent other than the dye multimer. Specifically, it is preferred to contain a pigment.

As the pigment used in the present invention, various conventional inorganic pigments or organic pigments can be used, and organic pigments are preferably used. As the pigment, it is preferred that the transmittance is high.

Examples of the inorganic pigment include a metal compound represented by a metal oxide or a metal salt, and specific examples thereof include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, lanthanum, and the like. a metal oxide, and a composite oxide of the metal.

Examples of the organic pigment include the following pigments and the like: CI Pigment Yellow 11, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 53, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 99, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 167, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 199; CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 43, CI Pigment Orange 71; CI Pigment Red 81, CI Pigment Red 105, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 155, CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 209, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI pigment red 255, CI pigment red 264, CI pigment red 270; CI pigment violet 19, CI pigment violet 23, CI pigment violet 32, CI pigment violet 39; CI pigment blue 1, CI pigment blue 2, CI pigment blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:3, CI Pigment Blue 15:6, CI Material Blue 16, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 66; CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37, CI Pigment Green 58; CI Pigment Brown 25, CI Pigment Brown 28; CI Pigment black 1, CI pigment black 7.

As the pigment which can be preferably used in the present invention, the following pigments can be mentioned. However, the present invention is not limited to these pigments.

C.I. Pigment Yellow 11, C.I. Pigment Yellow 24, C.I. Pigment Yellow 108, C.I. Yellow Y, 109 Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 154, CI Pigment Yellow 167, CI Pigment Yellow 180, CI Pigment Yellow 185; CI Pigment Orange 36, CI Pigment Orange 71; CI Pigment Red 122, CI Pigment Red 150, CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 177, CI Pigment Red 209, CI Pigment Red 224, CI Pigment Red 242, CI Pigment red 254, CI pigment red 255, CI pigment red 264; CI pigment violet 19, CI pigment violet 23, CI pigment violet 32; CI pigment blue 15:1, CI pigment blue 15:3, CI pigment blue 15:6, CI Pigment Blue 16, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 66; CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37, CI Pigment Green 58, CI Pigment Black 1, CI Pigment Black 7.

These organic pigments may be used alone or in combination for the purpose of adjusting the spectroscopic light or improving the color purity. Specific examples of the combination are shown below. For example, as the red pigment, an anthraquinone pigment, an anthraquinone pigment, a diketopyrrolopyrrole pigment may be used alone, or at least one of these pigments may be used together with a disazo yellow pigment or an isoporphyrin yellow pigment. Mixture of a quinophthalone yellow pigment or an anthraquinone yellow pigment. For example, CI Pigment Red 177 is exemplified as the ruthenium pigment, and CI Pigment Red 155 and CI Pigment Red 224 are mentioned as the ruthenium pigment, and as the diketopyrrolopyrrole pigment, CI Pigment Red 254 is used. From the viewpoint of color properties, it is preferably mixed with CI Pigment Yellow 139. In addition, the quality of the red pigment and the yellow pigment is preferably 100:5 to 100:50. If it is 100:4 or less, it is difficult In order to suppress the light transmittance of 400 nm to 500 nm, if the wavelength is 100:51 or more, the dominant wavelength may be shifted to a short wavelength, and the color separation ability may not be improved. In particular, as the mass ratio, the most suitable range is 100:10 to 100:30. Further, in the case of a combination of red pigments, it is possible to adjust in accordance with the required spectroscopic light.

Further, as the green pigment, a halogenated indigo pigment may be used alone, or it may be used together with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoporphyrin yellow. Mixing of pigments. For example, as such an example, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180 or Mixing of CI Pigment Yellow 185. The quality of green and yellow pigments is preferably 100:5~100:150. The mass ratio is particularly preferably in the range of 100:30 to 100:120.

As the blue pigment, an indigo pigment may be used alone or in combination with a dioxazine-based violet pigment. For example, a mixture of C.I. Pigment Blue 15:6 and C.I. Pigment Violet 23 is preferred. The quality of the blue pigment and the purple pigment is preferably from 100:0 to 100:100, more preferably 100:10 or less.

Further, as the pigment for the black matrix, carbon, titanium black, iron oxide, or titanium oxide may be used singly or in combination, and a combination of carbon and titanium black is preferred. In addition, the quality of carbon and titanium black is preferably in the range of 100:0 to 100:60.

The coloring composition of the present invention is preferably a pigment other than black, and is suitable for a blue pigment.

Regarding the primary particle diameter of the pigment, it is used as a color filter. In view of color unevenness or contrast, it is preferably 100 nm or less, and from the viewpoint of dispersion stability, it is preferably 5 nm or more. The primary particle diameter of the pigment is more preferably 5 nm to 75 nm, further preferably 5 nm to 55 nm, and particularly preferably 5 nm to 35 nm.

The primary particle diameter of the pigment can be measured by a known method such as an electron microscope.

Among them, as the pigment, a pigment selected from the group consisting of an anthraquinone pigment, a diketopyrrolopyrrole pigment, an indigo pigment, a quinophthalone pigment, an isoporphyrin pigment, a methylimine pigment, and a dioxazine pigment is preferred. In particular, it is especially preferred for CI Pigment Red 177 (anthraquinone pigment), CI Pigment Red 254 (diketopyrrolopyrrole pigment), CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Blue 15:6 ( Indigo pigment), CI Pigment Yellow 138 (quinacridone pigment), CI Pigment Yellow 139, CI Pigment Yellow 185 (isoporphyrin pigment), CI Pigment Yellow 150 (methylimine pigment), CI Pigment Violet 23 (two Oxazine pigment).

The content of the pigment is preferably from 10% by mass to 70% by mass, more preferably from 20% by mass to 60% by mass, even more preferably from 25% by mass to 50%, based on all the components other than the solvent contained in the coloring composition. quality%.

The composition of the present invention may contain only one type of pigment, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is in the above range.

Further, in the present invention, a dye other than the dye multimer or a pigment other than the above may be contained. For example, Japanese Patent Laid-Open Publication No. SHO-64-90403, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2, 592, 207, U.S. Patent No. 4,808,501, U.S. Patent No. 5,567,920, U.S. Patent No. 5,505,950, Japanese Patent Laid-Open No. Hei 5-333207, A dye disclosed in Japanese Laid-Open Patent Publication No. Hei 6-35183, Japanese Patent Application Laid-Open No. Hei No. Hei. As the chemical structure, a pyrazole azo type, an anilino azo type, a triphenylmethane type, an anthraquinone type, a benzylidene type, an oxaphthalocyanine type, a pyrazolotriazole azo type, and a pyridone can be used. A dye such as an azo system, a cyanine system, a phenothiazine system, or a pyrrolopyrazine-imine system.

<Pigment Dispersant>

When the coloring composition of the present invention has a pigment, a pigment dispersing agent may be used in combination as needed.

Examples of the pigment dispersant which can be used in the present invention include polymer dispersants [for example, polyamide amine and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyaminocarboxylic acids. Ester, modified polyester, modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formalin condensate], and polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine , surfactants such as alkanolamines, and pigment derivatives.

The polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer according to the structure.

For example, the terminal-modified polymer having a fixed portion on the surface of the pigment has a phosphate group at the terminal as described in JP-A-3-112992, JP-A-2003-533455, and the like. A polymer having a sulfonic acid group at the terminal, as described in JP-A-2002-273191, and a partial skeleton or a heterocyclic ring having an organic dye described in Japanese Laid-Open Patent Publication No. Hei 9-77994. Polymers, etc. In addition, the Japanese patent Dispersion stability of a polymer having two or more fixed sites (acid groups, basic groups, partial skeletons of organic dyes, heterocyclic rings, etc.) on the surface of the pigment introduced into the polymer terminal, as described in JP-A-2007-277514 Also excellent, and better.

Examples of the graft-type polymer having a fixed portion on the surface of the pigment include a polyester-based dispersant, and the like. Specific examples thereof include Japanese Patent Laid-Open No. 54-37082, and Japanese Patent Laid-Open No. Hei 8- The reaction product of the poly(lower alkylene imine) and the polyester described in JP-A-2009-258668, and the like, and the polyene described in JP-A-9-169821, and the like. The reaction product of a propylamine and a polyester, a macromonomer and a nitrogen atom monomer described in Japanese Patent Laid-Open No. Hei 10-339949, No. 2004-37986, and International Publication No. WO2010/110491, etc. Grafting of a partial skeleton or a heterocyclic ring having an organic dye described in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. A copolymer of a macromonomer and an acid group-containing monomer described in JP-A-2010-106268, and the like. In particular, in view of the dispersibility of the pigment dispersant, the dispersion stability, and the developability exhibited by the coloring composition using the pigment dispersant, it is described in Japanese Patent Laid-Open Publication No. 2009-203462. An amphoteric dispersion resin of a basic group and an acidic group.

As a macromonomer to be used for the production of a graft polymer having a fixed portion on the surface of the pigment by radical polymerization, a known macromonomer can be used, and a large amount of East Asian synthesis (share) can be used. Molecular monomer AA-6 (polymethyl methacrylate with terminal group of methacryl oxime), AS-6 (end group is methyl) Acrylic fluorenyl polystyrene), AN-6S (copolymer of styrene and acrylonitrile having a terminal group of methacryl fluorenyl group), AB-6 (polybutyl acrylate having a terminal group of methacryl fluorenyl group) , Placcel FM5 (ε-caprolactone 5 molar equivalent adduct of 2-hydroxyethyl methacrylate) manufactured by Daicel Chemical Industry Co., Ltd., FA10L (2-hydroxyethyl acrylate) The ε-caprolactone 10 molar equivalent adduct), and the polyester macromonomer described in JP-A No. 2-272009. Among these, a polyester which is excellent in flexibility and solvophilic property is particularly preferable from the viewpoint of dispersibility of the pigment dispersant, dispersion stability, and developability exhibited by the coloring composition using the pigment dispersant. The macromonomer is a polyester macromonomer represented by the polyester macromonomer described in JP-A No. 2-272009.

The block type polymer described in the above-mentioned Japanese Patent Publication No. 2003-49110, and the like.

The pigment dispersing agent which can be used in the present invention can also be obtained as a commercial product. Examples of such a specific example include "DA-7301" manufactured by Phoebe Chemical Co., Ltd., and "BYK Chemie". Disperbyk-101 (polyamidoamine phosphate), Disperbyk-107 (carboxylate), Disperbyk-110, Disperbyk-111 (copolymer containing acid group), Disperbyk-130 (polypyridinium) Amine), Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-164, Disperbyk-165, Disperbyk-166, Disperbyk-170 (polymer copolymer), "BYK-P104, BYK-P105 (high molecular weight not Saturated polycarboxylate Acid)" EFKA4047, EFKA4050~EFKA4010~EFKA4165 (polyurethane type), EFKA4330~EFKA4340 (block copolymer), EFKA4400~EFKA4402 (modified polyacrylate) manufactured by EFKA ), EFKA5010 (polyester decylamine), EFKA5765 (high molecular weight polycarboxylate), EFKA6220 (fatty acid polyester), EFKA6745 (anthraquinone derivative), EFKA6750 (azo pigment derivative), Ajinomoto fine chemistry "Ajisper PB821, Ajisper PB822, Ajisper PB880, Ajisper PB881" manufactured by Ajinomoto Fine-Techno Co., Ltd., "Florene TG-710 (Amino A) manufactured by Kyoritsu Chemical Co., Ltd. "Acetrate oligomers", "Polyflow No. 50E, Polyflow No. 300 (acrylic copolymer)", "Disparlon" KS-860, Disparlon, manufactured by Nanben Chemical Co., Ltd. 873SN, Disparlon 874, Disparlon #2150 (aliphatic polycarboxylic acid), Disparlon #7004 (polyether ester), Disparlon DA-703-50, Disparlon DA-705, Disparlon DA-725", De Mo, manufactured by Kao Corporation Demol RN, Demol N (formalin polycondensate), Demol MS, Demol C, Demol SN-B "Fomalin Sulfate Polycondensate)", "Homogenol L-18 (Polymer Polycarboxylic Acid)", "Emalgen 920, Emalgen 930, Emalgen 935, Emalgen 985 (Polyoxyethylene sulfhydryl) "Phenyl ether", "Acetamin 86 (stearylamine acetate)", "Solsperse 5000" manufactured by Lubrizol (shares), Japan Derivatives), Solsperse 22000 (azo pigment derivative), Solsperse 13240 (polyester amine), Solsperse 3000, Solsperse 17000, Solsperse 27000 (polymer with functional part at the end), Solsperse 24000, Solsperse 28000, Solsperse 32000, Solsperse 38500 (grafted polymer), Nikol T106 (polyoxyethylene sorbitan monooleate) manufactured by Nikko Chemicals, MYS-IEX (polyoxygen) "Ethylene monostearate"", Hinoact T-8000E manufactured by Kawaken Fine Chemicals Co., Ltd., etc., organic oxirane polymer manufactured by Shin-Etsu Chemical Co., Ltd. KP341, "W001: Cationic surfactant" manufactured by Yushang Co., Ltd., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, Non-ionic surfactants such as polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester, "W004, W005, W017" "Anion-based surfactant", "EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer100, EFKA Polymer400, EFKA Polymer401, EFKA Polymer450" manufactured by Morishita Industry Co., Ltd., Sannopco (shares) Made by Disperse Aid 6, Disperse Aid 8. Polymer dispersant such as Disperse Aid15 and Disperse Aid9100, Adeka Pluronic L31, Adeka Pluronic F38, Adeka Pluronic L42, Adeka Pluronic L44, Adeka manufactured by ADEKA Pluronic L61, Adeka Pluronic L64, Adeka Pluronic F68, Adeka Pluronic L72, Adeka Pluronic P95, Adeka Pluronic F77, Adeka Pluronic P84, Adeka Pluronic F87, Adeka Pluronic P94, Adeka Pluronic L101, Adeka Pluronic P103, Adeka Pluronic F108, Adeka Pluronic L121 , Adeka Pluronic P-123", and Sanyo Chemical (share) system "Ionet (trade name) S-20" made by the company.

These pigment dispersants may be used singly or in combination of two or more. In the present invention, it is particularly preferred to use a pigment derivative in combination with a polymer dispersant. Further, the pigment dispersant may be used by using the terminal modified polymer having a fixed portion on the surface of the pigment, a graft polymer, a block polymer, and an alkali-soluble resin. Examples of the alkali-soluble resin include a (meth)acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and the like, and a side chain. An acidic cellulose derivative having a carboxylic acid, particularly preferably a (meth)acrylic copolymer. In addition, the N-substituted maleimide monomer copolymer described in Japanese Patent Laid-Open Publication No. Hei 10-300922, and the ether dimer copolymer described in JP-A-2004-300204, The alkali-soluble resin containing a polymerizable group described in Japanese Laid-Open Patent Publication No. Hei 7-319161 is also preferable. Specifically, an alkali-soluble resin: benzyl methacrylate/methacrylic acid/-2-hydroxyethyl methacrylate copolymer can be exemplified.

In the coloring composition, when the pigment dispersant is contained, the total content of the pigment dispersant is preferably from 1 part by mass to 80 parts by mass, more preferably from 5 parts by mass to 70 parts by mass, per 100 parts by mass of the pigment. More preferably, it is 10 mass parts - 60 mass parts. Among the dispersant components contained in the coloring composition, the specific dispersion resin is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more.

The composition of the present invention may contain only one type of pigment dispersant, and may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is in the above range.

Specifically, when the polymer dispersant is used, the amount thereof is preferably in the range of 5 parts by mass to 100 parts by mass, more preferably 10 parts by mass to 80 parts by mass, based on 100 parts by mass of the pigment. The scope of the share.

In addition, when the pigment derivative is used in combination, the amount of the pigment derivative used is preferably in the range of 1 part by mass to 30 parts by mass, more preferably 3 parts by mass, based on 100 parts by mass of the pigment. In the range of 20 parts by mass, it is particularly preferably in the range of 5 parts by mass to 15 parts by mass.

In the coloring composition, the total content of the coloring agent and the dispersing agent component is preferably 50% by mass or more and 90% by mass or less based on the total solid content of the coloring composition in terms of the curing sensitivity and the color density. More preferably, it is 55 mass % or more, 85 mass % or less, More preferably, it is 60 mass % or more, and 80 mass % or less.

<(F) alkali soluble resin>

The colored composition of the present invention preferably further contains an alkali-soluble resin.

The molecular weight of the alkali-soluble resin is not particularly limited, but Mw is preferably from 5,000 to 100,000. Further, it is preferred that Mn is from 1,000 to 20,000.

The alkali-soluble resin may have at least one base which promotes alkali solubility and is a linear organic high molecular polymer from a molecule (preferably a molecule in which an acrylic copolymer or a styrene copolymer is used as a main chain). It is suitably selected among alkali-soluble resins. From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin is preferable, and the viewpoint of controlling developability is preferable. In particular, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin is preferable.

Examples of the base which promotes alkali solubility (hereinafter, also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and are preferably soluble in an organic solvent and can be carried out by a weakly basic aqueous solution. As the base to be developed, (meth)acrylic acid is mentioned as a particularly preferable one. These acid groups may be used alone or in combination of two or more.

Examples of the monomer capable of imparting an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, and a monomer having an epoxy group such as glycidyl (meth)acrylate. A monomer having an isocyanate group such as a body or 2-isocyanatoethyl (meth)acrylate. These single-quantity bodies for introducing an acid group may be used alone or in combination of two or more. When an acid group is introduced into an alkali-soluble resin, for example, a monomer having an acid group and/or a monomer capable of imparting an acid group after polymerization (hereinafter, sometimes referred to as "a single amount for introducing an acid group" may be used. The body ") can be polymerized as a single component.

In addition, when an acid group can be introduced as a monomer component after polymerization, a treatment for imparting an acid group as described later is required after the polymerization.

In the case of producing an alkali-soluble resin, for example, a method using a known radical polymerization method can be applied. The polymerization conditions such as the temperature, the pressure, the type and amount of the radical initiator, and the type of the solvent when the alkali-soluble resin is produced by the radical polymerization method can be easily set by a person skilled in the art, and experimental conditions can be specified.

The linear organic high molecular polymer which can be used as the alkali-soluble resin is preferably a polymer having a carboxylic acid in a side chain, and examples thereof include a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, and crotonic acid. An alkali-soluble phenol resin such as a copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer or a novolak-type resin, and an acidic cellulose derivative having a carboxylic acid in a side chain, Hydroxyl The addition of an acid anhydride to a polymer. In particular, a copolymer of (meth)acrylic acid and other monomeric materials copolymerizable therewith is suitable as the alkali-soluble resin. Examples of the other monomer to be copolymerizable with (meth)acrylic acid include an alkyl (meth)acrylate, an aryl (meth)acrylate, and a vinyl compound. Examples of the (meth)acrylic acid alkyl ester and the (meth)acrylic acid aryl ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate Examples of esters, toluene (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, and the like, and examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, and A. Glycidyl acrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, etc., as Japan The N-substituted maleimide monomer described in Japanese Laid-Open Patent Publication No. Hei 10-300922, the N-phenyl maleimide, N-cyclohexyl maleimide Wait. Further, these other monomeric substances which can be copolymerized with (meth)acrylic acid may be used alone or in combination of two or more.

It is also preferred that the alkali-soluble resin contains a polymer (a) obtained by polymerizing a monomer component as described below, and the monomer component is a compound represented by the following formula (ED) and/or The compound represented by the above formula (ED2) (hereinafter, these compounds may also be referred to as "ether dimer") is an essential component.

[化76]

In the general formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

General formula (ED2)

In the formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), the description of Japanese Patent Laid-Open Publication No. 2010-168539 can be referred to.

Thereby, the colored composition of the present invention can form a cured coating film which is extremely excellent in heat resistance and extremely excellent in transparency. In the above-mentioned general formula (ED) of the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, and examples thereof include, for example, Linear or branched such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-pentyl, stearyl, lauryl, 2-ethylhexyl Alkyl group such as phenyl; cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl, 2-methyl-2-gold An alicyclic group such as an alkyl group; an alkyl group substituted by an alkoxy group such as a 1-methoxyethyl group or a 1-ethoxyethyl group; an alkyl group substituted with an aryl group such as a benzyl group; and the like. Among these, from the viewpoint of heat resistance, a substituent of a primary carbon or a secondary carbon which is not easily removed by acid or heat such as a methyl group, an ethyl group, a cyclohexyl group or a benzyl group is particularly preferable.

Specific examples of the ether dimer include dimethyl-2,2'-[oxobis(methylene)]bis-2-acrylate and diethyl-2,2'-. [oxobis(methylene)]bis-2-acrylate, di(n-propyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, di(isopropyl) -2,2'-[oxobis(methylene)]bis-2-acrylate, di(n-butyl)-2,2'-[oxobis(methylene)]bis-2 - acrylate, di(isobutyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, di(t-butyl)-2,2'-[oxo double (methylene)] bis-2-acrylate, bis(third amyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, di(stearyl)- 2,2'-[oxobis(methylene)]bis-2-acrylate, bis(lauryl)-2,2'-[oxobis(methylene)]bis-2-acrylate, Bis(2-ethylhexyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, bis(1-methoxyethyl)-2,2'-[oxo Bis(methylene)]bis-2-acrylate, bis(1-ethoxyethyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, dibenzyl -2,2'-[oxobis(methylene)]bis-2-acrylate, diphenyl-2,2'-[oxobis(methylene)]bis-2-propene Acid ester, dicyclohexyl-2,2'-[oxobis(methylene)]bis-2-acrylate, bis(t-butylcyclohexyl)-2,2'-[oxo double (Asia Methyl)]bis-2-acrylate, bis(dicyclopentadienyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, bis(tricyclodecyl) -2,2'-[oxobis(methylene)]bis-2-acrylate, bis(isobornyl)-2,2'-[oxobis(methylene)]bis-2- Acrylate, diamantyl-2,2'-[oxobis(methylene)]bis-2-acrylate, bis(2-methyl-2-adamantyl)-2,2'-[ Oxygenated double Methyl)] bis-2-acrylate. Among them, dimethyl-2,2'-[oxobis(methylene)]bis-2-acrylate, diethyl-2,2'-[oxo-double (sub- Base]] bis-2-acrylate, dicyclohexyl-2,2'-[oxobis(methylene)]bis-2-acrylate, dibenzyl-2,2'-[oxo double ( Methylene)] bis-2-acrylate. These ether dimers may be used alone or in combination of two or more. The structure from which the compound represented by the above formula (ED) is derived may also be copolymerized with other monomer.

Further, the alkali-soluble resin may contain a structural unit derived from an ethylenically unsaturated monomer represented by the following formula (X).

General formula (X)

(In the formula (X), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 10 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. n represents an integer from 1 to 15)

In the formula (X), the alkyl group of R ² preferably has 2 to 3 carbon atoms. Further, the alkyl group of R ³ has a carbon number of 1 to 20, preferably 1 to 10, and the alkyl group of R ³ may contain a benzene ring. Examples of the benzene ring-containing alkyl group represented by R ³ include a benzyl group and a 2-phenyl (iso)propyl group.

Moreover, in order to improve the crosslinking efficiency of the coloring composition in the present invention, it is preferred to use an alkali-soluble resin having a polymerizable group. When such an alkali-soluble resin is used, solvent resistance tends to be further improved. Further, there is light resistance or resistance The tendency for heat to be further improved. The alkali-soluble resin having a polymerizable group is useful as an alkali-soluble resin such as an allyl group, a (meth)acrylic group or an allyloxyalkyl group in the side chain. Examples of the polymerizable group-containing polymer include Dianan NR series (manufactured by Mitsubishi Rayon Co., Ltd.) and Photomer 6173 (acrylic acid polyaminocarboxylic acid containing COOH). Polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd., Viscoat R-264, KS Resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.) , Cyclomer P series, Placcel CF200 series (all manufactured by Daicel Chemical Industry Co., Ltd.), Ebecryl 3800 (Daicel-UCB) Ltd. manufactured) and so on. The alkali-soluble resin containing a polymerizable group is preferably a resin containing a polymerizable double bond modified by a urethane, and reacting an isocyanate group with an OH group in advance. Obtaining an unreacted isocyanate group and a compound containing a (meth)acryloyl group and reacting with a carboxyl group-containing acrylic resin; and having an epoxy group and a polymerizable double in the molecule by an acrylic resin containing a carboxyl group; An unsaturated group-containing acrylic resin obtained by the reaction of a bond compound; an acid side group type epoxy acrylate resin; and a polymerization reaction obtained by reacting an OH group-containing acrylic resin with a dibasic acid anhydride having a polymerizable double bond An acrylic resin having a double bond; a resin obtained by reacting an OH group-containing acrylic resin with an isocyanate and a compound having a polymerizable group; and Japanese Patent Laid-Open No. 2002-229207, and Japanese Patent Laid-Open No. 2003- A resin having an ester group in a side chain as described in Japanese Patent No. 335814 A resin or the like obtained by alkaline treatment, wherein the ester has a leaving group such as a halogen atom or a sulfonate group at the α-position or the β-position.

As the alkali-soluble resin, a polyvalent copolymer containing a benzyl (meth)acrylate/(meth)acrylic copolymer or a benzyl (meth)acrylate/(meth)acrylic acid/other monomer is particularly preferable. Other than this, benzyl (meth)acrylate / (meth)acrylic acid / (meth)acrylic acid 2-hydroxyethyl ester copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate, Japanese patent 2-Hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-benzene acrylate described in JP-A-7-140654 Oxypropyl propyl ester / polymethyl methacrylate macromer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc., particularly preferably benzyl methacrylate / methyl Acrylic copolymer and the like.

As the alkali-soluble resin, the descriptions of the following paragraphs 0558 to 5571 of the corresponding Japanese Patent Application Laid-Open No. 2012/0235099 The content can be incorporated into the specification of this application.

Further, the copolymer (B) described in Paragraph No. 0029 to Paragraph 0063 described in JP-A-2012-32767, and the alkali-soluble resin used in the examples, and Japanese Patent Laid-Open No. 2012 are preferably used. Adhesive resin described in Paragraph No. 0088 to Paragraph No. 0098 of No. 208474 and used in the examples The binder resin described in paragraphs 0022 to 0032 of JP-A-2012-137531, and the binder resin used in the examples, and the paragraph number of JP-A-2013-024934 The adhesive resin described in paragraphs 0143 to 0143 and the adhesive resin used in the examples, the adhesive resin used in the paragraphs 0092 to 0098 of the Japanese Patent Laid-Open Publication No. 2011-242752, and the examples, The adhesive resin described in Paragraph No. 0030 to Paragraph No. 0072 of Japanese Laid-Open Patent Publication No. 2012-032770. Such content can be incorporated into the specification of the present application. More specifically, the following resins are preferred.

[化79]

The acid value of the alkali-soluble resin is preferably from 30 mgKOH/g to 200 mgKOH/g, more preferably from 50 mgKOH/g to 150 mgKOH/g, particularly preferably from 70 mgKOH/g to 120 mgKOH/g.

Further, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, particularly preferably 7,000 to 20,000.

When the alkali-soluble resin is contained in the coloring composition, the content of the alkali-soluble resin is preferably 1% by mass to 15% by mass, and more preferably 2% by mass to 12% by mass based on the total solid content of the coloring composition. , particularly preferably from 3 mass% to 10 mass%.

The composition of the present invention may contain only one type of alkali-soluble resin, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is in the above range.

<Other ingredients>

In addition to the above components, the colored composition of the present invention may contain an organic solvent, a crosslinking agent, a polymerization inhibitor, a surfactant, an organic carboxylic acid, an organic carboxylic anhydride, etc., within the range which does not impair the effects of the present invention. Other ingredients.

<<Organic solvent>>

The colored composition of the present invention may also contain an organic solvent.

The organic solvent is not particularly limited as long as it satisfies the solubility of each component or the coating property of the coloring composition, but it is particularly preferable to consider solubility, coating property, and safety of an ultraviolet absorber, an alkali-soluble resin, or a dispersant. Sex to choose. Further, when preparing the coloring composition of the present invention, it is preferred to contain at least two kinds of organic solvents.

As the organic solvent, as the ester, for example, acetic acid B can be suitably cited. Ester, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate An alkyl oxyacetate (for example: methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, Methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-oxopropionate (for example: methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (for example) Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-oxopropane Base esters (for example: methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (for example, methyl 2-methoxypropionate, 2-methoxyl) Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-oxy-2-methylpropanoate And ethyl 2-oxy-2-methylpropanoate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), pyruvic acid Methyl ester, acetone Ethyl acetate, propyl pyruvate, methyl acetate methyl acetate, ethyl acetate ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutanoate, etc., and, as the ether, for example, suitably Listed 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, etc., and, as ketones, For example, methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone are exemplified, and examples of the aromatic hydrocarbons include toluene and xylene.

Solubility of UV absorber and alkali-soluble resin, coating surface From the viewpoint of improvement or the like, it is also preferred to mix two or more kinds of these organic solvents. In this case, a mixed solution selected from the group consisting of the methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, and lactate B is particularly preferred. Ester, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate Two or more kinds of propylene glycol methyl ether and propylene glycol methyl ether acetate.

From the viewpoint of the coating property, the content of the organic solvent in the coloring composition is preferably such that the total solid content concentration of the composition becomes 5% by mass to 80% by mass, more preferably the total solid content of the composition. The concentration is 5% by mass to 60% by mass, and particularly preferably the total solid content of the composition is 10% by mass to 50% by mass.

The composition of the present invention may contain only one type of organic solvent, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is in the above range.

<<Crosslinker>>

Further, the crosslinking agent may be used in the colored composition of the present invention to further increase the hardness of the cured film obtained by curing the colored composition.

The crosslinking agent is not particularly limited as long as it can be cured by a crosslinking reaction, and examples thereof include (a) an epoxy resin; and (b) a methyl group selected from a methyl group and an alkoxy group. a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one substituent in the group and the methoxymethyl group; (c) selected from a methylol group, an alkoxymethyl group, and an anthracene oxygen group A phenol compound, a naphthol compound or a hydroxyquinone compound substituted with at least one substituent of the methyl group. Among them, a polyfunctional epoxy is preferred Resin.

For details of specific examples of the crosslinking agent, etc., reference is made to paragraphs 0134 to 0147 of JP-A-2004-295116.

When the crosslinking agent is contained in the coloring composition of the present invention, the amount of the crosslinking agent is not particularly limited, but it is preferably 2% by mass to 30% by mass, more preferably 3% by mass based on the total solid content of the composition. %~20% by mass.

The composition of the present invention may contain only one type of crosslinking agent, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is in the above range.

<<Polymerization inhibitor>>

In the colored composition of the present invention, in order to prevent unnecessary thermal polymerization of the polymerizable compound during or during the production of the colored composition, it is desirable to add a small amount of a polymerization inhibitor.

Examples of the polymerization inhibitor which can be used in the present invention include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, and benzene.醌, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N - nitrosophenylhydroxylamine trivalent phosphonium salt and the like.

When the polymerization inhibitor is contained in the colored composition of the present invention, the amount of the polymerization inhibitor added is preferably from about 0.01% by mass to about 5% by mass based on the mass of all the compositions.

The composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is in the above range.

<<Interfacial active agent>>

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

In particular, the coloring composition of the present invention further improves liquid characteristics (particularly fluidity) when it is prepared as a coating liquid by containing a fluorine-based surfactant, so that uniformity of coating thickness or liquid-saving property can be further improved. .

In other words, when a film is formed using a coating liquid to which a coloring composition containing a fluorine-based surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is lowered, whereby the wettability to the surface to be coated is lowered. It is improved and the coatability to the coated surface is improved. Therefore, even when a film having a thickness of about several μm is formed with a small amount of liquid, it is effective to form a film having a uniform thickness with a small thickness unevenness.

The fluorine content in the fluorine-based surfactant is suitably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, particularly preferably 7% by mass to 25% by mass. Fluorine content rate The fluorine-based surfactant in this range is effective from the viewpoint of the uniformity of the thickness of the coating film or the liquid-saving property, and the solubility in the colored composition is also good.

Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, and Megafac F475. , Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781 (above, manufactured by Di Ai Sheng (share)), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above, Sumitomo 3M (share) manufacturing), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above, manufactured by Asahi Glass Co., Ltd.).

Specific examples of the nonionic surfactant 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 octyl phenyl ether, polyoxygen Vinyl nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, Pluronic L31, Pluronic L61, Pluronic L62, manufactured by BASF Corporation, Pluronic 10R5, Pluronic 17R2, Pluronic 25R2, Tetronic304, Tetronic701, Tetronic704, Tetronic901, Tetronic904, Tetronic150R1), Solsperse20000 (Lubricol, Japan).

Specific examples of the cation-based surfactant include an indigo derivative (trade name: EFKA-745, manufactured by Morishita Industry Co., Ltd.), and an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (meth)acrylic (co)polymer Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.

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

Examples of the anthrone-based surfactant include Toray. "Toray Silicone DC3PA", "Toray Silicone SH7PA", "Toray Silicone SH11PA", "Toray Silicone SH21PA", "Toray Silicone SH28PA", "Toray Silicone SH29PA", "Toray" manufactured by Dow Corning (share) Silicone SH30PA", "Toray Silicone SH8400", "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", "TSF-4452" manufactured by Momentive Performance Materials "KP341", "KF6001", "KF6002" manufactured by Shintosu Silicon Co., Ltd., "BYK307", "BYK323", "BYK330" manufactured by BYK Chemical Co., Ltd., etc.

When the surfactant is contained in the colored composition of the present invention, the amount of the surfactant added is preferably from 0.001% by mass to 2.0% by mass, more preferably from 0.005% by mass to 1.0% by mass based on the total mass of the coloring composition. %.

The composition of the present invention may contain only one type of surfactant, and may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is in the above range.

<<Organic carboxylic acid, organic carboxylic anhydride>>

The colored composition of the present invention may further contain an organic carboxylic acid having a molecular weight of 1,000 or less and/or an organic carboxylic anhydride.

Specific examples of the organic carboxylic acid compound include an aliphatic carboxylic acid or an aromatic carboxylic acid. Examples of the aliphatic carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, glycolic acid, acrylic acid, and methacrylic acid, oxalic acid, malonic acid, and the like. Succinic acid, glutaric acid, adipic acid, pimelic acid, Dicarboxylic acid such as cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, 1,2,3-propanetricarboxylic acid, bird head A tricarboxylic acid or the like such as an acid. In addition, examples of the aromatic carboxylic acid include a carboxylic acid in which a carboxyl group such as benzoic acid or phthalic acid is directly bonded to a phenyl group, and a carboxylic acid in which a carboxyl group is bonded to a phenyl group via a carbon bond. Among these, a molecular weight of 600 or less, particularly a molecular weight of 50 to 500 is particularly preferable. Specifically, for example, maleic acid, malonic acid, succinic acid, and itaconic acid are preferable.

Examples of the organic carboxylic acid anhydride include an aliphatic carboxylic acid anhydride and an aromatic carboxylic acid anhydride. Specific examples thereof include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, and succinic anhydride. , maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylate An aliphatic carboxylic acid anhydride such as an acid anhydride. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Among these, a molecular weight of 600 or less, particularly a molecular weight of 50 to 500 is particularly preferable. Specifically, for example, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferable.

When the organic carboxylic acid or the organic carboxylic acid anhydride is contained in the colored composition of the present invention, the organic carboxylic acid and/or the organic carboxylic anhydride is usually added in an amount of from 0.01% by weight to 10% by weight, preferably 0.03, based on the total solid content. It is in the range of wt% to 5 wt%, more preferably 0.05 wt% to 3 wt%.

The composition of the present invention may contain only one type of organic carboxylic acid and/or organic carboxylic anhydride, and may contain two or more types. When two or more kinds are contained, it is preferable that the total amount thereof is For the stated range.

By adding these organic carboxylic acids having a molecular weight of 1,000 or less and/or an organic carboxylic anhydride, it is possible to further reduce the residual of the undissolved matter of the colored composition while maintaining high pattern adhesion.

In addition to the above, various additives such as a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomerating agent, and the like may be added to the coloring composition as needed. As such additives, those described in paragraphs 0155 to 0156 of JP-A-2004-295116 can be incorporated into the specification of the present application.

In the coloring composition of the present invention, the sensitizer or light stabilizer described in paragraph 0078 of JP-A-2004-295116, and the thermal polymerization inhibitor described in paragraph 0081 of the publication may be contained.

The composition of the present invention may contain only one type of the above-mentioned components, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is in the above range.

<Method for Preparing Colored Composition>

The colored composition of the present invention is prepared by mixing the ingredients.

Furthermore, when preparing the colored composition, the components constituting the colored composition may be formulated at one time, and the components may be dissolved. Disperse in the solvent and then mix. In addition, the order of input or the working conditions at the time of preparation are not particularly limited. For example, all ingredients can be dissolved at the same time. The composition is prepared by dispersing in a solvent, and if necessary, the components may be suitably prepared into two or more kinds of solutions. Dispersion, these solutions are used (when applied). The dispersion was mixed to prepare as a composition.

The colored composition prepared in the above manner can be used by filtration using a filter having a pore diameter of preferably 0.01 μm to 3.0 μm, more preferably a pore diameter of 0.05 μm to 0.5 μm.

The colored composition of the present invention can be preferably used as a coloring composition for forming a coloring layer of a color filter. More specifically, since the colored composition of the present invention can form a cured film excellent in heat resistance and color characteristics, it can be suitably used for forming a colored pattern (colored layer) of a color filter. Further, the colored composition of the present invention can be suitably used as a solid-state imaging device (for example, a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), or the like) or a liquid crystal display device (liquid crystal) A coloring composition for forming a coloring pattern such as a color filter used in an image display device such as a display (Liquid Crystal Display (LCD)) or an organic electroluminescence (EL) display device. Further, it can also be suitably used as a production use for printing inks, inkjet inks, paints, and the like. Among them, it can be suitably used as a color filter for solid-state imaging elements such as CCD and CMOS.

<Method for Producing Cured Film, Pattern Forming Method, Color Filter, and Color Filter>

Next, the cured film, the pattern forming method, and the color filter in the present invention will be described in detail by a method of production thereof.

The cured film of the present invention is formed by curing the colored composition of the present invention. The cured film can be preferably used for a color filter.

The pattern forming method of the present invention applies the coloring composition of the present invention The support is formed to form a colored composition layer, and unnecessary portions are removed to form a colored pattern.

The pattern forming method of the present invention can be suitably applied to the formation of a coloring pattern (pixel) which the color filter has.

The composition of the present invention can be used to form a color filter by pattern formation by a so-called photolithography method, and can also be patterned by dry etching.

That is, as a first method of manufacturing the color filter of the present invention, a method of producing a color filter comprising the step of forming a colored composition layer on a support using the colored composition of the present invention can be exemplified. a step of exposing the colored composition layer into a pattern; and a step of developing the unexposed portion of the exposed colored composition layer.

Moreover, as a second manufacturing method of the color filter of the present invention, a method of producing a color filter comprising: applying a colored composition to a support to form a colored composition layer and hardening can be exemplified. a step of forming a coloring layer; a step of forming a photoresist layer on the colored layer; a step of patterning the photoresist layer by performing exposure and development to obtain a resist pattern; and The resist pattern is a step of dry etching the colored layer as an etch mask.

In the present invention, it is more preferably produced by photolithography.

These will be described in detail below.

Hereinafter, each step in the pattern forming method of the present invention will be described in detail via a method of manufacturing a color filter for a solid-state image sensor, but the present invention is not limited to this method. Hereinafter, a color filter for a solid-state imaging device may be used. It is called "color filter".

<<Steps of forming a colored composition layer>>

In the step of forming the colored composition layer, the colored composition of the present invention is applied to a support to form a colored composition layer.

As a support which can be used in this step, for example, a solid-state image sensor in which an image pickup element (light receiving element) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (for example, a germanium substrate) can be used. Substrate.

The colored pattern in the present invention may be formed on the imaging element forming surface side (surface) of the solid-state imaging element substrate, or may be formed on the non-imaging element forming surface side (back surface).

A light shielding film may be provided between the colored patterns in the solid-state image sensor or on the back surface of the solid-state image sensor substrate.

Further, in order to improve the adhesion to the upper layer, prevent the diffusion of the substance, or to flatten the surface of the substrate, an undercoat layer may be provided on the support as needed. The solvent may be added to the undercoat layer, an alkali-soluble resin, a polymerizable compound, a polymerization inhibitor, a surfactant, a photopolymerization initiator, etc., and the components are preferably self-adapted into the composition of the present invention. Suitable for the selection of ingredients.

As a method of imparting the coloring composition of the present invention to a support, various coating methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing can be applied.

The drying (prebaking) of the colored composition layer coated on the support can be carried out at a temperature of 50 ° C to 140 ° C for 10 seconds to 300 seconds by means of a hot plate, an oven or the like.

<Step of forming a pattern by photolithography>

<<Exposure step>>

In the exposure step, for example, a coloring composition layer formed in the colored composition layer forming step is subjected to pattern exposure by using an exposure device such as a stepper through a mask having a predetermined mask pattern. Thereby, a cured film can be obtained.

As the radiation (light) which can be used for exposure, in particular, ultraviolet rays (particularly i-rays) such as g-rays and i-rays can be preferably used. Irradiation amount (exposure amount) is preferably ^{30mJ / cm 2 ~ 1500mJ / cm} 2, more preferably ^{50mJ / cm 2 ~ 1000mJ / cm} 2, and particularly preferably ^{80mJ / cm 2 ~ 500mJ / cm} 2.

The film thickness of the cured film (colored film) is preferably 1.0 μm or less, more preferably 0.1 μm to 0.9 μm, still more preferably 0.2 μm to 0.8 μm.

By setting the film thickness to 1.0 μm or less, high resolution and high adhesion can be obtained, which is preferable.

Further, in this step, a cured film having a thin film thickness of 0.7 μm or less can be suitably formed, and the obtained cured film can be developed by a pattern forming step to be described later, whereby not only a film can be obtained. And a coloring pattern excellent in developability, suppression of surface roughness, and pattern shape.

<<Development step>>

Then, an alkali development treatment is performed, whereby the colored composition layer of the unirradiated portion of the light in the exposure step is eluted into the alkaline aqueous solution, and only the photohardened portion remains.

As the developer, an organic alkaline developer which does not cause damage to an image pickup element or a circuit of the substrate is preferable. The development temperature is usually 20 ° C ~ 30 ° C, the development time first The front is 20 seconds to 90 seconds. In order to further remove the residue, in recent years, there have been cases in which 120 seconds to 180 seconds have been carried out. Further, in order to further improve the residue removal property, the following steps may be repeated a plurality of times: the developer is shaken off every 60 seconds, and the developer is supplied again.

Examples of the alkaline agent to be used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and hydroxide. Organic basic compounds such as tetrabutylammonium, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5,4,0]-7-undecene, As the developer, an alkaline aqueous solution obtained by diluting the alkali agents with pure water so as to have a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass, is preferably used.

Further, an inorganic base may be used in the developer, and as the inorganic base, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate or sodium metasilicate may be used.

Further, when a developer containing such an aqueous alkaline solution is used, it is usually washed (rinsed) with pure water after development.

Then, it is preferred to carry out heat treatment (post-baking) after drying. If a color pattern of a plurality of colors is formed, the steps can be sequentially repeated for each color to produce a hardened film. Thereby, a color filter can be obtained.

The post-baking is a heat treatment for developing after development which is completely hardened, and is usually subjected to a heat hardening treatment at 100 ° C to 240 ° C, preferably 200 ° C to 240 ° C.

Can use heating plate or convection oven (hot air circulation dryer), high frequency heating machine The post-baking treatment is performed on the developed coating film by a continuous or batch method in such a manner as to be the above-described condition.

<Case where a pattern is formed by dry etching>

When the pattern is formed by dry etching, the description of Japanese Patent Laid-Open Publication No. 2013-64993 can be incorporated into the specification of the present application.

In addition, the manufacturing method of the present invention may have a step known as a method of producing a color filter for a solid-state image sensor as a step other than the above. For example, after the colored composition layer forming step, the exposing step, and the pattern forming step, a hardening step of hardening the formed colored pattern by heating and/or exposure may be included as needed.

Further, when the colored composition of the present invention is used, for example, there is a case where clogging of the nozzle or the piping portion of the coating device discharge portion or adhesion of the colored composition or pigment in the coating machine occurs. precipitation. Pollution caused by drying, etc. Therefore, in order to efficiently clean the contamination caused by the colored composition of the present invention, it is preferred to use the solvent associated with the present composition as a cleaning liquid. In addition, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The cleaning liquid described in the Japanese Patent Laid-Open Publication No. Hei. No. 2007-281523, the Japanese Patent Publication No. 2007-2102, and the Japanese Patent Publication No. 2007-281523, and the like can also be used. It is suitably used for the cleaning and removal of the colored composition of the present invention.

Among them, an alkylene glycol monoalkyl ether carboxylate and an alkylene glycol monoalkyl ether are preferred.

These solvents may be used singly or in combination of two or more. When two or more kinds are mixed, it is preferred to mix a solvent having a hydroxyl group with a solvent having no hydroxyl group. The mass ratio of the solvent having a hydroxyl group to 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. Particularly preferred is a mixed solvent of Propylene Glycol Monomethyl Ether Acetate (PGMEA) and Propylene Glycol Monomethyl Ether (PGME) in a ratio of 60/40. Furthermore, in order to increase the permeability of the cleaning solution to the contaminants, the surfactant associated with the composition may also be added to the cleaning solution.

Since the color filter of the present invention uses the coloring composition of the present invention, it is possible to perform exposure with excellent exposure margin, and the formed color pattern (colored pixel) has an excellent pattern shape, and the surface of the pattern is rough or Since the residue in the developing unit is suppressed, it is excellent in color characteristics.

The color filter of the present invention can be suitably used for a solid-state imaging device such as a CCD or a CMOS, and is particularly suitable for a high-resolution CCD or CMOS such as more than one million pixels. The color filter for a solid-state image sensor of the present invention can be used, for example, as a color filter disposed between a light receiving portion constituting each pixel of a CCD or CMOS and a microlens for collecting light.

In addition, the film thickness of the colored pattern (colored pixel) in the color filter of the present invention is preferably 2.0 μm or less, more preferably 1.0 μm or less, and still more preferably 0.7 μm or less.

Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less.

<Solid image sensor>

The solid-state imaging device of the present invention includes the color filter of the present invention described above. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it is a color filter of the present invention and functions as a solid-state imaging device. For example, the following configuration is exemplified.

The configuration includes a plurality of photodiodes constituting a light receiving region of a solid-state imaging device (a CCD image sensor, a CMOS image sensor, etc.) and a transfer electrode including a polysilicon or the like on the support, and the light is The polarizer and the transfer electrode have a light-shielding film containing tungsten or the like which is opened only to the light-receiving portion of the photodiode, and is formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion. The element protective film containing a tantalum nitride or the like has the color filter for a solid-state image sensor of the present invention on the element protective film.

Further, a configuration may be employed in which a light collecting means (for example, a microlens or the like) is provided on the element protective layer and under the color filter (on the side close to the support). The configuration of the following is the same or the configuration of the light collecting means on the color filter.

<Image display device>

The color filter of the present invention can be used not only for the solid-state imaging device but also for an image display device such as a liquid crystal display device or an organic EL display device, and is particularly suitable for use in a liquid crystal display device. A liquid crystal display device having the color filter of the present invention can display a high-quality image, and the display image of the high-quality image has good color tone and display Excellent characteristics.

For the definition of the display device or the details of each display device, for example, "Electronic display elements (Kosyo Chosakai Publishing (shares) issued in 1990)", "Display elements (Ibuki Shunzhang, The industrial book (Sangyo Tosho) (issued in 1989) is listed in the book. In addition, the liquid crystal display device is described in, for example, "Next-generation liquid crystal display technology (edited by Uchida Natsuo, Industrial Research Association (share), 1994). The liquid crystal display device to which the present invention is applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the "next generation liquid crystal display technology".

The color filter of the present invention can also be used for a color film transistor (Thin Film Transistor (TFT) type liquid crystal display device. A color TFT liquid crystal display device is described in, for example, "Color TFT Liquid Crystal Display (Kyoritsu Publishing Co., Ltd., 1996)". Further, the present invention can also be applied to a liquid crystal whose viewing angle is expanded, such as a horizontal electric field driving method such as In-Plane Switching (IPS) or a pixel division method such as Multi-Domain Vertical Alignment (MVA). Display device, or Super Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), Optically Compensated Splay (OCS), Fringe Field Switching ( Fringe Field Switching (FFS), and Reflective Optically Compensated Bend (R-OCB).

In addition, the color filter of the present invention is also available for bright and high-definition color. Color-filter On Array (COA) mode. In the COA liquid crystal display device, in addition to the usual required characteristics as described above, the required characteristics of the color filter layer may require characteristics for the interlayer insulating film, that is, low dielectric constant and peeling resistance. . In the color filter of the present invention, since a dye multimer having excellent hue is used, color purity, light transmittance, and the like are excellent, and color tone (pixel) is excellent in color tone, so that high resolution and long-term durability can be provided. Excellent COA liquid crystal display device. Further, in order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.

For the image display methods, for example, "EL, Plasma Display Panel (PDP), LCD Display - Technology and Market Trends - (Toray Research Center Research and Research Department 2001) It is described on page 43 of the issue).

The liquid crystal display device including the color filter 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 securing 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 including these well-known members. For example, "The market of the '94 liquid crystal display peripheral materials and chemicals (Island Kentaro CMC (share) issued in 1994), "2003 liquid crystal related market status and future prospects (volume) (Table Liangji Fuji It is described in the Fuji Chimera Research Institute (shares, issued in 2003).

For the backlight, in "The Society for Information Display (Meeting Digest)" 1380 (2005) (A. Iino (A.Konno) et al., or "Monthly Display" December 2005, pages 18 to 24 (Island Kang Yu), "Monitor Monthly", December 2005, page 25~ It is recorded on page 30 (Yumu Longming).

When the color filter of the present invention is used for a liquid crystal display device, high contrast can be achieved when combined with a three-wavelength tube of a previously known cold cathode tube, and further, by using red, green, and blue LED light sources ( As a backlight, RGB-LED can provide a liquid crystal display device having high luminance, high color purity, and good color reproducibility.

[Examples]

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to the following examples as long as the scope of the invention is not exceeded. In addition, "%" and "parts" are quality standards unless otherwise specified.

<Synthesis Example of Pigment Compound A-1>

(Synthesis of Intermediate 1)

In the synthesis example of the compound No. 2 of the handbook of International Publication WO 2013/082409, the methyl iodide was changed to ethyl iodide to obtain the intermediate 1.

(Synthesis of Intermediate 2)

In the hydrazine chlorination of the acid red 289 of the exemplified compound 1 of the International Publication WO 2013/031838, the intermediate 1 was used to obtain the intermediate 2.

(Synthesis of Intermediate 3)

Intermediate 2 (7.98 g) was dissolved in 40 ml of dichloromethane and stirred in an ice bath. N-ethylethanolamine (1.88 g) was added dropwise to the solution, and the mixture was stirred at room temperature for three hours, and then washed with 100 ml of 1N hydrochloric acid water, and then washed with saturated brine. The organic layer was dried over sodium sulfate, and the residue was concentrated in vacuo to 50 ml of chloroform and purified by column chromatography (chloroform: ethyl acetate = 7:3) to give 6.65 g. Intermediate 3.

Maximum absorption wavelength: 543nm (methanol)

(Synthesis of Intermediate 4)

Intermediate 3 (5 g), 2-isocyanatoethyl methacrylate (0.96 g), Neostann U-600 (manufactured by Nitto Kasei Co., Ltd.) 10 mg, 2,6-di-t-butyl 4-Methylphenol (5 mg) was dissolved in 30 ml of dimethylacetamide and stirred at 60 ° C for 4 hours. The reaction liquid was added to 100 ml of water, and extracted with 100 ml of ethyl acetate. Thereafter, it was dried with sodium sulfate and concentrated under reduced pressure. 100 ml of acetonitrile was added to the residue and stirred for 1 hour, followed by filtration to obtain 4.5 g of Intermediate 4.

Maximum absorption wavelength: 543nm (methanol)

(Synthesis of Pigment Compound A-1)

Intermediate 4 (4 g) was dissolved in 20 ml of methanol, and lithium N,N-bis(trifluoromethanesulfonyl) phthalimide (1.16 g) was added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the mixture was extracted with 100 ml of water and 100 ml of ethyl acetate, and the organic layer was dried over sodium sulfate and concentrated under reduced pressure. 50 ml of acetonitrile was added to the obtained residue, followed by dispersion washing, followed by filtration to obtain a pigment compound A-1 (4 g).

Maximum absorption wavelength: 543nm (methanol)

<Synthesis Example of Pigment Compound A-2>

In the synthesis example of the pigment compound A-1, lithium N,N-bis(trifluoromethanesulfonyl) sulfoximine is converted into potassium N,N-bis(nonafluorobutyrylsulfonyl) sulfoxide. The synthesis was carried out in the same manner to obtain the pigment compound A-2.

Maximum absorption wavelength: 543nm (methanol)

<Synthesis Example of Pigment Compound A-3>

In the synthesis example of the pigment compound A-1, lithium N,N-bis(trifluoromethanesulfonyl) sulfoximine is converted into potassium N,N-hexafluoropropane-1,3-disulfonyl sulfoximine In the same manner as above, the synthesis was carried out in the same manner to obtain the pigment compound A-3.

Maximum absorption wavelength: 543nm (methanol)

<Synthesis Example of Pigment Compound A-4>

In the synthesis example of the dye compound A-1, the lithium N,N-bis(trifluoromethanesulfonyl) sulfoximine is converted into lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex, and the same is true. The synthesis was carried out to obtain the pigment compound A-4.

Maximum absorption wavelength: 543nm (methanol)

<Pigment Compound A-5~ Pigment Compound A-15>

According to the synthesis example, a monomer which is a raw material of the repeating unit A-5 to repeating unit A-15 which will be described later is synthesized.

<Synthesis Example of Pigment Polymer P-1>

24 g of cyclohexanone was added to a three-necked flask and heated to 90 ° C under a nitrogen atmosphere. To the solution was added dropwise a pigment compound A-1 (31.3 g, 25 mmol), methacrylic acid (6.45 g, 75 mmol), dodecyl mercaptan (1.89 g, 9.35 mmol), 2,2'-even over 1 hour. A mixed solution of nitrogen bis(isobutyrate) dimethyl ester [trade name: V601, manufactured by Wako Pure Chemical Industries, Ltd.) (4.31 g, 18.7 mmol) and cyclohexanone (65.9 g). Thereafter, the mixture was stirred at 90 ° C for 3 hours, and then cooled to room temperature, and added dropwise to a mixed solvent of ethyl acetate / acetonitrile = 1156 mL / 144 mL to carry out reprecipitation. After drying at 40 ° C for 1 day, 20.1 g of Intermediate P-1 was obtained. The acid value of the intermediate P-1 was 2.02 mmol/g, and the composition ratio (mole ratio) was confirmed by ¹ H-nuclear magnetic resonance (NMR). As a result, the dye portion: methacrylic acid portion = 25:75 .

The intermediate P-1 (12.5 g) obtained above, glycidyl methacrylate (2.68 g), tetraethylammonium bromide (0.5 g), and p-methoxyphenol (0.015 g) were added to a three-necked flask. Cyclohexanone (83.3 g) was stirred at 105 ° C for 4 hours under air. Thereafter, the mixture was allowed to cool to room temperature, and added dropwise to a mixed solvent of ethyl acetate / acetonitrile = 748 mL / 39 mL to carry out reprecipitation. After drying at 40 ° C for 1 day, 5.52 g of the dye multimer P-1 was obtained. The acid value of the dye polymer P-1 was 0.94 mmol/g, and the composition ratio (mol ratio) was confirmed by ¹ H-NMR. As a result, the dye portion: methacrylic acid portion: polymerizable group-containing portion = 25: 40 :35.

<Synthesis Example of Pigment Polymer P-2 to Pigment Polymer P-15>

The monomer was changed in such a manner that the dye compound A-1 and other compounds in the dye multimer P-1 were changed to the repeating unit described in the following Table 1, and the same operation was carried out to carry out the synthesis.

The respective repeating units constituting the dye multimer are shown below.

[化81]

[化83]

[Examples and Comparative Examples]

1. Preparation of resist liquid

A component for the undercoat layer was prepared by mixing and dissolving the components of the following composition.

<Composition of resist liquid for undercoat layer>

(TAZ-107, manufactured by Green Chemical Co., Ltd.)

2. Fabrication of tantalum wafer substrate with undercoat

The 6-inch wafer was heat-treated at 200 ° C for 30 minutes in an oven. Then, the resist liquid was applied onto the tantalum wafer so as to have a dry film thickness of 1.5 μm, and further dried in an oven at 220 ° C for 1 hour to form an undercoat layer. A silicon wafer substrate with an undercoat layer.

3. Preparation of coloring composition

3-1. Preparation of Blue Pigment Dispersion

The blue pigment dispersion 1 was prepared in the following manner.

Using a beads mill (zirconia beads, diameter 0.3 mm), containing 13.0 parts of CI Pigment Blue 15:6 (blue pigment, average particle diameter of 55 nm), and 5.0 parts as a pigment dispersant A mixture of Disperbyk 111 and 82.0 parts of PGMEA was mixed for 3 hours. Dispersion to prepare a pigment dispersion. Thereafter, a high-pressure disperser NANO-3000-10 (manufactured by BEE Co., Ltd.) equipped with a pressure reducing mechanism was used, and dispersion treatment was carried out at a flow rate of 500 g/min under a pressure of 2000 kg/cm ³ . This dispersion treatment was repeated 10 times, and the blue pigment dispersion liquid 1 (CI Pigment Blue 15:6 dispersion liquid having a pigment concentration of 13%) used in the coloring composition of the example or the comparative example was obtained.

The particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)), and the result was 24 nm.

3-2. Preparation of coloring composition

Each of the components described below was mixed, dispersed, and dissolved to obtain each of the colored compositions of the examples and the comparative examples.

Sclerosing compound

KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate)

A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated modified dipentaerythritol hexaacrylate) [Chem. 86]

4. Production of color filters using coloring compositions

<pattern formation>

Each of the colored compositions of the examples and the comparative examples prepared in the manner described above was applied onto the undercoat layer of the undercoated germanium wafer substrate obtained in the above, to form a colored composition layer. (Coating film). Then, a heating plate of 100 ° C was used, and heat treatment (prebaking) was performed for 120 seconds so that the dry film thickness of the coating film became 0.6 μm.

Then, using an i-ray stepwise exposure apparatus FPA-3000i5+ (manufactured by Canon), a square island mask having a pattern of 1.0 μm on each side was transmitted at a wavelength of 365 nm to 50 mJ. The exposure was performed at various exposure amounts of /cm ² to 1200 mJ/cm ² .

Thereafter, the germanium wafer substrate on which the irradiated coating film is formed is placed on the rotation. Spray-developer (DW-30 type, manufactured by Chemitronics), using CD-2000 (Fujifilm Electronic Materials Co., Ltd.) for 60 seconds at 23 ° C Developing, and forming a colored pattern on the germanium wafer substrate.

The germanium wafer on which the colored pattern is formed is fixed on the horizontal rotating table by a vacuum chuck method, and the germanium wafer substrate is rotated by a rotating device at a rotation speed of 50 rpm, and is above the center of rotation thereof. The pure water was supplied from the discharge nozzle in a shower form to perform a rinsing treatment, and then spray-dried.

In the manner described above, a monochrome color filter having a colored pattern formed by the coloring composition of the embodiment or the comparative example was produced.

Thereafter, the size of the colored pattern was measured using a Scanning Electron Microscope (SEM) "S-9260A" (manufactured by Hitachi High-Technologies Co., Ltd.). The exposure amount in which the pattern size was changed to 1.0 μm was set as the optimum exposure amount.

5. Performance evaluation

5-1. Heat resistance

The tantalum wafer substrate coated with the coloring composition obtained above was placed on a hot plate at 200 ° C so as to be in contact with the substrate surface, and heated for 1 hour, and then a colorimeter MCPD-1000 was used ( Otsuka Electronics (share manufacturing), measuring heating The color difference (ΔE*ab value) before and after was used as an index for evaluating the heat fastness, and was evaluated based on the following criteria. The smaller the value of the ΔE*ab value, the better the heat resistance. Furthermore, the ΔE*ab value is a value obtained by the following color difference formula using the CIE1976 (L*, a*, b*) spatial color system (Japanese Color Society, New Color Science Handbook (1985) p .266).

△E*ab={(△L*) ² +(△a*) ² +(△b*) ² } ^1/2

The evaluation was performed by the following criteria.

A: The value of △E*ab is 0 or more and less than 1.0.

B: The value of ΔE*ab is 1.0 or more and less than 3.0.

C: ΔE*ab has a value of 3.0 or more

5-2. Cyclohexane solubility

The solvent solubility of the obtained coloring composition to PGMEA at 25 ° C was evaluated by the following criteria.

A: shows a solubility of 12.5 mass% or more

B: 10% by mass or more and less than 12.5% by mass

C: 5 mass% or more and less than 10 mass%

D: less than 5 mass%

5-3. Color shift evaluation

The absorbance (absorbance A) of the colored pattern in each color filter was measured by MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.).

A CT-2000L solution (manufactured by Fujifilm Electronic Materials Co., Ltd.; transparent base agent) was applied onto the colored pattern forming surface of the color filter so as to have a dry film thickness of 1 μm, and dried to form a transparent film. Heat treatment was carried out at 280 ° C for 5 minutes.

After the completion of the heating, the absorbance (absorbance B) of the transparent film adjacent to the colored pattern was measured by MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.).

With respect to the value of the absorbance B of the obtained transparent film, the ratio [%] of the value of the absorbance A of the colored pattern measured before heating was calculated [the following (Formula A)]. This is used as an index for evaluating the color shift of adjacent pixels.

(Formula A) Color shift (%) = absorbance B / absorbance A × 100

A: The value of the formula A is 0 or more and less than 2

B: The value of the formula A is 2 or more ~ less than 5

C: the value of the formula A is 5 or more

5-4. Spectral evaluation before and after development

A CT-4000L solution (manufactured by Fujifilm Electronic Materials Co., Ltd.; transparent base agent) was applied onto a ruthenium wafer so that the dry film thickness became 0.1 μm, and dried to form a transparent film at 220 ° C. Heat treatment was carried out for 5 minutes.

The colored composition was applied so as to have a film thickness of 0.6 μm using a spin coater, and subjected to heat treatment (prebaking) for 120 seconds using a hot plate at 100 °C.

Then, exposure was performed at an exposure dose of 500 mJ/cm ² at a wavelength of 365 nm using an i-ray stepwise exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.).

The transmittance of the color filter obtained in the above manner was measured in a wavelength range of 300 nm to 800 nm by a spectrophotometer (see: glass substrate) of an ultraviolet-visible near-infrared spectrophotometer UV3600 (manufactured by Shimadzu Corporation).

Loaded in rotation. On a horizontal rotary table of a DJ-30 type (manufactured by Chemitronics Co., Ltd.), a CD-2000 (manufactured by Fujifilm Electronic Materials Co., Ltd.) was used for liquid-coat development at 23 ° C for 60 seconds, and then used. The crucible wafer was rotated by a rotating device at a rotation speed of 50 rpm, and pure water was supplied from a discharge nozzle from above to the center of rotation to perform rinsing treatment, followed by spray drying. After the drying, the spectrometry was again performed, and the transmittance change before and after the development was evaluated as follows (when the transmittance before development was T0 and the transmittance after development was T1, the formula |T0- The value represented by T1|). Above B is a practical level.

AA: The transmittance change before and after development is less than 2% in all areas from 300 nm to 800 nm.

A: The transmittance change before and after development is 2% or more and less than 5% in all areas from 300 nm to 800 nm.

B: The transmittance change before and after development is 5% or more and less than 10% in all regions from 300 nm to 800 nm.

C: The transmittance change before and after development is 10% or more in all regions from 300 nm to 800 nm.

As is clear from the above table, it is understood that the composition of the present invention has high light resistance and can effectively suppress spectral change during development. Further, it is also effective in suppressing heat resistance, solvent solubility, and color shift change.

On the other hand, when the xanthene dye structure is not a multimer (Comparative Example 1 to Comparative Example 3), the light resistance and/or the spectral split at the time of development are likely to change. Further, each of the evaluations of heat resistance, solvent solubility, and color shift change tends to be unsatisfactory.

Claims (16)

A coloring composition comprising: a dye multimer comprising at least one of a repeating unit represented by the formula (A1-1) and a repeating unit represented by the formula (A1-2); and a curable compound ; In the general formula (A1-1), one of R ¹ to R ¹⁵ is a main chain structure represented by the following general formula (A1-1-1), and at least one of R ¹ to R ¹⁵ is an anion. a substituent or an anion group-containing substituent, R ¹ and R ³ are each independently an aliphatic hydrocarbon group, R ² and R ⁴ are each independently an aromatic hydrocarbon group, and R ⁵ to R ¹⁰ each independently represent a hydrogen atom or a halogen. An atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and R ¹¹ to R ¹⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carbonyl group, a nitro group, an amine group, an alkylamino group, an arylamino group, or Sulfonyl In the formula (A1-1-1), L ¹¹ represents a single bond or a divalent linking group, and R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group; In the general formula (A1-2), one of R ¹ to R ¹⁵ includes a main chain structure represented by the above formula (A1-1-1), and R ¹ and R ³ are each independently an aliphatic hydrocarbon group. R ² and R ⁴ are each independently an aromatic hydrocarbon group, and R ⁵ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and R ¹¹ to R ¹⁵ each independently represent a hydrogen atom or a halogen. An atom, an alkyl group, an aryl group, a carbonyl group, a nitro group, an amine group, an alkylamino group, an arylamino group, or a sulfonyl group; and X represents an anion which forms a relative salt with a cation of xanthene. The coloring composition according to claim 1, wherein the anionic group in the formula (A1-1) comprises a carboxylate anion, a sulfonate anion, represented by the formula (A1-1-2) An anion or an anion represented by the formula (A1-1-3), or X in the formula (A1-2) is a carboxylate anion, a sulfonate anion, a quinone anion, a methide anion, and a boric acid Any one of the salt anions; In the formula (A1-1-2), L ¹ represents a single bond or a divalent linking group, L ² represents -SO ₂ - or -CO-, and G represents a carbon atom or a nitrogen atom, and when G is a carbon atom, N1 represents 2, when G is a nitrogen atom, n1 represents 1, R ⁶ represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom, and when n1 is 2, two R ^{6 's} may be the same or different; In the formula (A1-1-3), L ¹ represents a single bond or a divalent linking group, L ² represents -SO ₂ - or -CO-, L ³ represents a divalent linking group, and G represents a carbon atom or nitrogen. An atom, when G is a carbon atom, n2 represents 1, and when G is a nitrogen atom, n2 represents 0, and R ^7A and R ^7B each independently represent an alkylene group containing a fluorine atom or an extended aryl group containing a fluorine atom, R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group. The colored composition according to claim 1 or 2, wherein the dye multimer further has an alkali-soluble group. The colored composition according to Item 1 or 2, wherein the dye multimer further has a polymerizable group. The colored composition according to Item 1 or 2, wherein the curable compound is a polymerizable compound and further contains a photopolymerization initiator. Such as the coloring composition described in claim 1 or 2, A pigment having an indigo skeleton is included. The scope of the patent application to item 1 or 2 of the coloring composition, R wherein R formula (A1-1) and a formula of ¹¹ ~ R ¹⁵ is (A1-2) of ¹¹ ~ R ¹⁵ is One is a main chain structure represented by the general formula (A1-1-1). The patentable scope herein to item 1 or 2 of the coloring composition, wherein R and R of the general formula R ² (A1-1) is ^4, and the formula (A1-2) ^2, and R ⁴ is phenyl . The colored composition according to claim 1 or 2, wherein R ² and R ^{4 of the} formula (A1-1) and at least 1 of R ² and R ⁴ of the formula (A1-2) One is represented by the following general formula (A1-1-2); In the formula (A1-1-2), R ²³ to R ²⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group having 1 to 12 carbon atoms, a carbonyl group, a carbonyl guanamine group, or a sulfonate. a mercapto group, a sulfonylamino group, a nitro group, an amine group, an aminocarbonyl group, an aminosulfonyl group, a sulfonyl quinone imine group or a carbonyl fluorenylene group, and R ²² and R ²⁶ each independently represent a carbon The number is 1 to 5 alkyl groups. The scope of the patent application to item 1 or 2 of the coloring composition, wherein R R formula (A1-1) is ¹ and R ^3, and the formula (A1-2) is ¹ and R ³ are each independently It is an alkyl group having 1 to 5 carbon atoms. The colored composition according to claim 1 or 2, which is used for forming a coloring layer of a color filter. A cured film obtained by curing the colored composition according to any one of the first to eleventh aspects of the invention. A method of producing a color filter, comprising: forming a colored composition layer on a support using the colored composition according to any one of claims 1 to 11; a step of exposing the composition layer to a pattern; and developing the unexposed portion of the exposed colored composition layer. A color filter comprising the cured film according to claim 12 of the patent application or the method for producing a color filter according to claim 13 of the patent application. A solid-state image pickup element comprising the color filter of claim 14 of the patent application. An image display device comprising the color filter of claim 14 of the patent application.