KR20160102272A - Coloring composition, cured film, manufacturing method for color filter, color filter, solid state imaging element, and image display device - Google Patents

Abstract

A color filter, a color filter, a solid-state image pickup device, and an image display device using the coloring composition, a color filter, a solid-state image pickup device, and an image display device, wherein a cured film having excellent heat resistance is obtained.
A colorant composition comprising a dye multimer having a repeating unit represented by the following formula and a curable compound; 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 are each independently a hydrogen atom, a halogen atom, an aliphatic 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 amino group, an alkylamino group, an arylamino group, or a sulfone Represents a diary.

Description

TECHNICAL FIELD [0001] The present invention relates to a color filter, a color filter, a color filter, a color filter, a color filter, a color filter,

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

Conventionally, a color filter is manufactured by forming a coloring pattern by a photolithography method, a dry etching method, or the like using a coloring composition containing a dye compound, a curing compound and, if necessary, other components. Such a coloring composition is used for forming a color filter layer of a solid-state image pickup device or an image display device.

The xanthine compounds are described in, for example, Patent Document 1 and Patent Document 2. Patent Document 3 discloses a colored curable composition containing a pigment multimer containing a pigment part derived from a xanthene compound as a partial structure.

Patent Document 1: International Publication No. WO2013 / 089197 Patent Document 2: International Publication No. WO2013 / 146218 Patent Document 3: JP-A-2012-32754

Here, it is believed that a dye multimer can increase the dye concentration in the coloring composition as compared with a low molecular compound as described in Patent Document 1 and Patent Document 2, and that the dye compound is hardly dropped off as a cured film have. However, when the inventors of the present invention have studied, it has been found that a zeta potential dye having a specific structure tends to undergo spectral fluctuation or poor light resistance at the time of development. SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a colored composition which does not cause spectral fluctuation during development and which can provide a cured film having excellent light resistance and a cured film using the colored composition, , A solid-state image pickup device and an image display device.

Under such circumstances, the present inventors have conducted intensive studies and, as a result, have found that the above problems can be solved by employing a predetermined xanthan gum structure in a colorant multimer containing a repeating unit having a xanthan gum structure. Specifically, the above-mentioned problem is solved by the following means <1>, preferably by <2> to <16>.

<1> A dye multimer having a repeating unit represented by the general formula (A1-1) and / or a repeating unit represented by the general formula (A1-2)

Curable compound

A coloring composition;

In general formula (A1-1)

[Chemical Formula 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 anionic group or an anionic group substituent 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, R ⁵ ~ R ¹⁰ each independently represent a hydrogen atom, a halogen 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 amino group, an alkylamino group, an arylamino group , Or a sulfonyl group;

In general formula (A1-1-1)

(2)

In the general 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 general formula (A1-2)

(3)

In the general formula (A1-2), one of R ¹ to R ¹⁵ includes a main chain structure represented by the general formula (A1-1-1), 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, a halogen atom, an alkyl group, an aryl group, a carbonyl group, a nitro group, an amino group, an alkylamino group, an arylamino group or a sulfonyl group; X represents an anion forming a counter salt with the cation of xanthine.

&Lt; 2 > The positive photosensitive resin composition according to < 2 >, wherein the anionic group in formula (A1-1) is at least one compound selected from the group consisting of carboxylic acid anion, sulfonic acid anion, an anion represented by formula (A1-1-2) , Or a coloring composition according to <1>, wherein X in the general formula (A1-2) is any one of a carboxylic acid anion, a sulfonic acid anion, an imide anion, a methide anion and a borate anion.

In general formula (A1-1-2)

[Chemical Formula 4]

In the general formula (A1-1-2), L ¹ represents a single bond or a divalent linking group, L ² represents -SO ₂ - or -CO-, G represents a carbon atom or a nitrogen atom, n1 is the case when G is a carbon atom represents a 2, G represents a 1 if the nitrogen atom, R ⁶ is each represents an aryl group containing alkyl group or a fluorine atom containing a fluorine atom, which n1 is 2, 2 Each R &lt; ⁶ &gt; may be the same or different;

In general formula (A1-1-3)

[Chemical Formula 5]

In 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, G Is a carbon atom or a nitrogen atom, n2 is 1 when G is a carbon atom, 0 when G is a nitrogen atom, ^R7A and ^R7B are each independently an alkylene group containing a fluorine atom or An arylene group containing a fluorine atom, and R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group.

<3> The coloring composition according to <1> or <2>, wherein the dye compound (A) further has an alkali-soluble group.

<4> The coloring composition according to any one of <1> to <3>, wherein the dye compound (A) further comprises a polymerizable group.

<5> The coloring composition according to any one of <1> to <4>, wherein the curable compound is a polymerizable compound and further contains a photopolymerization initiator.

&Lt; 6 > A coloring composition according to any one of < 1 > to < 5], further comprising a pigment having a phthalocyanine skeleton.

<7> A compound represented by the general formula (A1-1-1) wherein one of R ¹¹ to R ¹⁵ of the general formula (A1-1) and one of R ¹¹ to R ¹⁵ of the general formula (A1-2) A colored composition according to any one of < 1 > to < 6 &gt;;

<8> The coloring composition according to any one of <1> to <7>, wherein R ² and R ⁴ in the general formula (A1-1) and R ² and R ^{4 in} the general formula (A1-2) are phenyl groups.

<9> R ² and R ^{4 in} the general formula (A1-1) Further, at least one of R ² and R ⁴ in the general formula (A1-2) is a compound represented by the following general formula (A1-1-2) A coloring composition according to any one of < 1 > to < 8 &gt;;

[Chemical Formula 6]

In the general 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 carbonylamido group, A sulfonyl group, a sulfonyl group, a sulfonyl group, a nitro group, an amino group, an aminocarbonyl group, an aminosulfonyl group, a sulfonylimide group or a carbonylimide group, R ²² and R ²⁶ each independently represent a Alkyl group.

<10> is R ¹ and R ³ in the formula (A1-1), R ¹ and R ³ also general formula (A1-2) of, each independently, is, <1> to <9 alkyl group of 1 to 5 carbon atoms &Lt; / RTI &gt;

<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 a colored composition according to any one of <1> to <11>.

&Lt; 13 > A process for producing a colored composition, comprising the steps of: forming a coloring composition layer on a support using a coloring composition according to any one of < 1 > And a step of developing the light portion.

<14> A color filter obtained by a color filter having a cured film according to <12> or a method of manufacturing a color filter according to <13>.

<15> A solid-state imaging device having a color filter according to <14>.

&Lt; 16 > An image display apparatus having a color filter according to < 14 >.

According to the present invention, there is provided a colored composition which does not cause spectral fluctuation during development and which is excellent in light resistance, a cured film using the colored composition, a method of manufacturing a color filter, a color filter, a solid-state image pickup device and an image display device It became possible.

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

The following description of constituent elements in the present invention is based on a representative embodiment of the present invention, but the present invention is not limited to such embodiments.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The term "radiation " in the present specification means, for example, a line spectrum of a mercury lamp, far ultraviolet ray, extreme ultraviolet ray (EUV light) represented by an excimer laser, X-ray or electron ray. In the present invention, light means an actinic ray or radiation. The term "exposure" in this specification refers to not only exposure by deep ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, etc., but also imaging by particle beams such as electron beams and ion beams, .

In the present specification, the numerical range indicated by using "~ " means a range including numerical values written before and after" ~ "as a lower limit value and an upper limit value.

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

In the present specification, the solid content concentration refers to the solid content concentration at 25 占 폚.

In the present specification, the term " (meth) acrylate "refers to both or either acrylate and methacrylate, and" (meth) acrylate " refers to both acrylate and methacrylate, The term "(meth) acryloyl" refers to both acryloyl and methacryloyl.

In the present specification, the terms "monomer" and "monomer" are synonyms. Monomers in the present specification are distinguished from oligomers and polymers and refer to compounds 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. The polymerizable functional group refers to a group involved in the polymerization reaction.

In the present specification, the term " process "is included in this term, not only in the independent process but also in the case where the desired action of the process is achieved even if it can not be clearly distinguished from other processes.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a colored composition excellent in color characteristics.

In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene reduced values by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by TOSOH CORPORATION) and TSKgel Super AWM-H , 6.0 mm ID x 15 cm) can be obtained by using 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

In the present specification, the methyl group may be represented by Me, the ethyl group by Et, the propyl group by Pr, the butyl group by Bu, and the phenyl group by PH or Ph.

The coloring composition of the present invention (hereinafter occasionally referred to simply as "composition of the present invention") may contain repeating units represented by formula (A1-1) and / or repeating units represented by formula (A1-2) , And a curable compound.

In general formula (A1-1)

(7)

In the general formula (A1-1), one of R ¹ to R ¹¹ is a main chain structure represented by the following general formula (A1-1-1), and at least one of R ¹ to R ¹¹ is an anionic group or an anionic group substituent 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, R ⁵ ~ R ¹⁰ each independently represent a hydrogen atom, a halogen 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 amino group, an alkylamino group, an arylamino group , Or a sulfonyl group;

In general formula (A1-1-1)

[Chemical Formula 8]

In the general 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 general formula (A1-2)

[Chemical Formula 9]

In Formula (A1-2), one of R ¹ to R ¹⁵ includes a main chain structure represented by Formula (A1-1-1), R ¹ and R ³ are each independently an aliphatic hydrocarbon group, R ² and R ⁴ are each independently an aromatic hydrocarbon group, R ⁵ ~ R ¹⁰ are, each independently, represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon, R ¹¹ ~ R ¹⁵ is, Each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carbonyl group, a nitro group, an amino group, an alkylamino group, an arylamino group or a sulfonyl group; X represents an anion which forms an opposite salt to the cation of xanthine.

With such a constitution, a colored composition can be obtained which does not cause spectral fluctuation upon alkali development and which can provide a cured film excellent in heat resistance.

This mechanism is presumed to be as follows.

A plurality of light discoloration passages of dyes are known, and under light-resistance test conditions, chemical species are always exposed to light. Under such conditions, there is a path in which a globular electron species represented by singlet oxygen is generated and fading occurs due to the reaction of the dye with the dye. The reactivity with the former electron species is dominated by the oxidation potential of the dye, and the higher the oxidation potential, the more electrons are lost and easily discolored. However, since the dye has an electron distribution, a portion having a relatively high dislocation such as HOMO is a portion that is easy to react with a former electron, but it may be difficult to fade if there is a factor that lowers the reactivity such as three- .

In the case of the xanthene structure used in the present invention, it is considered that the nitrogen atom is a part which is likely to react with the former electron species. When the substituent of the nitrogen atom is an electron-donating group such as an alkyl group, it is likely to be discolored because the oxidation potential becomes higher, and if the electron-withdrawing group such as phenyl group is lowered, the oxidation potential becomes lower and it is hard to fade. In the present invention, it is presumed that the light resistance can be increased by making the group bonding to the nitrogen atom of the xanthene structure an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

The coloring composition of the present invention is usually subjected to an alkali development treatment to remove unexposed portions. At that time, since a part of the alkali developing solution penetrates the pattern of the exposed portion, the dye is exposed to the basic condition. When a proton having a high acidity is present in the xanthene structure, the spectral characteristics fluctuate under basic conditions and the original spectral characteristics are impaired. In the case of the xanthene structure, the proton on the nitrogen atom is considered to be susceptible to the influence of the pH, and when the acidity is high, the spectral fluctuation may occur in the alkali development.

In the present invention, it is presumed that the spectroscopic fluctuation during alkaline development can be suppressed by making the group bonding to the nitrogen atom of the xanthene structure an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

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

&Lt;

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

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

In general formula (A1-1)

[Chemical formula 10]

In the general formula (A1-1), one of R ¹ to R ¹⁵ includes a main chain structure represented by the general formula (A1-1-1), 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, a halogen atom, an alkyl group, an aryl group, a carbonyl group, a nitro group, an amino group, an alkylamino group, an arylamino group or a sulfonyl group; X represents an anion which forms an opposite salt to the cation of xanthine.

In the general 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, More preferably a methyl group, an ethyl group, an n-propyl group, an iso-propyl group or an n-butyl group. R ¹ and R ³ may be the same, but the same ones are preferable. The alkyl group as R ¹ and R ³ may have a substituent, but preferably has no substituent.

In the general formula (A1-1), R ² and R ⁴ are each independently an aromatic hydrocarbon group, and a phenyl group is more preferable. The aromatic hydrocarbon group as 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, more preferably a methyl group, an ethyl group, a propyl group or a butyl group, , Ethyl group, n-propyl group and n-butyl group are particularly preferable.

General formula (A1-1) are, it is more preferably R ² and R ⁴ also at least one of R ² and R ⁴ in the formula (A1-2) are, represented by the following general formula (A1-1-2).

(11)

In the general 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 carbonylamido group, A sulfonyl group, a sulfonyl group, a sulfonyl group, a nitro group, an amino group, an aminocarbonyl group, an aminosulfonyl group, a sulfonylimide group or a carbonylimide group, R ²² and R ²⁶ each independently represent a Alkyl group.

In the general 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 general formula (A1-1-2), it is preferable that R ²² and R ²⁶ each independently represent 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, more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group or an n- .

In the general formula ^{(A1-1), R 5 ~ R} 10 are, each independently, represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon, it is preferably a hydrogen atom. As the halogen atom, a fluorine atom, a chlorine atom and a bromine atom are exemplified, and a fluorine atom or a chlorine atom is preferable. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms. As the aliphatic hydrocarbon group, an alkyl group, an alkenyl group and an alkenyl group are exemplified, and an alkyl group is preferable. As the aromatic hydrocarbon group, an aryl group is preferable, and a phenyl group is more preferable.

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

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

Substituent group A:

The substituent which the dye may have includes 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, An alkoxy group, an aryloxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an amino group (including an alkylamino group and an anilino group), an acylamino group, an aminocarbonylamino group, An alkylsulfonylamino group, an alkylsulfonylamino group, a sulfonylamino group, a sulfonylamino group, a sulfonylamino group, a sulfamoylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, An acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl or a heterocyclic azo group, an imido group, a phosphino group, a phosphinyl group, a phosphinyloxy group, A silyl group, and the like. The details will be described below.

A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a linear or branched alkyl group (linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms (Preferably 3 carbon atoms) such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2- chloroethyl, 2-cyanoethyl, Substituted or unsubstituted cycloalkyl group having from 5 to 30 carbon atoms, preferably a cycloalkyl group having from 5 to 30 carbon atoms (preferably a substituted or unsubstituted cycloalkyl group having from 5 to 30 carbon atoms), a substituted or unsubstituted cycloalkyl group having from 3 to 30 carbon atoms, such as cyclohexyl and cyclopentyl, Cyclohexyl [2, 2] octan-3-yl) or tricycloalkyl group, and the like can be mentioned , Preferably a monocyclic cycloalkyl group, bicyclo Kilgi is, a monocyclic cycloalkyl group is particularly preferred),

(Linear or branched substituted or unsubstituted alkenyl groups, preferably alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, furanyl, geranyl, oleyl), cyclic (Preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, A diacyl group, for example, a bicycloalkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, such as bicyclo [2,2,1] hept-2-en- 2-en-4-yl) or tricycloalkenyl group and monocyclic cycloalkenyl group is particularly preferable), an alkynyl group (preferably having 2 to 6 carbon atoms, A substituted or unsubstituted alkynyl group having 1 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilyl ethynyl group),

(Preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecyloylaminophenyl), a heterocyclic group Is preferably a 5- to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or polycyclic heterocyclic group, more preferably the ring constituent atom is selected from a carbon atom, a nitrogen atom and a sulfur atom, A heterocyclic group having at least one hetero atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. , 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl and 2-benzothiazolyl), a cyano group, a hydroxyl group, a nitro group,

(Preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy (Preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 2,4-di-tert-amylphenoxy, 3-nitrophenoxy, 2-tetradecanylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, tert-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, a heterocyclic group is preferably a heterocyclic group described by the above-mentioned heterocyclic group, For example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy),

An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyl (Preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, and examples thereof include a carbamoyloxy group, a substituted or unsubstituted carbamoyloxy group, a substituted or unsubstituted carbamoyloxy group, a substituted or unsubstituted carbamoyloxy group, N, N-diethylcarbamoyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), An alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, n-octyl Carbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms P-methoxycarbonyloxy, p-n-hexadecyloxyphenoxycarbonyloxy), and the like,

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a heterocyclic amino group having 0 to 30 carbon atoms, (Preferably a formylamino group, an alkylamino group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, A substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, and examples thereof include formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, Tri- n-octyloxyphenylcarbonylamino), an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino, N , N-dimethylaminocarbonylamino, N, N- Ethylaminocarbonylamino, morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino, ethoxycarbonyl Amino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino),

An aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxy (Preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octyl (Preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, and examples thereof include an alkylsulfonylamino group, Methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group,

(Preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a carbon number A substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably having 2 to 30 carbon atoms A substituted or unsubstituted heterocyclic thio group, and the heterocyclic moiety is preferably a heterocyclic moiety described for the above-mentioned heterocyclic group, and examples thereof include 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio ), A sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N- Dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), sulfo groups,

Alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenyl (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, and examples thereof include a methylsulfonyl group, (Preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted phenylcarbonyl group having 7 to 30 carbon atoms, or a substituted or unsubstituted alkylcarbonyl group having 7 to 30 carbon atoms), a sulfonyl group An unsubstituted arylcarbonyl group such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), aryloxycarbonyl group (preferably having 7 to 30 carbon atoms A substituted or unsubstituted aryloxycarbonyl group such as phenoxycarbonyl, o-Cl M-nitrophenoxycarbonyl, p-tert-butylphenoxycarbonyl), &lt; / RTI &gt;

An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl) , A carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N- (Preferably a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic group having 3 to 30 carbon atoms) The azo group (the hetero ring is preferably a hetero ring described by the above-mentioned heterocyclic group), for example, phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4- (Preferably, a substituted or unsubstituted imide group having 2 to 30 carbon atoms, such as N-succinimide, N-phthalate, (Preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphine group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, Is a substituted or unsubstituted phosphinil group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl),

(Preferably, a substituted or unsubstituted phosphiniloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group Is a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably a substituted or unsubstituted C 3-30 alkyl group) Substituted silyl groups such as trimethylsilyl, tert-butyldimethylsilyl, phenyldimethylsilyl).

Of the above functional groups, those having a hydrogen atom may be those in which the hydrogen atom in the functional group is substituted with any of the above-mentioned groups. Examples of the functional group that can be introduced as a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group, and specific examples thereof include methylsulfonylaminocarbonyl , p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

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

The dye multimer used in the present invention is a dye multimer having a main chain structure in which one of R ¹ to R ¹⁵ is represented by the general formula (A1-1-1) in the general formula (A1-1) ) R ¹¹ ~ R ¹⁵ is one or a main chain structure represented by the general formula (A1-1-1) wherein the general formula (A1-1) of R ^1, R ^2, R ³ and R ⁴ at least one of the general formula (A1-1-1), and it is preferable that one of R ¹¹ to R ¹⁵ of the general formula (A1-1) is a backbone structure represented by the general formula (A1-1-1) And more preferably R ¹⁵ is a main chain structure represented by general formula (A1-1-1).

When ^one of R ¹ , R ² , R ³ and R ⁴ of the general formula (A1-1) includes a main chain structure, R ² or R ⁴ includes a main chain structure represented by the general formula (A1-1-1) , More preferably one of R ²² to R ²⁶ in the general formula (A1-1-2) is a main chain structure represented by the general formula (A1-1-1), R ²² is a general formula (A1- 1-1). &Lt; / RTI &gt;

In general formula (A1-1-1)

[Chemical Formula 12]

In the general 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, preferably a divalent linking group. Examples of the divalent linking group include a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (e.g., a methylene group, an ethylene group, a trimethylene group, a propylene group, and a butylene group), a substituted or unsubstituted A substituted or unsubstituted heterocyclic linking group, -CH = CH-, -O-, -S-, -C (= O) -, -CO ₂ - _{, -NR-, -CONR-, -O 2 C-} , -SO-, -SO 2 - , and these represent a bonding group formed by linking two or more. It is also preferable that L ¹¹ contains an anion.

L ¹¹ is preferably -CO ₂ - and phenylene 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.

The main chain structure represented by the general formula (A1-1-1) may be contained in one molecule of the dye multimer, or two or more kinds may be contained.

Hereinafter, the main chain structure preferably used in the present invention is exemplified, but it is needless to say that the present invention is not limited to these.

Particularly, the linking group represented by the following formulas (XX-1) to (XX-24) is preferable and the (meth) acrylic linkage chain represented by (XX-1) (XX-1) and (XX-2), more preferably selected from a styrene-based linking chain represented by the following formula (XX-18) More preferably selected from a (meth) acrylic linkage chain represented by the following formula (XX), a styrene-based linkage chain represented by the formula (XX-10) (Meth) acrylic linkage chain represented by the formula (1) and (XX-2) and the styrene-based linkage chain represented by the formula (XX-11) are more preferable.

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

[Chemical Formula 13]

[Chemical Formula 14]

<< Negative ionic group >>

The general formula (A1-1) includes an anionic group. The anionic group is included depending on the number of cations included in the dye multimer.

In the formula (A1-1), the anionic group, R ¹ ~ R ^15, or any one of, R ¹ ~ R ¹⁵ is a group contained as a substituent of any one of, or any one of R ¹¹ and R ^15, R &lt; ¹¹ &gt; and R &lt; ¹⁵ &gt;.

When the general formula (A1-1) includes a structure represented by the general formula (A1-1-2), it is also preferable that R ²² or R ²⁶ is an anionic group or an anionic group.

The number of anionic groups contained in the dye multimer of the present invention may be one kind or two or more kinds.

The anionic group in the general formula (A1-1) includes a carboxylic acid anion, a sulfonic acid anion, an anion represented by the general formula (A1-1-2) or an anion represented by the general formula (A1-1-3) desirable.

In general formula (A1-1-2)

[Chemical Formula 15]

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

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

The number of carbon atoms of the alkyl group containing a fluorine atom is preferably from 1 to 6, more preferably from 1 to 4, and still more preferably from 1 to 3. The alkyl group containing a fluorine atom may be straight-chain, branched or cyclic, more preferably a straight-chain group.

The number of carbon atoms of the aryl group containing a fluorine atom is preferably 6 to 18, more preferably 6 to 12, and even more preferably 6.

The alkyl group containing a fluorine atom or the aryl group containing a fluorine atom preferably has a fluorine atom content of 50% or more, more preferably a perfluoro group. The fluorine atom content is shown below.

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

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

Hereinafter, examples of the general formula (A1-1-2) are shown, but it is needless to say that the present invention is not limited thereto.

[Chemical Formula 16]

In general formula (A1-1-3)

[Chemical Formula 17]

In 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, G Is a carbon atom or a nitrogen atom, n2 is 1 when G is a carbon atom, 0 when G is a nitrogen atom, ^R7A and ^R7B are each independently an alkylene group containing a fluorine atom or An arylene group containing a fluorine atom, and R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group.

In the general 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 arylene group having 6 to 12 carbon atoms, -O-, -S-, or a combination thereof.

In the general 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 arylene group having 6 to 18 carbon atoms, -O-, -CO-, -S-, -SO ₂ -, -NR ^A R ^B - or And a group comprising a combination of these. The alkylene group having 1 to 6 carbon atoms may be linear, branched or cyclic. The arylene group having 6 to 18 carbon atoms may be monocyclic or polycyclic. 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 general formula (A1-1-3), R ^7A and R ^7B each independently represent an alkylene group containing a fluorine atom or an arylene group containing a fluorine atom, and the number of carbon atoms of the alkyl group containing a fluorine atom is 1 - More preferably 1 to 4, and even more preferably 1 to 3. The alkyl group containing a fluorine atom may be straight-chain, branched or cyclic, more preferably a straight-chain group.

The number of carbon atoms of the aryl group containing a fluorine atom is preferably 6 to 18, more preferably 6 to 12, and even more preferably 6.

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

In the general 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 carbon number of the alkoxymethyl group is preferably from 1 to 3.

Hereinafter, examples of the general formula (A1-1-3) are shown, but it is needless to say that the present invention is not limited thereto. Rx represents a hydrogen atom or a methyl group.

[Chemical Formula 18]

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

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

In general formula (A1-2)

[Chemical Formula 19]

In the general formula (A1-2), one of R ¹ to R ¹⁵ includes a main chain structure represented by the general formula (A1-1-1), 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, a halogen atom, an alkyl group, an aryl group, a carbonyl group, a nitro group, an amino group, an alkylamino group, an arylamino group or a sulfonyl group; X represents an anion which forms an opposite salt to the cation of xanthine.

In the general formula (A1-2), when R ¹ and R ³ are each independently an aliphatic hydrocarbon group, when R ² and R ⁴ are each independently an aromatic hydrocarbon group, R ⁵ to R ¹⁰ are each independently hydrogen An atom, a halogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, the preferred range is the same as that of R ¹ to R ^{15 in} formula (A1-2), and the preferable range is also the same.

The dye multimer used in the present invention is a dye multimer having a main chain structure in which one of R ¹ to R ¹⁵ is represented by the general formula (A1-1-1) in the general formula (A1-2) ) R ¹¹ ~ R ¹⁵ is one or a main chain structure represented by the general formula (A1-1-1) wherein the general formula (A1-2) of R ^1, R ^2, R ³ and R ⁴ at least one of the general formula (A1-1-1), and it is preferable that one of R ¹¹ to R ¹⁵ in the general formula (A1-2) is a backbone structure represented by the general formula (A1-1-1) And more preferably R ¹⁵ is a main chain structure represented by general formula (A1-1-1).

When ^one of R ¹ , R ² , R ³ and R ⁴ of the general formula (A1-2) includes a main chain structure, R ² or R ⁴ includes a main chain structure represented by general formula (A1-1-1) , More preferably one of R ²² to R ²⁶ in the general formula (A1-1-2) is a main chain structure represented by the general formula (A1-1-1), R ²² is a general formula (A1- 1-1). &Lt; / RTI &gt;

<< Negative ion X in general formula (A1-2) >>

In the general formula (A1-2), X represents an anion which forms an opposite salt with the cation of xanthane. Anions are included depending on the number of cations included in the dye multimer.

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

X is preferably an anion of any one of a carboxylic acid anion, a sulfonic acid anion, an imide anion, a methide anion, and a borate anion, and is preferably an anion selected from the group consisting of bis (sulfonyl) imide anion, tris (sulfonyl) methyl anion, A borate anion is more preferable.

As the bis (sulfonyl) imide anion, a structure represented by the following general formula (AN-1) is preferable.

[Chemical Formula 20]

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

X ¹ and X ² each independently represents an alkyl group having 1 to 10 carbon atoms and a fluorine atom or a fluorine atom and is preferably an alkyl group having 1 to 10 carbon atoms and having a fluorine atom or a fluorine atom, More preferably a perfluoroalkyl group having 1 to 4 carbon atoms, and still more preferably a trifluoromethyl group.

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

[Chemical Formula 21]

(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 carbon atoms.)

X ³ , X ⁴ and X ⁵ are, each independently, the same as X ¹ and X ² , and the preferred range is also synonymous.

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

[Chemical Formula 22]

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

Each of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms.

The aryl group represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may have a substituent. A halogen atom, an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbonyloxy group, a carbamoyl group, a sulfo group, a sulfonamido group and a nitro group, 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 each independently a phenyl group having an alkyl group having a halogen atom and / or a halogen atom, more preferably a phenyl group having an alkyl group having a fluorine atom and / More preferable.

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

(23)

&Lt; EMI ID =

(25)

(26)

Examples of the repeating unit represented by the general formula (A1-1) or the repeating unit represented by the general formula (A1-2) used in the present invention are shown below. It is needless to say that the present invention is not limited to these.

(27)

(28)

[Chemical Formula 29]

The dye multimer used in the present invention preferably contains 1 to 100 mol% of the total of the repeating units represented by the general formula (A1-1) and the repeating unit represented by the general formula (A1-2) Is preferably 5 to 40 mol%, and more preferably 10 to 30 mol%. The repeating unit represented by the general formula (A1-1) and the repeating unit represented by the general formula (A1-2) may each contain only one kind or two or more kinds.

<< Other functional groups and repeating units >>

The dye multimer of the present invention may have another functional group in the repeating unit containing the above-mentioned dye multimer. Examples of other functional groups include a polymerizable group and an alkali-soluble group.

The dye multimer of the present invention may contain other repeating units in addition to the repeating units containing the above-described dye structures. The other repeating unit may have a functional group.

As other repeating units, repeating units containing at least one of a polymerizable group and an alkali-soluble group (preferably, an acid group) are exemplified.

<<< Polymerizable groups of pigment multimers >>>

The dye multimer of the present invention preferably contains a polymerizable group. The polymerizable group may be contained only in one kind or in two or more kinds.

The polymerizable group may contain a polymerizable group in the dye structure, or may contain other portions. In the present invention, it is preferable that the dye structure includes a polymerizable group. With such a constitution, the heat resistance tends to be improved.

Further, in the present invention, an aspect in which a portion other than the dye structure includes a polymerizable group is also preferable.

As the polymerizable group, known polymerizable groups which can be crosslinked by radicals, acids and heat can be used. Examples thereof include groups containing ethylenic unsaturated bonds, cyclic ethers (epoxy groups, oxetane groups), methylol groups In particular, a group containing an ethylenic unsaturated bond is preferable, and a (meth) acryloyl group is more preferable, and glycidyl (meth) acrylate and 3,4-epoxy-cyclohexylmethyl (meth) Meth) acryloyl group is more preferable.

The polymerizable group is preferably contained as a repeating unit having a polymerizable group in the polymeric oligomer, more preferably as a repeating unit having an ethylenically unsaturated bond. That is, an example of a preferred embodiment of the dye multimer of the present invention is a mode in which the dye multimer contains a repeating unit including a dye monomer and a repeating unit having a polymerizable group, wherein the repeating unit containing a dye monomer and the ethylenically unsaturated It is more preferable to contain a repeating unit having a bond.

As a method of introducing the polymerizable group, there are (1) a method of modifying a dye multimer with a polymerizable group-containing compound, and (2) a method of copolymerizing the dye monomer and a polymerizable group-containing compound. Hereinafter, this will be described in detail.

(1) Method of modifying a dye multimer with a polymerizable group-containing compound and introducing it:

As a method for modifying a dye multimer with a polymerizable group-containing compound and introducing it, a known method can be used without particular limitation. (B) a method in which a hydroxyl group or an amino group having a dye oligomer is reacted with an unsaturated bond-containing isocyanate compound; (c) a method of reacting a carboxylic acid having an unsaturated bond- c) a method of reacting an epoxy compound possessed by a dye multimer with an unsaturated bond-containing carboxylic acid compound is preferable from the standpoint of production.

Examples of the unsaturated bond-containing epoxy compound in the method of reacting the carboxylic acid having the dye oligomer (a) with the unsaturated bond-containing epoxy compound include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 4-epoxy-cyclohexylmethyl acrylate, and 3,4-epoxy-cyclohexylmethyl methacrylate. Particularly, glycidyl methacrylate and 3,4-epoxy-cyclohexylmethyl methacrylate, The crosslinking property and the storage stability are excellent. As the reaction conditions, known conditions can be used.

As the unsaturated bond-containing isocyanate compound in the method of reacting the hydroxyl group or amino group of the dye oligomer (b) with the unsaturated bond-containing isocyanate compound, there may be mentioned 2-isocyanatoethyl methacrylate, Isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, and 1,1-bis (acryloyloxymethyl) ethyl isocyanate. However, it is preferable that 2-isocyanatoethyl methacrylate has cross- Is preferable. As the reaction conditions, known conditions can be used.

As the unsaturated bond-containing carboxylic acid compound in the method of reacting the epoxy compound of the above-mentioned (c) dye oligomer with the unsaturated bond-containing carboxylic acid compound, a known carboxylic acid compound having a (meth) acryloyloxy group can be used without particular limitation , Methacrylic acid and acrylic acid are preferable, and methacrylic acid is particularly preferred because of its excellent crosslinking property and storage stability. As the reaction conditions, known conditions can be used.

(2) Method of copolymerizing and introducing the dye monomer and the polymerizable group-containing compound:

(2) A method of copolymerizing and introducing the dye monomer and the polymerizable group-containing compound is not particularly limited and known methods can be used. (D) a method of copolymerizing a radically polymerizable dye monomer and a radically polymerizable group containing a polymerizable group, (e) a method of copolymerizing a middle part-capable dye monomer and a middle part capable polymerizable group-containing compound is preferable.

(d) an allyl group-containing compound (for example, allyl (meth) acrylate, etc.) as a radically polymerizable group containing a polymerizable compound in a method of copolymerizing a radically polymerizable dye monomer with a radically polymerizable polymerizable group- Epoxy group-containing compounds (e.g., (meth) acrylate glycidyl, 3,4-epoxy-cyclohexylmethyl (meth) acrylate, (Meth) acrylate), methylol group-containing compounds (e.g., N- (hydroxymethyl) acrylamide, etc.), and epoxy compounds and oxetane compounds are particularly preferable. As the reaction conditions, known conditions can be used.

(e) a polymerizable group-containing intermediate compound capable of being polymerized in a method of copolymerizing a middle part-capable colorant monomer with a middle-partable polymerizable group-containing compound, wherein the unsaturated bond-containing diol compound (for example, 2,3-dihydroxy Propyl (meth) acrylate, etc.). As the reaction conditions, known conditions can be used.

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

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

When the polymeric multimer contains a repeating unit having a polymerizable group, the proportion of the repeating unit is preferably 1 to 60 mol%, more preferably 10 to 50 mol, and more preferably 15 to 40 mol, % Is more preferable.

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

Examples of the repeating unit having a polymerizable group include the following specific examples. However, the present invention is not limited thereto.

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Of the above specific examples, from the viewpoint of substrate adhesion and surface roughness, a dye monomer having an ethylenic unsaturated bond is preferable, and among these, a methacryloyl group, an acryloyl group, a styryl group, or a vinyloxy group is preferable, A diaryl group and an acryloyl group are more preferable, and a methacryloyl group is more preferable.

<<< Alkali-soluble group possessed by the dye oligomer >>>

Examples of the alkali-soluble group which may be contained in the dye multimer in the present invention are an acid group, and examples of the acid group include a carboxylic acid group, a sulfonic acid group and a phosphoric acid group. The alkali-soluble group may be contained only in one kind or in two or more kinds.

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

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

Examples of the method of introducing an alkali-soluble group into a dye multimer include a method of previously introducing an alkali-soluble group into the dye monomer and a method of introducing a monomer other than the dye monomer having an alkali-soluble group (such as (meth) acrylic acid, caprolactone modified product of acrylic acid, (Meth) acrylate modified with phthalic anhydride of 2-hydroxyethyl (meth) acrylate, 1,2-cyclohexanedicarboxylic anhydride modified product of 2-hydroxyethyl (meth) acrylate, Containing monomers such as stearic acid, styrene carboxylic acid, itaconic acid, maleic acid and norbornenecarboxylic acid, phosphoric acid-containing monomers such as acid phosphoxyethyl methacrylate and vinylphosphonic acid, vinyl sulfonic acid, 2-acrylamido- Sulfonic acid-containing monomers such as sulfonic acid, sulfonic acid, and sulfonic acid), and it is more preferable to use both methods.

The amount of the alkali soluble group possessed by the dye oligomer is preferably 0.3 mmol to 2.0 mmol, more preferably 0.4 mmol to 1.5 mmol, and particularly preferably 0.5 mmol to 1.0 mmol, per 1 g of the colorant multimer.

When the dye multimer contains a repeating unit containing a dye monomer and a repeating unit having an acid group, the proportion of repeating units containing an acid group-containing repeating unit is preferably 5 to 70 moles per mole of all repeating units in the dye monomer , More preferably 10 to 60 mol%, and still more preferably 10 to 50 mol%.

Examples of other functional groups of the dye oligomer include a development promoter such as lactone, acid anhydride, amide, -COCH ₂ CO- and cyano group, a long chain and cyclic alkyl group, an aralkyl group, an aryl group, a polyalkylene oxide group, , A maleimide group, and an amino group, and the like, and they can be suitably introduced.

As an introduction method, there may be mentioned a method of preliminarily introducing into a dye monomer, and a method of copolymerizing a monomer having the functional group.

The dye multimer used in the present invention is a repeating unit containing an alkali-soluble group, which is a repeating unit having a repeating unit of 2 to 20 unsubstituted alkyleneoxy chains on the side chain (hereinafter referred to as "(b) repeating unit" May be included). By including such an alkali-soluble group, a colored composition having better discoloration resistance can be obtained.

The number of repeating units of the alkyleneoxy group contained in the repeating unit (b) is preferably from 2 to 10, more preferably from 2 to 15, and still more preferably from 2 to 10.

One alkyleneoxy group is represented by - (CH ₂ ) _n O-, n is an integer, n is preferably 1 to 10, more preferably 1 to 5, and still more preferably 2 or 3.

In the present invention, the repeating unit of 2 to 20 unsubstituted alkyleneoxy chains may contain only one type of alkyleneoxy group, or two or more types may be contained.

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

In general formula (P)

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(In the general formula (P), X ¹ represents a linking group formed by polymerization, L ¹ represents a single bond or a divalent linking group, and P represents a group containing a group consisting of repeating alkyleneoxy chains.)

X ¹ and L ¹ in the general formula (P) agree with X ¹ and L ¹ in the general formula (A), respectively, and preferable ranges are also the same.

P represents a group containing a group consisting of repetitions of an alkyleneoxy chain, more preferably consisting of a group-terminal atom or a terminal group formed by repetition of -alkyleneoxy chains.

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 or a hydroxyl group, more preferably a hydrogen atom, , And a hydrogen atom is particularly preferable.

(b) a repeating unit having a repeating unit of 2 to 20 unsubstituted alkyleneoxy chains in the side chain is preferably 2 to 20 mol% of all repeating units constituting the colorant multimer, and 5 To 15 mol% is more preferable.

Hereinafter, examples of the repeating unit (b) usable in the present invention are shown, but it is needless to say that the present invention is not limited thereto.

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Examples of other functional groups of the dye oligomer include a development promoter such as lactone, acid anhydride, amide, -COCH ₂ CO- and cyano group, a long chain and cyclic alkyl group, an aralkyl group, an aryl group, a polyalkylene oxide group, , A maleimide group, and an amino group, and the like, and they can be suitably introduced.

As an introduction method, there may be mentioned a method of preliminarily introducing into a dye monomer, and a method of copolymerizing a monomer having the functional group.

Specific examples of the repeating unit having an alkali-soluble group and other functional groups that the dye multimer may have are shown, but the present invention is not limited thereto.

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(36)

(37)

(38)

[Chemical Formula 39]

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<<< Structural unit having at least one of structures represented by formulas (1) to (5) >>>

The dye multimer used in the present invention may have at least one of the structures represented by the formulas (1) to (5) in the same molecule. With such a constitution, when the cured film is produced, 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 improvement of exposure sensitivity and light resistance. Further, the adhesion can be improved. In addition, generation of development residue can be suppressed. Although this mechanism is presumed, by using a pigment multimer having at least one of the pigment structure and the structure represented by the formulas (1) to (5) in the same molecule, The distance of the structure gets closer. As a result, it is considered that the exposure sensitivity and the light resistance can be improved more effectively.

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

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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 bond to each other to represent an aliphatic ring having 4 to 12 carbon atoms. "*" Represents the bonding of 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 is preferably an alkyl group having 1 to 18 carbon atoms.

The alkyl group having 1 to 18 carbon atoms may be straight chain, branched chain or cyclic, and is preferably straight-chain. 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, further 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, and more preferably a methyl group.

The carbon number of the aryl group may be 6 to 18, may be 6 to 12, or may be 6 to 6. Specific examples thereof include a phenyl group.

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

In the formula (1), R ² and R ³ each independently represent a methyl group or an ethyl group, and a methyl group is preferable. R ² and R ³ may bond 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 backbone. The bonding hand may be bonded to the polymer backbone directly or via a linking group, or may be bonded to the above-mentioned pigment 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 the present invention is not limited thereto. In the structure shown below, "*" represents the bonding of the structure represented by formula (2) and the polymer backbone.

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

In the formula (2), R ⁴ represents the formula (2A), the alkyl group or the aryl group having 1 to 18 carbon atoms, and is preferably represented by the formula (2A). The alkyl group having 1 to 18 carbon atoms and the aryl group are the same as the alkyl group and aryl group having 1 to 18 carbon atoms described for R ¹ in formula (1). In addition, "*" is a combination hand and an agreement described in equation (1).

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In the formula (2A), each R ⁶ independently represents an alkyl group having 1 to 18 carbon atoms. "*" Represents the combined hand of the structure represented by the formula (2A) and the structure represented by the formula (2).

In the formula (2A), R ⁶ is the same as the alkyl group having 1 to 18 carbon atoms described for R ¹ in the formula (1). In addition, "*" is a combination hand and an agreement described in equation (1).

Specific examples of the structure represented by the formula (2) are shown below, but the present invention is not limited thereto. In the structure shown below, "*" represents the bonding of the structure represented by formula (2) and the polymer backbone.

[Chemical Formula 45]

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

In the formula (3), R ⁷ is the same as the alkyl group having 1 to 18 carbon atoms described for 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, and 0 or 1 is preferable.

In Equation (3), "*" is the combined hand and agreement described in Equation (1).

Specific examples of the structure represented by the formula (3) are shown below, but the present invention is not limited thereto. In the following structures, "*" represents the bonding of the structure represented by formula (3) and the polymer backbone.

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In formula (4), R ⁸ and R ⁹ each independently represent an alkyl group having 1 to 18 carbon atoms. n2 represents an integer of 0 to 3; n3 represents an integer of 0 to 4; When n2 is 2 or 3, each R ⁸ may be the same or different. when n3 represents an integer of 2-4, and each R ⁹ is, it may be the same or different. "*" Represents the combined hand of the structure represented by the formula (4) and the polymer skeleton.

In the formula (4), R ⁸ and R ⁹ are the same as the alkyl group having 1 to 18 carbon atoms 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, and 0 or 1 is preferable.

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

In Equation (4), "*" is the combined hand and agreement described in Equation (1).

Specific examples of the structure represented by the formula (4) are shown below, but the present invention is not limited thereto. In the structure shown below, "*" represents the bonding of the structure represented by the formula (4) and the polymer backbone.

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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. "*" Represents the combined hand of the structure represented by formula (5) and the polymer skeleton.

When R ¹⁰ in the formula (5) represents an alkyl group having 1 to 18 carbon atoms, it is preferably an alkyl group having 1 to 3 carbon atoms, which is the same as the alkyl group having 1 to 18 carbon atoms described for R ¹ in formula (1) desirable. When R ¹⁰ represents an alkoxy group having 1 to 8 carbon atoms, the carbon number of the alkoxy group is preferably 1 to 6, more preferably 1 to 5, and further preferably 1 to 4.

R ¹⁰ in the formula (5) may further have a substituent. As the substituent which may be contained, a substituent selected from the above-mentioned substituent group A can be mentioned.

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

R ¹¹ in the formula (5) agrees with R ¹⁰ in the formula (5), and the preferable range is also the same.

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

R ¹² in the formula (5) agrees with R ¹⁰ in the formula (5), and the preferable range is also the same.

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

N7 to n9 in the formula (5) each independently represent 0 or 1, and at least one of n7 to n9 represents 1. In particular, it is preferable that only n7 represents 1, only n8 and n9 represent 1, or n7, and only one of n8 and n9 represents 1.

In Equation (5), "*" is the combined hand and agreement described in Equation (1).

Specific examples of the structure represented by the formula (5) are shown below, but the present invention is not limited thereto. In the structure shown below, "*" represents the bonding bond between the structure represented by the formula (5) and the polymer backbone.

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

(E)

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In the general formula (E), X ³ is synonymous with R ^x in the general formula (A-1-1). L ⁴ is synonymous with L ¹¹ in the general formula (A-1-1). Z ¹ represents a structure represented by the above-mentioned formulas (1) to (5).

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

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The pigment multimer may not have a constitutional unit having at least one of the structures represented by the formulas (1) to (5), but when it has the constitutional unit, when the total constitutional unit in the pigment multimer is 100% ) To (5) is preferably from 0.5 to 20% by mass, more preferably from 1 to 10% by mass, and particularly preferably from 1 to 5% by mass.

<<< Specific end >>>

The dye multimer used in the present invention preferably has a group represented by formula (I) or a group represented by formula (II) (hereinafter sometimes referred to as "specific end group"). With such a constitution, solvent resistance and light resistance can be imparted. Further, since it is synthesized by, for example, living radical polymerization, the dispersion degree (Mw / Mn) of the colorant multimer can be reduced. That is, the light resistance can be further improved by slightly decreasing the proportion of the high molecular weight component as the pigment multimer, and the solvent resistance can be improved by slightly decreasing the proportion of the low molecular weight component. Further, heat resistance, coating ability, and developability can be further improved.

The compound of formula (I)

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In the general formula (I), Z represents a hydrogen atom or a monovalent substituent. * Represents the bonding position with the main chain terminal.

In the general formula (I), Z represents a monovalent substituent. Z represents 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, a total of 3 atoms of a carbon atom and a bicyclic atom a monovalent heterocyclic group 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 preferably univalent group having a polymer chain and, -SR ^1, aryl group, a heteroaryl group, an alkyl group and / or an amino group substituted with an aryl group, an alkoxy group, and aryloxy, and preferably selected from a group, -SR ¹ (preferably, coming alkylthio, aryl Im import), an aryl group, More preferably an alkylthio group or an aryl group, and 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 amino group substituted with an alkyl group and / or an aryl group as Z is preferably an alkyl group having 1 to 5 carbon atoms or an amino group substituted with 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 monovalent aromatic hydrocarbon group having 3 to 30 A monovalent heterocyclic group having 3 to 30 total atoms of carbon atoms and a bivalent atom, R &lt; ¹ &gt; and R &lt; ² &gt; ² may be all substituted or not substituted. Examples of the substituent when it is substituted include an alkyl group and an aryl group.

R ¹ and R ² are each independently preferably 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 a phenyl group.

In general formula (II)

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In the general formula (II), A and B each independently represent a monovalent substituent. A and B may be connected to form a ring. * Represents the bonding position with the main chain terminal.

The monovalent substituents represented by A and B are each independently preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. The alkyl group having 1 to 30 carbon atoms preferably has 3 to 10 carbon atoms.

Particularly, it is preferable that one of A and B is a secondary or tertiary alkyl group having 1 to 30 carbon atoms and the other is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, Is preferably a tertiary alkyl having 1 to 30 carbon atoms and the other of A and B is preferably an alkyl group having 1 to 30 carbon atoms and one of A and B is a tertiary alkyl having 1 to 30 carbon atoms, And one of them is particularly preferably a secondary or tertiary alkyl group having 1 to 30 carbon atoms (more preferably a secondary alkyl group having 1 to 30 carbon atoms).

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

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

Specific examples of the terminal groups are shown, but the present invention is not limited thereto.

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Examples of the method for introducing the terminal group represented by the general formula (I) or (II) into the main chain of the polymer include a compound represented by the general formula (Ia), a compound represented by the general formula (IIa), and a radical represented by the general formula (IIb) A radical polymerization of a polymerizable compound having a dye structure is preferred.

(Ia)

[Chemical Formula 59]

In the general formula (Ia), Z is synonymous with the general formula (I). C represents a monovalent organic group.

The compound of formula (IIa)

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In the general formula (IIa), Z is synonymous with the general formula (II). D represents a monovalent organic group.

(IIb)

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In the general formula (IIb), A and B are synonymous with the general formula (II).

By incorporating such an additive, the radical activity inactivation at the end of the radical polymerization becomes an equilibrium state, so that the radicals are not inactivated in appearance. By such polymerization by living radical polymerization, a multimer having a small degree of dispersion can be obtained.

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

The ratio [Mw / (Mn)] of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the pigment multimer is preferably 1.0 to 2.0, more preferably 1.1 to 1.8, To 1.5 is particularly preferable.

The glass transition temperature (Tg) of the colorant multimer according to the present invention is preferably 50 占 폚 or higher, and more preferably 100 占 폚 or higher. It is preferable that the reduction temperature by 5 weight% by thermogravimetric analysis (TGA measurement) be 120 deg. C or higher, more preferably 150 deg. C or higher, and still more preferably 200 deg. In this region, when the coloring composition of the present invention is applied to the production of a color filter or the like, the concentration change due to the heating process can be reduced.

When the polymeric multimer used in the present invention contains a repeating unit having a dye structure and another repeating unit, it is preferable that the polymer is a random polymer of a polymerizable compound other than the dye. When the polymer is a random polymer, the dye structure is randomly present in the dye multimer, and the effect of the present invention is more effectively exhibited.

The absorption coefficient per unit weight of the colorant multimer according to the present invention (hereinafter referred to as? ') Is preferably 30 or more, more preferably 60 or more, in terms of?' =? / Average molecular weight More preferably 100 or more. Within this range, it is possible to produce a color filter having good color reproducibility when a color filter is manufactured by applying the coloring composition of the present invention.

The molar extinction coefficient of the colorant multimer used in the coloring composition of the present invention is preferably as high as possible from the viewpoint of coloring power.

The reduced viscosity of the colorant multimer used in the coloring composition of the present invention is preferably 4.0 to 10.0, more preferably 5.0 to 9.0, and still more preferably 6.0 to 7.0 from the viewpoint of mordanting. The reduced viscosity can be measured using, for example, a Ubero type viscometer.

The pigment multimer according to the present invention is preferably a compound dissolved in the following organic solvent.

Examples of the organic solvent include esters (e.g., methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate and methyl 3-methoxypropionate), ethers Acetone, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate), ketones (methyl ethyl ketone, cyclohexanone, 2-heptanone, 3- , And aromatic hydrocarbon (for example, toluene, xylene, etc.). The solvent is preferably dissolved in an amount of 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% % Or less, more preferably 10 mass% or more and 30 mass% or less. When the coloring composition of the present invention is applied to the production of a color filter or the like in this region, it is possible to reduce the concentration drop due to a suitable application surface shape or elution after coating with other colors.

In the coloring composition of the present invention, the pigment multimer may be used singly or in combination of two or more. When two or more kinds are used, it is preferable that the total amount corresponds to the content to be described later.

The content of the pigment multimer in the coloring composition of the present invention is set after considering the content ratio with the pigment to be described later.

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

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

The coloring composition of the present invention includes a curable compound in addition to the above-mentioned pigment oligomer. In addition, the coloring composition of the present invention may contain other components. For example, in order to control the color value, it is preferable to include, in addition to the pigment multimer, other coloring agents (preferably a pigment) and a pigment dispersing agent.

In addition, the coloring composition of the present invention is used for forming a colored layer of a color filter. In the case of the formation of the color filter, in general, in addition to the above-mentioned pigment oligomers and pigments, pigment dispersions, curable compounds are included. As the curable compound, a polymerizable compound or an alkali-soluble resin (including an alkali-soluble resin containing a polymerizable group) is exemplified and appropriately selected according to the application and the production method. The curable compound is preferably a polymerizable compound. Further, the coloring composition of the present invention preferably contains a photopolymerization initiator.

For example, when a coloring layer is formed by photoresist, the coloring composition of the present invention may contain a colorant, a pigment, a pigment dispersion, and a photopolymerization initiator as a pigment multimer, an alkali-soluble resin as a curable compound, Compositions are preferred. In addition, it may contain components such as a surfactant and a solvent.

In the case of forming a colored layer by dry etching, a composition containing a pigment multimer, a polymerizable compound as a curable compound, a pigment, a pigment dispersion and a photopolymerization initiator in the present invention is preferable. In addition, it may contain components such as a surfactant and a solvent.

The details of these will be described below.

<Polymerizable compound>

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

Known polymerizable compounds capable of crosslinking by radicals, acids, and heat can be used, and examples thereof include polymerizable compounds including ethylenically unsaturated bonds, cyclic ethers (epoxy, oxetane), methylol, and the like. The polymerizable compound is suitably selected from compounds having at least one, and preferably two or more, terminal ethylenic unsaturated bonds from the viewpoint of sensitivity. Of these, polyfunctional polymerizable compounds having four or more functionalities are preferable, and polyfunctional polymerizable compounds having five or more functionalities are more preferable.

Such a group of compounds are widely known in the industrial field of the present invention, and they can be used without particular limitation in the present invention. These may be, for example, monomers, prepolymers, i.e., dimers, trimer and oligomers, or mixtures thereof, or their chemical forms such as oligomers. The polymerizable compounds 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 unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And amides of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound, and also oligomers thereof. The term &quot; unsaturated carboxylic acid &quot; Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or multifunctional isocyanate or an epoxide, a monofunctional or polyfunctional A dehydration condensation reaction product with a carboxylic acid, and the like are suitably used. In addition, it is also possible to use an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group, an addition reaction product of monofunctional or polyfunctional alcohols, amines, thiols, Unsaturated carboxylic acid esters or amides having a desilyl substituent group and mono- or polyfunctional alcohols, amines, and thioes are also suitable. As another example, in place of the above unsaturated carboxylic acid, it is also possible to use a compound group substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an ally ether or the like.

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

The polymerizable compound is also preferably a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and a boiling point of at least 100 캜 at normal pressure. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; (Meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylol propol paint (acryloyloxypropyl) ether (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylol ethane, and (meth) acrylate, Japanese Examined Patent Publication 48 (Meth) acrylates described in JP-A-41708, JP-A-50-6034, JP-A-51-37193, Polyester acrylates described in JP-A-48-64183, JP-A-49-43191, JP-A-52-30490, epoxies which are reaction products of epoxy resin and (meth) acrylic acid And polyfunctional acrylates and methacrylates such as acrylates, and mixtures thereof.

(Meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether such as glycidyl (meth) acrylate and a compound having an ethylenic unsaturated group.

As other preferable polymerizable compounds, those having a fluorene ring and having an ethylenic unsaturated group as a bifunctional group, such as those described in JP-A-2010-160418, JP-A-2010-129825 and JP-B-4364216, Or more, and a carboxy resin can also be used.

As the compound having at least one addition-polymerizable ethylenic unsaturated group having a boiling point of 100 占 폚 or higher at normal pressure, the compounds described in paragraphs [0254] to [0257] of Japanese Laid-Open Patent Publication No. 2008-292970 are also suitable.

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

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In the above general formula, n is 0 to 14, and m is 1 to 8. R and T present in plural in one molecule may be the same or different.

At least one of the plural Rs present in each of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5) is -OC (= O) CH = CH ₂ or -OC ) C (CH ₃₎ represents a group represented by = CH _2.

Specific examples of the polymerizable compounds represented by the above general formulas (MO-1) to (MO-5) include compounds described in paragraphs 0248 to 0251 of JP-A No. 2007-269779 Can be used.

Further, in JP-A 10-62986, ethylene oxide or propylene oxide is added to the polyfunctional alcohol represented by the general formulas (1) and (2) together with the specific examples thereof and then (meth) acrylated The compound may also be used as a polymerizable compound.

Among them, dipentaerythritol triacrylate (KAYARAD D-330, manufactured by Nippon Kayaku Kabushiki Kaisha) and dipentaerythritol tetraacrylate (commercially available products such as KAYARAD D-320; Nippon Kayaku Co., (KAYARAD D-310 manufactured by Nippon Kayaku K.K.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) (Trade name: A-DPH-12E, manufactured by Shin-Nakamura Kagaku K. K.) and ethylene glycol-modified diethylene glycol diacrylate (ethylene glycol diacrylate) , And a structure in which a propylene glycol residue is interposed. These oligomer types can also be used.

As the polymerizable compound, a polyfunctional monomer may have an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. If the ethylenic compound has an unreacted carboxyl group as in the case of the mixture as described above, it can be used as it is. If necessary, the nonylromatic carboxylic acid anhydride is reacted with the hydroxyl group of the above- . In this case, specific examples of the non-aromatic carboxylic acid anhydrides to be used include anhydrous tetrahydrophthalic acid, alkylated anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, alkylated anhydrous hexahydrophthalic acid, succinic anhydride, and maleic anhydride.

In the present invention, examples of the monomer having an acid group include esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, which are obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a nonaromatic carboxylic acid anhydride to give an acid group . Especially preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers made by Toagosei Co., Ltd.

These monomers may be used singly or in combination of two or more in view of difficulty in using a single compound in the production process. If necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as a monomer.

The preferable acid value of the polyfunctional monomer having an acid group is 0.1 mg KOH / g to 40 mg KOH / g, particularly preferably 5 mg KOH / g to 30 mg KOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are deteriorated. If the acid value is too high, the production and handling become difficult, and the photopolymerization performance deteriorates and the curability such as surface smoothness of the pixel becomes poor. Therefore, when two or more kinds of polyfunctional monomers having different acid groups are used in combination or when polyfunctional monomers having no acid group are used in combination, it is preferable to adjust the acid groups as the entire polyfunctional monomer to fall within the above range.

It is also preferable that the polymerizable compound contains a polyfunctional monomer having a caprolactone structure.

The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in its molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, (Meth) acrylic acid and? -Caprolactone obtained by esterifying polyhydric alcohols such as glycerin, diglycerol, trimethylolmelamine and the like with (meth) acrylic acid and? -Caprolactone, Modified polyfunctional (meth) acrylate. Among them, a polyfunctional monomer having a caprolactone structure represented by the following general formula (Z-1) is preferable.

&Lt; EMI ID =

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

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

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

Such a polyfunctional monomer having a caprolactone structure is commercially available, for example, as KAYARAD DPCA series from Nippon Kayaku Co., and DPCA-20 (m = 1 in the above formulas (1) to (3) (2) = 2, R ¹ are both a hydrogen atom), the group represented by, DPCA-30 (the same formula, m = 1, equation (2) of the group represented by = 3, R ¹ is hydrogen atom DPCA-120 (the same formula, m = 1, the number of groups represented by formula (2) = 6 and R ¹ are all hydrogen atoms), DPCA-120 The number of groups represented by formula (2) = 6, and R ¹ are all hydrogen atoms).

In the present invention, the polyfunctional monomers having a caprolactone structure may be used alone or in combination of two or more.

It is also preferable that the specific monomer in the present invention is at least one member selected from the group of compounds represented by the following general formula (Z-4) or (Z-5).

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E in the general formulas (Z-4) and (Z-5) each independently represents - ((CH ₂ ) yCH ₂ O) - or - ((CH ₂ ) yCH (CH ₃ ) , Y represents independently an integer of 0 to 10, and X represents, independently of each other, an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.

In the general formula (Z-4), the sum of the acryloyl group and the methacryloyl group is 3 or 4, m is independently an integer of 0 to 10, and the sum of m is 0 to 40 It is an integer. Provided that when the sum of each m is 0, any one of X is a carboxyl group.

In the general formula (ii), the sum of the acryloyl group and the methacryloyl group is 5 or 6, each n independently represents an integer of 0 to 10, and the sum of n is an integer of 0 to 60 . Provided that when the sum of each n is 0, any one of X is a carboxyl group.

In the general formula (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. The sum of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and an integer of 4 to 8 is particularly preferable.

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

The sum 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.

The - ((CH ₂ ) yCH ₂ O) - or - ((CH ₂ ) yCH (CH ₃ ) O) - in the general formula (Z-4) or the general formula A form in which the terminal is bonded to X is preferable.

The compounds represented by the general formula (Z-4) or (Z-5) may be used singly or in combination of two or more. Particularly, in the general formula (ii), all of the six X's are preferably acryloyl groups.

The total content of the compound represented by the formula (Z-4) or (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 general formula (Z-4) or the general formula (Z-5) can be produced by subjecting pentaerythritol or dipentaerythritol, which is a conventionally known process, to ring opening skeleton And (meth) acryloyl groups are introduced into the terminal hydroxyl groups of the ring-opening skeleton by reaction with, for example, (meth) acryloyl chloride. Each process is a well-known process, and one skilled in the art can easily synthesize the compound represented by the general formula (i) or (ii).

Among the compounds represented by the general formula (Z-4) or the general formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.

(A), (b), (f), (f), (f) and (f) , (e) and (f) are preferable.

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Examples of commercially available products of the polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains of Satomar Co., DPCA-60, which is a hexafunctional acrylate having six pentylene oxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of the polymerizable compound include those described in JP-A-48-41708, JP-A-51-37193, JP-A-2-32293, and JP-A-2-16765 And the ethylene oxide described in JP-A-62-39418, JP-A-58-49860, JP-A-56-17654, JP-A-62-39417, Also suitable are urethane compounds having a skeleton. Examples of the polymerizable compound include compounds having an amino or sulfide structure in the molecule, such as those described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238 By using the polymerizable compounds, a curable composition having an extremely high photosensitive speed can be obtained.

UA-7200 (manufactured by Shin Nakamura Kagaku), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H (manufactured by Sanyo Chemical Industries, Ltd.) , UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyowa Chemical Industry Co., Ltd.).

JER-827, JER-834, JER-1001, JER-1002, JER-1003, and JER-823 as the bisphenol A type epoxy resin having an epoxy group, as the cyclic ether (epoxy, oxetane) EPICLON1050, EPICLON1051, EPICLON1055 (manufactured by DIC Corporation), and the like, and bisphenol F type epoxy resins such as bisphenol F type epoxy resin (trade name: JER-1055, JER-1007, JER-1009, JER-1010 manufactured by Japan Epoxy Resin Co., (Manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 (manufactured by DIC Co., Ltd.) as the resin, and JER-806, JER-4007, JER-4005, JER- , JER-152, JER-157, JER-157S70 and JER-157S65 (above, Japan Epoxy Resin Co., Ltd.) as the phenol novolak type epoxy resin, EPICLON N-760, EPICLON N-770 and EPICLON N-775 (manufactured by DIC Corporation), and EPICLON N-660 and EPICLON N-760 as cresol novolac epoxy resins, EPICLON N-670, EPICLON N-670, EPICLON N-680, EPICLON N-690, ), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), ADEKA RESIN EP-4080S, EP-4085S and EP-4088S (manufactured by ADEKA Corporation) as the aliphatic epoxy resin, Celloxide 2021P , 2-epoxy-4- (2-oxiranyl) cyclohexyl of 2,2-bis (hydroxymethyl) -1-butanol, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE- EX-214L, EX-216L, EX-321L, EX-321L, EX-321L, EX-321L, EX- NC-2000 (manufactured by Nippon Oil &amp; Chemical Co., Ltd.), ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP- , NC-7300, XD-1000, EPPN-501, EPPN-502 (manufactured by ADEKA) and JER-1031S (manufactured by Japan Epoxy Resin Co., Ltd.). Such a polymerizable compound is suitable for forming a pattern by a dry etching method.

The details of the structure of the polymerizable compound, whether or not the polymerizable compound is used alone, whether or not the polymerizable compound is used alone, and the amount thereof to be added can be arbitrarily set in accordance with the final performance design of the coloring composition. For example, from the viewpoint of sensitivity, a structure having a large number of unsaturated groups per molecule is preferable, and in most cases, a bifunctionality or more is preferable. Further, from the viewpoint of enhancing the strength of the cured film formed by the coloring composition, it is preferable to use trifunctional or more functional groups and the number of functional groups different from each other (e.g., acrylic acid ester, methacrylic acid ester, styrene series compound, vinyl ether group compound) A method of controlling both sensitivity and strength is also effective. It is also preferable to use a polymerizable compound having three or more functional groups and having different ethylene oxide chain lengths from the viewpoint that the developability of the colored composition can be controlled and an excellent pattern forming ability can be obtained.

The compatibility and dispersibility with other components (for example, a photopolymerization initiator, a dispersant, an alkali-soluble resin, etc.) contained in the coloring composition is also an important factor in selecting and using a polymerizable compound. For example, The compatibility may be improved by the use of the purity compound or by the combined use of two or more species. In addition, a specific structure may be selected from the viewpoint of improving adhesion with a hard surface such as a support.

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

The composition of the present invention may contain only one type of polymerizable compound or two or more types of the polymerizable compound. When two or more kinds are included, the total amount is preferably in the above range.

<Polyfunctional thiol compound>

The coloring 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 and the like. The polyfunctional thiol compound is preferably a secondary alkane thiol compound, particularly preferably a compound having a structure represented by the following general formula (I).

The compound of formula (I)

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(Wherein n represents an integer of 2 to 4, and L represents a linking group having 2 to 4 valences.)

In the general formula (I), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, n is 2, and L is particularly preferably an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (II) to (IV), and compounds represented by (II) are particularly preferable. These polyfunctional thiols can be used singly or in combination.

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The blending amount of the polyfunctional thiol in the composition of the present invention is preferably 0.3 to 8.9% by weight, more preferably 0.8 to 6.4% by weight, based on the total solid content excluding the solvent. The polyfunctional thiol may be added for the purpose of improving stability, odor, resolution, developability and adhesion.

<Photopolymerization initiator>

The coloring composition of the present invention preferably contains a photopolymerization initiator from the viewpoint of further improving the sensitivity.

The photopolymerization initiator is not particularly limited as long as the photopolymerization initiator has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferable to have photosensitivity to a visible ray from an ultraviolet ray region. In addition, it may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, or may be an initiator that initiates cationic polymerization depending on the type of the monomer.

It is also preferable that the photopolymerization initiator contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton and oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, An oxime compound such as an imidazole or an oxime derivative, an organic peroxide, a thio compound, a ketone compound, an aromatic onium salt, a ketoxime, an aminoacetophenone compound, or a hydroxyacetophenone.

From the viewpoint of exposure sensitivity, it is also possible to use a trihalomethyltriazine compound, a benzyldimethylketal compound, an? -Hydroxyketone compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, Oxime compounds, triallyl imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, 3 -Aryl-substituted coumarin compound is preferable.

More preferably, a trihalomethyltriazine compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, an oxime compound, a triallylimidazole dimer, a triarylimidazole compound, a benzimidazole compound , An onium compound, a benzophenone compound, and an acetophenone compound, and is a trihalomethyltriazine compound, an? -Amino ketone compound, an oxime compound, a triallylimidazole compound, a benzophenone compound, a triarylimidazole compound, And at least one compound selected from the group consisting of a thiol compound and a thiol compound is particularly preferable. The triarylimidazole compound may be a mixture with benzimidazole.

Specifically, as the trihalomethyltriazine compound, the following compounds are exemplified. Ph is a phenyl group.

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As the triarylimidazole compound and the benzimidazole compound, the following compounds are exemplified.

(73)

As the trihalomethyltriazine compound, a commercially available product may also be used. For example, TAZ-107 (Midori Kagaku) may be used.

Particularly, when the coloring composition of the present invention is used in the production of a color filter provided in a solid-state image pickup device, it is necessary to form a fine pattern in a sharp shape, and therefore it is important that the coloring composition is developed with no caking Do. From this viewpoint, it is particularly preferable to use an oxime compound as the polymerization initiator. Particularly, in the case of forming a fine pattern in a solid-state image pickup device, stepper exposure is used for curing exposure. Since this exposure device may be damaged by halogen, and the addition amount of the polymerization initiator should also be suppressed to a low level, Taking this into consideration, it is particularly preferable to use an oxime compound as a photopolymerization initiator in order to form a fine pattern such as a solid-state image pickup device.

As the halogenated hydrocarbon compound having a triazine skeleton, for example, Wakabayashi et al., Bull. Chem. Soc. Japanese Patent Publication No. 53-133428, the compound described in German Patent Publication No. 3337024, the compound described in JP-A-3337024 by FC Schaefer et al. Org. Chem .; 29, 1527 (1964), compounds described in Japanese Laid-Open Patent Publication No. 62-58241, compounds described in Japanese Laid-Open Patent Publication No. 5-281728, compounds described in Japanese Laid-Open Patent Publication No. 5-34920, A compound described in Japanese Patent Publication No. 4212976, particularly a compound described in Japanese Patent Application Laid-Open No. 2013-077009, paragraph No. 0075, and the like.

As other photopolymerization initiators other than the above, acridine derivatives are exemplified. Specific examples thereof include compounds described in Japanese Patent Application Laid-Open No. 2013-077009, paragraph number 0076, and the contents thereof are incorporated herein by reference.

Examples of the ketone compound include compounds described in Japanese Patent Application Laid-Open No. 2013-077009, paragraph number 0077, and the contents thereof are incorporated herein by reference.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be suitably used. More specifically, for example, the aminoacetophenone-based initiator disclosed in Japanese Patent Application Laid-Open No. 10-291969 or the acylphosphine oxide-based initiator disclosed in Japanese Patent Publication No. 4225898 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 (all trade names, manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all trade names, manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which the absorption wavelength is matched to a long-wavelength light source such as 365 nm or 405 nm may be used. As the acylphosphine-based initiator, commercially available IRGACURE-819 and DAROCUR-TPO (trade names, all manufactured by BASF) can be used.

The photopolymerization initiator is more preferably an oxime compound. As specific examples of the oxime compounds, compounds described in JP 2001-233842 A, compounds described in JP-A 2000-80068, and JP 2006-342166 A can be used.

Examples of the oxime compounds such as oxime derivatives suitably used as the photopolymerization initiator in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan- 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

As oxime compounds, see J. C. S. Perkin II (1979) pp. Pp. 1653-1660, J. C. S. Perkin II (1979) pp. Pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-A 2004-534797, JP-A 2006-342166, etc. .

IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF) and TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.) are also suitably used in commercial products .

As oxime compounds other than the above-mentioned materials, compounds described in Japanese Unexamined Patent Publication No. 2009-519904 in which oxime is linked to carbazole N, compounds described in U.S. Patent No. 7626957 in which a hetero substituent is introduced into a benzophenone moiety, Compounds disclosed in Japanese Unexamined Patent Application Publication Nos. 2002-15025 and 2009-292039 in which nitro groups are introduced, ketoxime compounds described in International Patent Publication No. 2009-131189, triazine skeleton and oxime skeleton in the same molecule A compound described in U.S. Patent Publication No. 7556910, a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source, or the like may be used.

Preferably, the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744 can be suitably used. Of the cyclic oxime compounds, cyclic oxime compounds which are condensed in the carbazol dye described in JP-A-2010-32985 and JP-A-2010-185072 are particularly preferable from the viewpoint of high light absorbability and high sensitivity.

The compound described in Japanese Unexamined Patent Application Publication No. 2009-242469 having an unsaturated bond at a specific site of an oxime compound can also be suitably used because high sensitivity can be achieved by regenerating active radicals from polymerization inert radicals.

Particularly preferred are oxime compounds having a specific substituent group as disclosed in Japanese Patent Application Laid-Open No. 2007-269779 and oxime compounds having a thioaryl group as disclosed in Japanese Patent Application Laid-Open No. 2009-191061.

Specifically, as the oxime compound which is a photopolymerization initiator, a compound represented by the following general formula (OX-1) is preferable. Further, the N-O bond of the oxime may be an oxime compound of the (E) form, an oxime compound of the (Z) form, or a mixture of the form (E) and the form (Z).

&Lt; EMI ID =

In the general 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), the monovalent substituent represented by R is preferably a monovalent non-metallic atomic group.

Examples of the monovalent non-metallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. These groups may have one or more substituents. In addition, the substituent described above may be further substituted with another substituent.

Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

Specific examples of the general formula (OX-1) are shown below, but it is needless to say that the present invention is not limited thereto.

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

The molar extinction coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000 from the viewpoint of sensitivity.

Specific examples of the molar extinction coefficient of the compound include an ultraviolet visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian), an ethyl acetate solvent at a concentration of 0.01 g / L It is preferable to measure it.

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% by mass or more and 30% , More preferably 1 mass% or more and 20 mass% or less. Within this range, more excellent sensitivity and pattern formability can be obtained.

The composition of the present invention may contain only one kind of photopolymerization initiator, or may contain two or more kinds. When two or more kinds are included, the total amount is preferably in the above range.

<Pigment>

The coloring composition of the present invention may further contain a colorant other than the colorant multimer. Concretely, it is preferable to contain a pigment.

As the pigment used in the present invention, various conventionally known inorganic pigments or organic pigments can be used, and it is preferable to use an organic pigment. As the pigment, a high transmittance is preferable.

Specific examples of the inorganic pigments include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony, And composite oxides of the above metals.

As the organic pigment, for example,

C. I. Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;

C. I. Pigment Orange 36, 38, 43, 71;

C. I. Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;

C. I. Pigment Violet 19, 23, 32, 39;

C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

C. I. Pigment Green 7, 36, 37, 58;

C. I. Pigment Brown 25, 28;

C. I. Pigment Black 1, 7

And the like.

Examples of pigments that can be preferably used in the present invention include the following pigments. However, the present invention is not limited thereto.

CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,

C. I. Pigment Orange 36, 71,

C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,

C. I. Pigment Violet 19, 23, 32,

C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,

C. I. Pigment Green 7, 36, 37, 58,

C. I. Pigment Black 1, 7

These organic pigments can be used singly or in various combinations in order to enhance spectral control and color purity. Specific examples of the combination are shown below. As the red pigment, for example, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone, or at least one of them, a disazo yellow pigment, an isoindolin yellow pigment, a quinophthalone pigment A yellow pigment or a mixture with a perylene red pigment can be used. Examples of the anthraquinone pigments include CI Pigment Red 177, and the perylene pigments include CI Pigment Red 155 and CI Pigment Red 224. As the diketopyrrolopyrrole pigments, CI Pigment Red 254, and is preferably mixed with CI Pigment Yellow 139 in view of color resolution. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. When the ratio is 100: 4 or less, it is difficult to suppress the light transmittance of 400 nm to 500 nm. When the ratio is 100: 51 or more, the dominant wavelength approaches the short wavelength and the color resolution can not be increased. Particularly, the mass ratio is preferably in the range of 100: 10 to 100: 30. Further, in the case of a combination of red pigments, it can be adjusted in accordance with the obtained spectroscopy.

As the green pigment, it is possible to use a halogenated phthalocyanine-based pigment alone or in combination with a disazo-based yellow pigment, a quinophthalone-based yellow pigment, an azomethan-based yellow pigment or an isoindolene-based yellow pigment Can be used. For example, such examples include CI Pigment Green 7, 36, 37 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, Lt; / RTI &gt; 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

As the blue pigment, a phthalocyanine-based pigment may be used singly or a mixture of the phthalocyanine-based pigment and a dioxazine-based purple pigment may be used. For example, a mixture of C. I. Pigment Blue 15: 6 and C. I. Pigment Violet 23 is preferred. The mass ratio of the blue pigment to the purple pigment is preferably 100: 0 to 100: 100, more preferably 100: 10 or less.

As the pigment for black matrix, carbon, titanium black, iron oxide, titanium oxide alone or a mixture thereof is used, and a combination of carbon and titanium black is preferable. The mass ratio of carbon to titanium black is preferably in the range of 100: 0 to 100: 60.

The coloring composition of the present invention is preferably blended with pigments other than black, and is suitable for blue pigments.

When the pigment is used for a color filter, the primary particle size of the pigment is preferably 100 nm or less from the viewpoint of color unevenness or contrast, and is preferably 5 nm or more from the viewpoint of dispersion stability. The primary particle size of the pigment is more preferably 5 to 75 nm, further preferably 5 to 55 nm, and particularly preferably 5 to 35 nm.

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

Among them, the pigment is preferably a pigment selected from anthraquinone pigment, diketopyrrolopyrrole pigment, phthalocyanine pigment, quinophthalone pigment, isoindoline pigment, azomethine pigment, and dioxazine pigment . Particularly, CI Pigment Red 177 (anthraquinone pigment), CI Pigment Red 254 (diketopyrrolopyrrole pigment), CI Pigment Green 7, 36, 58, CI Pigment Blue 15: 6 ), CI Pigment Yellow 138 (quinophthalone pigment), CI Pigment Yellow 139, 185 (isoindoline pigment), CI Pigment Yellow 150 (azomethine pigment), CI Pigment Violet 23 Is particularly preferable.

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, and still more preferably from 25% by mass to 60% by mass, relative to the total components excluding the solvent contained in the coloring composition. 50% by mass.

The composition of the present invention may contain only one kind of pigment or two or more kinds of pigments. When two or more kinds are included, the total amount is preferably in the above range.

In the present invention, dyes other than the above-mentioned colorant multimer and pigments other than those described above may be contained. For example, Japanese Patent Application Laid-Open Nos. 64-90403, 64-91102, 1-94301, 6-11614, 2592207, 4808501, US 5667920, US 505950, US 5667920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 And JP-A-6-194828 can be used. Examples of the chemical structure include a pyrazole azo group, an anilino group, a triphenylmethane group, an anthraquinone group, a benzylidene group, an oxolane group, a pyrazolotriazoazo group, a pyridazo group, a sacynide, a phenothiazine group, And a pyrazole azo methane-based dye.

<Pigment dispersant>

When the coloring composition of the present invention has a pigment, the pigment dispersant may be used in combination with the purpose.

Examples of the pigment dispersant usable in the present invention include polymer dispersants such as polyamide amines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethane, modified polyester, modified poly ), A surfactant such as polyoxyethylene alkylphosphoric acid ester, a polyoxyethylene alkylamine, an alkanolamine, and a pigment derivative, and the like can be given .

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

Examples of the end-modified polymer having an anchor site on the surface of the pigment include polymers having a phosphate group at the terminals described in JP-A-3-112992, JP-A-2003-533455, JP- 273191 and the like, polymers having a partial skeleton of an organic dye described in JP-A No. 9-77994 and the like, and polymers having a heterocyclic ring, and the like. Further, a polymer in which an anchor site (an acid group, a basic group, a partial structure of an organic dye, a heterocycle, etc.) is introduced into two or more pigment surfaces on the polymer terminal end as disclosed in Japanese Patent Application Laid-Open No. 2007-277514 is also excellent in dispersion stability desirable.

Examples of the graft polymer having an anchor portion to the surface of the pigment include a polyester dispersant and the like. Specific examples thereof include those disclosed in JP-A-54-37082, JP-A-8-507960, Reaction products of poly (lower alkyleneimine) and polyester described in JP-A-2009-258668 and the like, reaction products of polyallylamine and polyester described in JP-A-9-169821 and the like, 10-339949, JP-A-2004-37986, WO2010 / 110491 and the like, copolymers of nitrogen atom monomers, JP-A-2003-238837, JP-A-2008-9426 , A graft polymer having a partial skeleton of an organic dye or a heterocycle described in JP-A-2008-81732 and the like, a macromonomer described in JP-A-2010-106268 And copolymers of acid group-containing monomers. Particularly, the amphoteric dispersing resin having a basic group and an acidic group described in JP-A-2009-203462 is particularly preferable from the viewpoints of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the coloring composition using the pigment dispersion Do.

A known macromonomer can be used as the macromonomer used when the graft polymer having an anchor site to the pigment surface is produced by radical polymerization. Macromonomer AA-6 (a macromonomer having a terminal group of methacryloyl AS-6 (polystyrene having a terminal group of methacryloyl group), AN-6S (copolymer of styrene and acrylonitrile having a terminal group of methacryloyl group), AB-6 (methyl methacrylate) Polylactic acid butyl ester whose terminal group is methacryloyl group), Flaccel FM5 (5-molar equivalent of 2-hydroxyethyl methacrylate-epsilon -caprolactone) manufactured by Daicel Chemical Industries, Ltd., FA10L (acrylic acid 2 - 10-molar equivalent of ε-caprolactone of hydroxyethyl), and polyester-based macromonomers described in JP-A-2-272009. Among them, polyester-based macromonomers having particularly good flexibility and good solvent-solubility are particularly preferable from the viewpoints of dispersibility of the pigment dispersion, dispersion stability, and developability exhibited by the coloring composition using the pigment dispersion, Polyester macromonomers represented by the polyester-based macromonomers described in JP-A-2-272009 are particularly preferable.

As block type polymers having anchor sites to the pigment surface, block type polymers described in JP-A-2003-49110 and JP-A-2009-52010 are preferable.

Specific examples of such a pigment dispersant usable in the present invention are commercially available products such as "DA-7301" manufactured by Goosumoto Kasei Co., Ltd., "Disperbyk-101" (polyamide amine phosphate) manufactured by BYK Chemie, 107 (Copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymeric copolymer) "," BYK-P104, P105 EFKA4047, 4050 to 4010 to 4165 (polyurethane resin), EFKA4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyester amide) (High molecular weight polycarboxylic acid salt), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ", Ajinomoto Fine Techno Corporation" Ajisper PB821, PB822, PB880, PB881 " Fluorene TG-710 (uretene oligomer) ", "Polyflow No. 50E, No. 300 (Arc 873, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725 ", "Demol RN, N (naphthalene sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "," Homogenol L- , "Acetamine 86 (Stearylamine Acetate)", "Nippon Lubrizol Co., Ltd.", "Solpres 5000" (manufactured by Nippon Polyurethane Industry Co., Ltd.), "Emulsion 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) (Graft polymer) ", 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 17000, 27000 (polymer having functional group at the terminal), 24000, 28000, 32000, 38500 (Polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Kawaken Fine Chemicals Co., Ltd.," Hinoact T-8000E "manufactured by Kawaken Fine Chemicals Co., Quot; "W001: cationic surfactant", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl (trade name) Nonionic surfactants such as phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic surfactants such as "W004, W005, W017 & Based surfactant, EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450, manufactured by Morishita Sangyo Co., F38, L42, L44, L61, L64, F68, L72, L64, L64, L64, P95, F77, P84, F87, P94, L101, P103, F108, L121 and P-123 "manufactured by Sanyo Chemical Industries, 0 "and the like.

These pigment dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymeric dispersing agent. The pigment dispersant may be used in combination with an alkali-soluble resin together with an end-modified polymer having an anchor portion on the surface of the pigment, a graft-type polymer, and a block-type polymer. Examples of the alkali-soluble resin include (meth) acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and acidic cellulose derivatives having a carboxylic acid in the side chain. Particularly, a (meth) acrylic acid copolymer is preferable. The N-substituted maleimide monomer copolymer described in JP-A No. 10-300922, the ether dimer copolymer disclosed in JP-A No. 2004-300204, the polymerizable group described in JP-A No. 7-319161 Is also preferable. Specifically, an alkali-soluble resin: benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer is exemplified.

In the case of containing the pigment dispersant in the coloring composition, the total content of the pigment dispersant is preferably 1 part by mass to 80 parts by mass, more preferably 5 parts by mass to 70 parts by mass, and more preferably 10 parts by mass per 100 parts by mass of the pigment To 60 parts by mass is more preferable. The specific dispersion resin is preferably 50 mass% or more, more preferably 60 mass% or more, and most preferably 70 mass% or more, of the dispersant components contained in the coloring composition.

The composition of the present invention may contain only one kind of pigment dispersing agent or two or more kinds of pigment dispersing agents respectively. When two or more kinds are included, the total amount is preferably in the above range.

Concretely, in the case of using a polymer dispersant, the amount to be used is preferably in the range of 5 parts by mass to 100 parts by mass, more preferably in the range of 10 parts by mass to 80 parts by mass, based on 100 parts by mass of the pigment.

When the pigment derivative is used in combination, the amount of the pigment derivative to be used is preferably in the range of 1 to 30 parts by mass, more preferably in the range of 3 to 20 parts by mass, based on 100 parts by mass of the pigment And most preferably in the range of 5 parts by mass to 15 parts by mass.

In view of curing sensitivity and color density, the total content of the colorant and the dispersant component in the coloring composition is preferably 50% by mass or more and 90% by mass or less, more preferably 55% by mass or more and 85% By mass or less, more preferably 60% by mass or more and 80% by mass or less.

<(F) Alkali-soluble resin>

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

The molecular weight of the alkali-soluble resin is not particularly limited, but Mw is preferably 5000 to 100,000. Mn is preferably 1,000 to 20,000.

As the alkali-soluble resin, a linear organic polymer can be appropriately selected from an alkali-soluble resin having at least one group capable of promoting alkali solubility in a molecule (preferably an acrylic copolymer, a styrene-based copolymer as a main chain) . From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin and an acryl / acrylamide copolymer resin are preferable. From the viewpoint of development control, an acrylic resin, an acrylamide resin , An acrylic / acrylamide copolymer resin is preferable.

Examples of the group capable of promoting alkali solubility (hereinafter also referred to as acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and it is preferable that the group can be developed by a weakly alkaline aqueous solution , And (meth) acrylic acid are particularly preferable. These acid groups may be one kind or two or more kinds.

Examples of the monomer capable of imparting an acid group after the polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, monomers having an epoxy group such as glycidyl (meth) acrylate, And monomers having an isocyanate group such as cyanatoethyl (meth) acrylate. The monomers for introducing these acid groups may be one kind or two or more kinds. In order to introduce an acid group into an alkali-soluble resin, for example, a monomer having an acid group and / or a monomer capable of giving an acid group after polymerization (hereinafter sometimes referred to as a " monomer for introducing an acid group & .

When an acid group is introduced as a monomer component capable of imparting an acid group after polymerization, a treatment for imparting an acid group as described later, for example, is required after polymerization.

For the production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as the temperature, pressure, kind and amount of the radical initiator and the kind of solvent at the time of producing the alkali-soluble resin by the radical polymerization method can be easily set by those skilled in the art and can be determined experimentally .

As the linear organic polymer used as an alkali-soluble resin, a polymer having a carboxylic acid in its side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, Maleic anhydride copolymers, maleic acid copolymers and novolac resins, and acidic cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to the polymer having a hydroxyl group. Particularly, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as an alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (Meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl , And cyclohexyl (meth) acrylate. Examples of the vinyl compound include styrene,? -Methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, Furfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like as the N-substituted maleimide monomer described in JP-A No. 10-300922 , N-phenylmaleimide, N-cyclohexylmaleimide and the like. In addition, these monomers copolymerizable with (meth) acrylic acid may be only one type, or two or more types may be used.

As the alkali-soluble resin, a monomer component essentially comprising a compound represented by the following formula (ED) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may also be referred to as " (A).

[Formula 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.

(ED2)

[Formula 77]

In the general 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), reference can be made to the disclosure of Japanese Laid-Open Patent Publication No. 2010-168539.

As a result, the colored composition of the present invention can form a cured coating film having excellent heat resistance as well as transparency. In the general formula (1) representing 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 includes, for example, methyl, ethyl, , Straight-chain or branched alkyl groups such as isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl and 2-ethylhexyl; An aryl group such as phenyl; Alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl and the like; An alkyl group substituted by alkoxy such as 1-methoxyethyl or 1-ethoxyethyl; An alkyl group substituted with an aryl group such as benzyl; And the like. Of these, an acid such as methyl, ethyl, cyclohexyl, benzyl and the like and a substituent of a primary or secondary carbon which is difficult to desorb by heat are preferable from the viewpoint of heat resistance.

Specific examples of the ether dimer include dimethyl-2,2'- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2 '- [oxybis (methylene)] bis- (Isopropyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, di (n-propyl) ] Bis-2-propenoate, di (n-butyl) -2,2 '- [oxybis (Methylene)] bis-2-propenoate, di (tert-butyl) -2,2 '- [oxybis Di (lauryl) -2,2'- [oxybis (methylene)] bis-2-propenoate, di (lauryl) Bis (2-ethylhexyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di- Methoxyethyl) -2,2 '- [oxybis Bis (2-propenyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, dibenzyl- Bis (2-propenyl) bis [2-propenyl] biphenyl-2, 2 '- [oxybis (methylene)] bis-2-propenoate, dicyclohexyl- (Methylene)] bis-2-propenoate, di (tert-butylcyclohexyl) -2,2 '- [oxybis Di (tricyclodecanyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di Bis (2-propenyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, diadamanthyl- Di (2-methyl-2-adamantyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate. Among these, dimethyl-2,2'- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2 '- [oxybis (methylene)] bis- Propylene glycol dicyclohexyl-2,2 '- [oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2' - [oxybis (methylene)] bis-2-propenoate. These ether dimers may be one kind or two or more kinds. The structure derived from the compound represented by the formula (ED) may be copolymerized with another monomer.

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

In general formula (X)

(78)

(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 a benzene ring, Alkyl group, and n represents an integer of 1 to 15.)

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

In order to improve the crosslinking efficiency of the coloring composition of the present invention, it is preferable to use an alkali-soluble resin having a polymerizable group. When such an alkali-soluble resin is used, the solvent resistance, which is an effect of the present invention, tends to be further improved. In addition, light resistance and heat resistance tend to be improved. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. Examples of the above-mentioned polymer containing a polymerizable group include DYNAL NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (manufactured by Diamond Shamrock Co., Ltd., containing COOH), BisCot R-264, 106 (all manufactured by Osaka Yuki Kagaku Kogyo Kabushiki Kaisha), Cyclomer P series, Flackcell CF200 series (all manufactured by Daicel Chemical Industries Ltd.), Ebecryl 3800 (manufactured by Daicel Chemical Industries, Ltd.) . As the alkali-soluble resin containing these polymerizable groups, it is preferable that an isocyanate group and an OH group are previously reacted to leave an unreacted isocyanate group, and a compound containing a (meth) acryloyl group and a Acrylic resin containing an unsaturated group obtained by the reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule, a polymerizable double bond-containing acrylic resin obtained by a reaction of an acrylic resin, Acid pendant epoxy acrylate resin, a polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond, an acrylic resin containing an OH group, an isocyanate and a polymerizable group , A resin obtained by reacting a compound having an epoxy group-containing compound 207 and JP-A No. 2003-335814, a resin obtained by basic treatment of a resin having on its side chain an ester group having a leaving group such as a halogen atom or a sulfonate group on?

As the alkali-soluble resin, a multi-component copolymer composed of a (meth) acrylic acid benzyl / (meth) acrylic acid copolymer and a (meth) benzyl acrylate / (meth) acrylic acid / other monomer is suitable. (Meth) acrylic acid benzylate / (meth) acrylic acid / (meth) acrylic acid-2-hydroxyethyl copolymer copolymerized with 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate copolymer disclosed in Japanese Patent Application Laid-open No. 7-140654 (Meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / Methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / meta Acrylic acid copolymers, and particularly preferable examples thereof include copolymers of benzyl methacrylate / methacrylic acid and the like.

As the alkali-soluble resin, reference may be made to Japanese Patent Laid-Open Publication No. 2012-208494, paragraphs 0558 to 0571 (corresponding to [0685] to [0700] of US Patent Application Publication No. 2012/0235099) Which is incorporated herein by reference.

In addition, the copolymer (B) described in paragraphs Nos. 0029 to 0063 described in JP-A-2012-32767 and the alkali-soluble resin used in the examples, and the copolymer described in paragraphs 0088 to 0098 of JP-A- The binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of Japanese Laid-Open Patent Publication No. 2012-137531 and the binder resin used in the examples, and the binder resin used in the examples of Japanese Laid-Open Patent Publication No. 2013-024934 To 0143 and binder resins used in the examples, paragraphs 0092 to 0098 of Japanese Laid-Open Patent Publication No. 2011-242752 and binder resins used in the examples, and Japanese Laid-Open Patent Publication No. 2012-032770, paragraph No. 0030 It is preferable to use the binder resin as described in [0072]. The contents of which are incorporated herein by reference. More specifically, the following resins are preferable.

(79)

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

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and 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, more preferably 2% by mass to 12% by mass relative to the total solid content of the coloring composition , And particularly preferably 3% by mass to 10% by mass.

The composition of the present invention may contain only one alkali-soluble resin, or may contain two or more kinds of alkali-soluble resins. When two or more kinds are included, the total amount is preferably in the above range.

<Other Ingredients>

The coloring composition of the present invention may further contain other components such as an organic solvent, a crosslinking agent, a polymerization inhibitor, a surfactant, an organic carboxylic acid, and an organic carboxylic acid anhydride, in addition to the above- .

<< Organic solvents >>

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

The organic solvent is not particularly limited so long as it satisfies the solubility of each component and the coating property of the coloring composition, but is preferably selected in consideration of solubility, coating ability, and safety of an ultraviolet absorber, an alkali-soluble resin or a dispersing agent . In preparing the coloring composition of the present invention, it is preferable to include at least two kinds of organic solvents.

Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, , Methyl lactate, ethyl lactate, alkyloxyacetate (such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, Ethoxyacetic acid ethyl, etc.), 3-oxypropionic acid alkyl esters (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl ethoxypropionate, ethyl 3-ethoxypropionate), 2-oxypropionic acid alkyl esters (e.g., methyl 2-oxypropionate, 2-oxypropionion Propyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate) , Methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy- Examples of the ethers include methylene, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate and ethyl 2-oxobutanoate, and ethers such as diethylene glycol dimethyl ether, tetra Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Ether, diethylene glycol Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and also ketones such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, Cyclohexanone, 2-heptanone, 3-heptanone, and the like, and examples of the aromatic hydrocarbon include toluene, xylene, and the like.

From the viewpoints of solubility of the ultraviolet absorber and the alkali-soluble resin, and improvement of the shape of the coated surface, these organic solvents are also preferably mixed with two or more kinds. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3- A mixed solution composed of two or more kinds selected from methyl propionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate to be.

The content of the organic solvent in the coloring composition is preferably such that the total solid content concentration of the composition is 5% by mass to 80% by mass, more preferably 5% by mass to 60% by mass, And particularly preferably from 10% by mass to 50% by mass.

The composition of the present invention may contain only one kind of organic solvent or two or more kinds of organic solvents. When two or more kinds are included, the total amount is preferably in the above range.

<< Cross-linking agent >>

By using a crosslinking agent as a complement to the coloring composition of the present invention, the hardness of the cured film formed by curing the coloring composition can be further increased.

The crosslinking agent is not particularly limited as long as it can perform film curing by a crosslinking reaction. Examples of the crosslinking agent include (a) an epoxy resin, (b) at least one substituent selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group A phenol compound, a naphthol compound or a hydrolyzate substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group; (c) And a hydroxyanthracene compound. Among them, a polyfunctional epoxy resin is preferable.

Details of specific examples of crosslinking agents and the like can be found in paragraphs 0134 to 0147 of Japanese Laid-Open Patent Publication No. 2004-295116.

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

The composition of the present invention may contain only one type of crosslinking agent or two or more types of crosslinking agents. When two or more kinds are included, the total amount is preferably in the above range.

<< Polymerization inhibitor >>

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

Examples of the polymerization inhibitor usable in the present invention include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'- (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N- have.

When the polymerization inhibitor is contained in the coloring composition of the present invention, the addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the entire composition.

The composition of the present invention may contain only one kind of polymerization inhibitor or two or more kinds thereof. When two or more kinds are included, the total amount is preferably in the above range.

<< Surfactant >>

To the coloring composition of the present invention, various surfactants may be added in order to further improve the applicability. As the surfactant, various surfactants such as a fluorine surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.

Particularly, since the coloring composition of the present invention contains the fluorine-containing surfactant, the uniformity of the coating thickness and the liquid-repellency (liquid-repellency) can be improved in that the liquid property (particularly, fluidity) Can be further improved.

That is, in the case of forming a film using a coating liquid to which a coloring composition containing a fluorine-containing surfactant is applied, the wettability of the surface to be coated is improved by lowering the interfacial tension between the surface to be coated and the coating liquid, Thereby improving the stability. Thus, even when a thin film of about several micrometers is formed in a small amount of liquid, it is effective in that it is possible to more appropriately form a film having a uniform thickness with a small thickness deviation.

The fluorine content in the fluorine surfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. The fluorine-containing surfactant having a fluorine content within this range is effective from the viewpoints of the uniformity of the thickness of the coating film and the liquid-repellency, and the solubility in the coloring composition is also good.

Examples of the fluorine-based surfactant include Megapak F171, Dong F172, Dong F173, Dong F176, Dong F177, Dong F141, Dong F142, Dong F143, Dong F144, Dong R30, Dong F437, Dong F475, Dong F479, Dong F482 (Manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, and SC-101 (manufactured by Sumitomo 3M Limited), F554, F780, and F781 (manufactured by DIC Corporation), Fluorad FC430, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393 and KH-40 (manufactured by Asahi Glass Co., Ltd.) have.

Specific examples of the nonionic surfactants include glycerol, trimethylol propane, trimethylol ethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerin ethoxylate and the like), polyoxyethylene Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol diallylate, polyethylene glycol Diisostearate and consumptive fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904 and 150R1 from BASF) Ltd.) and the like.

Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) Acrylic acid-based (co) polymer Polflor No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusoh Co., Ltd.).

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

Examples of silicon based surfactants include fluororesins such as "TORAY Silicon DC3PA", "TORAY Silicone SH7PA", "TORAY Silicon DC11PA", "TORAY Silicone SH21PA", "TORAY Silicone SH28PA", "DORAY Silicone SH29PA TSF-4440 "," TSF-4445 "," TSF-4460 "," TSF-4452 "," Tory Silicone SH8400 "and" TSF-4440 "manufactured by Momentive Performance Materials "KF341", "KF6001", and "KF6002" manufactured by Shin-Etsu Silicones Co., Ltd., "BYK307", "BYK323", and "BYK330" manufactured by Big Chemie.

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

The composition of the present invention may contain only one type of surfactant or two or more types of surfactant. When two or more kinds are included, the total amount is preferably in the above range.

<< Organic carboxylic acid, organic carboxylic acid anhydride >>

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

Specific examples of the organic carboxylic acid compound include an aliphatic carboxylic acid and 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, pivalic acid, caproic acid, glycolic acid, acrylic acid and methacrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid , Dicarboxylic acids such as adipic acid, pimelic acid, cyclohexane dicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, tricarboxylic acids such as tricarballylic acid and aconitic acid, and the like have. Examples of the aromatic carboxylic acid include a carboxylic acid in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid or phthalic acid, and a carboxylic acid in which a carboxyl group is bonded through a carbon bond from a phenyl group. Among these, particularly preferred are those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically, maleic acid, malonic acid, succinic acid and itaconic acid.

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, anhydrous trichloroacetic acid, trifluoroacetic anhydride, anhydrous tetrahydrophthalic acid, N-octadecyl succinic anhydride, anhydrous 5-norbornene-2,3-dicarboxylic acid, and the like can also be used in the presence of an acid anhydride such as maleic anhydride, citraconic anhydride, itaconic anhydride, anhydroglutaric acid, And an aliphatic carboxylic acid anhydride. Examples of the aromatic carboxylic acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and anhydrous naphthalic acid. Among these, particularly preferred are those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, such as maleic anhydride, succinic anhydride, citraconic anhydride and itaconic anhydride.

When the coloring composition of the present invention contains an organic carboxylic acid or an organic carboxylic acid anhydride, the addition amount of the organic carboxylic acid and / or organic carboxylic acid anhydride is usually 0.01 to 10% by weight, preferably 0.03 to 5% by weight, Preferably 0.05 to 3% by weight.

The composition of the present invention may contain only one kind of the organic carboxylic acid and / or the organic carboxylic acid anhydride, respectively, or two or more kinds thereof. When two or more kinds are included, the total amount is preferably in the above range.

By adding these organic carboxylic acids and / or organic carboxylic anhydrides having a molecular weight of 1000 or less, it is possible to further reduce the remnant of the undissolved product of the coloring composition while maintaining high pattern adhesion.

In addition to the above, various additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like can be added to the coloring composition, if necessary. Examples of these additives include those described in paragraphs 0155 to 0156 of Japanese Patent Application Laid-Open No. 2004-295116, the contents of which are incorporated herein by reference.

The coloring composition of the present invention may contain a sensitizer or light stabilizer described in paragraph 0078 of Japanese Patent Application Laid-Open No. 2004-295116 or a thermal polymerization inhibitor described in paragraph 0081 of the same.

The composition of the present invention may contain only one kind of each of the above components, or two or more kinds of the above components. When two or more kinds are included, the total amount is preferably in the above range.

&Lt; Preparation method of colored composition >

The coloring composition of the present invention is prepared by mixing the above-described components.

Further, at the time of preparing the coloring composition, each component constituting the coloring composition may be blended at one time, and each component may be dissolved and dispersed in a solvent and then blended continuously. In addition, the order of application and the working conditions at the time of compounding are not particularly limited. For example, the composition may be prepared by dissolving and dispersing the entire components in a solvent at the same time. If necessary, the components may be appropriately mixed into two or more solutions and dispersions, .

The coloring composition prepared as described above is preferably filtered and separated by using a filter having a pore diameter of 0.01 to 3.0 m, more preferably a pore diameter of about 0.05 to 0.5 m, have.

The coloring composition of the present invention is preferably used for forming a colored layer of a color filter. More specifically, the coloring composition of the present invention is suitably used for forming a coloring pattern (coloring layer) of a color filter, because it can form a cured film having excellent heat resistance and color characteristics. The coloring composition of the present invention can be used for forming a coloring pattern such as a color filter used in a solid-state image pickup device (for example, a CCD or a CMOS) or an image display device for a liquid crystal display (LCD) For example. In addition, it can be suitably used for producing printing ink, inkjet ink, and paint. Among them, a color filter for a solid-state image pickup device such as CCD and CMOS can be suitably used for production.

&Lt; Cured Film, Pattern Forming Method, Color Filter, and Manufacturing Method of Color Filter >

Next, the cured film, the pattern forming method and the color filter according to the present invention will be described in detail with reference to its manufacturing method.

The cured film of the present invention is obtained by curing the coloring composition of the present invention. Such a cured film is preferably used for a color filter.

In the pattern forming method of the present invention, the coloring composition of the present invention is applied on a support to form a coloring composition layer, and unnecessary portions are removed to form a coloring pattern.

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

The composition of the present invention may be patterned by a so-called photolithography method to produce a color filter, or a pattern may be formed by a dry etching method.

That is, as a first method for producing the color filter of the present invention, there is provided a method of producing a color filter, comprising the steps of: forming a coloring composition layer on a support using the coloring composition of the present invention; exposing the coloring composition layer in a pattern; A method of manufacturing a color filter including a step of developing an unexposed portion of a layer is exemplified.

As a second manufacturing method of the color filter of the present invention, there is provided a process for producing a color filter, comprising the steps of applying a coloring composition on a support to form a coloring composition layer and curing to form a colored layer, a step of forming a photoresist layer on the colored layer , A step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry-etching the colored layer using the resist pattern as an etching mask.

In the present invention, a photolithography method is more preferable.

The details of these will be described below.

Hereinafter, each step in the pattern forming method of the present invention will be described in detail with reference to a method of manufacturing a color filter for a solid-state imaging device, but the present invention is not limited to this method. Hereinafter, a color filter for a solid-state imaging device may be simply referred to as a "color filter ".

&Lt; Step of forming coloring composition layer &gt;

In the step of forming the coloring composition layer, a step of forming a coloring composition layer is formed on the support by applying the coloring composition of the present invention.

Examples of the support that can be used in the present step include a solid-state imaging device (solid-state imaging device) provided with an imaging element (light-receiving element) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) A substrate for a device can be used.

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

The color pattern of the solid-state imaging element or the back surface of the substrate for a solid-state imaging element may be provided with a light-shielding film.

If necessary, an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or planarizing the surface of the substrate. The undercoat layer may contain a solvent, an alkali-soluble resin, a polymerizable compound, a polymerization inhibitor, a surfactant, a photopolymerization initiator, and the like. These components may be appropriately selected from components incorporated in the composition of the present invention .

As a method of applying the coloring composition of the present invention onto a support, various coating methods such as slit coating, ink-jetting, spin coating, flexible coating, roll coating, screen printing and the like can be applied.

Drying (prebaking) of the coloring composition layer applied on the support can be performed in a hot plate, an oven or the like at a temperature of 50 ° C to 140 ° C for 10 seconds to 300 seconds.

<Step of forming a pattern by photolithography method>

<< Process of Exposure >>

In the exposure step, the coloring composition layer formed in the step of forming the coloring composition layer is subjected to pattern exposure through a mask having a predetermined mask pattern using, for example, an exposure apparatus such as a stepper. Thus, a cured film is obtained.

As the radiation (light) usable at the time of exposure, ultraviolet rays such as g-line and i-line are preferably used (particularly preferably i-line). Irradiation dose (exposure dose) is preferably ^{30mJ / cm 2 ~ 1500mJ / cm} 2 is preferably 50mJ / cm ² ~ 1000mJ / cm ^2, and more ^{preferably, 80mJ / cm 2 ~ 500mJ /} cm 2 in particular.

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

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

In this step, a cured film having a thin film thickness of 0.7 m or less can be suitably formed, and the obtained cured film is subjected to a development treatment in a pattern formation step described later, whereby a thin film can be obtained, , And a colored pattern excellent in the pattern shape can be obtained.

<< Development Process >>

Subsequently, the alkali developing process is carried out so that the coloring composition layer in the tailing part in the exposure step is eluted into the aqueous alkaline solution, leaving only the photo-cured part.

As the developing solution, an organic alkali developing solution which does not cause damage to the imaging element, circuit, etc. on the ground (base) is preferable. The developing temperature is usually 20 to 30 DEG C, and the developing time is conventionally 20 to 90 seconds. In order to remove the residues, it is sometimes carried out 120 to 180 seconds in recent years. Further, in order to further improve the removability of the residue, the step of removing the developer every 60 seconds and supplying the fresh developer may be repeated a number of times.

Examples of the alkali agent used in the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide , Benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo- [5,4,0] -7-undecene, and these alkaline agents An alkaline aqueous solution diluted with pure water to a concentration of 0.001 mass% to 10 mass%, preferably 0.01 mass% to 1 mass% is preferably used as the developer.

As the developing solution, an inorganic alkali may be used, and examples of the inorganic alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate and the like.

When a developer comprising such an alkaline aqueous solution is used, it is generally cleaned (rinsed) with purified water after development.

Subsequently, it is preferable to carry out a heat treatment (post-baking) after drying. If a multicolor colored pattern is formed, a cured film can be produced by repeating the above steps for each color in sequence. As a result, a color filter is obtained.

The post-baking is a post-development heat treatment for making the curing to be complete, and is generally subjected to a heat curing treatment at 100 캜 to 240 캜, preferably at 200 캜 to 240 캜.

The post-baking treatment can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot-air circulation type drier), or a high-frequency heater so as to satisfy the above conditions.

&Lt; Case where pattern is formed by dry etching >

In the case of forming a pattern by dry etching, reference can be made to the disclosure of Japanese Laid-Open Patent Publication No. 2013-64993, the contents of which are incorporated herein by reference.

Further, the manufacturing method of the present invention may have a known process as a manufacturing method of a color filter for a solid-state image pickup device, as the other process, if necessary. For example, the curing step may include a curing step of curing the colored pattern formed by heating and / or exposure after the coloring composition layer forming step, the exposure step and the pattern forming step described above, if necessary.

In addition, when the coloring composition of the present invention is used, for example, clogging of nozzles and piping in the dispenser discharge portion, contamination due to deposition, sedimentation and drying of the coloring composition or pigment into the coater may occur. Therefore, in order to efficiently clean the contamination caused by the coloring composition of the present invention, it is preferable to use the solvent relating to the present composition described above as a cleaning liquid. Also, Japanese Patent Application Laid-Open Nos. 7-128867, 7-146562, 8-278637, 2000-273370, 2006-85140, The cleaning liquids described in JP-A-2006-291191, JP-A-2007-2101, JP-A-2007-2102 and JP-A-2007-281523 are also suitable as a cleaning liquid for the coloring composition of the present invention Can be used to make.

Among these, alkylene glycol monoalkyl ether carboxylates and alkylene glycol monoalkyl ethers are preferred.

These solvents may be used alone or in combination of two or more. When mixing two or more species, it is preferable 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. The mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) is particularly preferably 60/40. Further, in order to improve the permeability of the cleaning liquid to the contaminants, the surfactant relating to the present composition described above may be added to the cleaning liquid.

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 excellent pattern shape, and the roughness of the pattern surface And the residue in the developing portion is suppressed, so that the color characteristic is excellent.

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

The thickness of the colored pattern (colored pixel) in the color filter of the present invention is preferably 2.0 占 퐉 or less, more preferably 1.0 占 퐉 or less, and even more preferably 0.7 占 퐉 or less.

The size (pattern width) of the coloring pattern (coloring pixel) is preferably 2.5 占 퐉 or less, more preferably 2.0 占 퐉 or less, and particularly preferably 1.7 占 퐉 or less.

<Solid-state image sensor>

The solid-state image pickup device of the present invention includes the above-described color filter of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it has the color filter according to the present invention and functions as a solid-state imaging device.

A plurality of photodiodes constituting a light receiving area of a solid-state image sensor (a CCD image sensor, a CMOS image sensor, or the like) and a transfer electrode composed of polysilicon or the like are formed on a support, and on the photodiode and the transfer electrode, And a device shielding film made of silicon nitride or the like formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving portion. The device protective film is provided with the color filter for solid- Filter.

Further, it may be a configuration having the light-converging means (for example, a microlens or the like hereinafter) on the device protective layer and below the color filter (near the support) or a configuration having the light-

<Image Display Device>

The color filter of the present invention can be used not only for the solid-state image pickup device but also for an image display apparatus such as a liquid crystal display apparatus and an organic EL display apparatus, and is particularly suitable for use in a liquid crystal display apparatus. The liquid crystal display device provided with the color filter of the present invention can display a high-quality image with a good color tone of the display image and excellent display characteristics.

For the definition of the display device and the details of each display device, refer to, for example, "Electronic display device (Sasaki Akio Kogyo Co., Ltd., Sakai, 1990 issued by Sakai Corporation)", "Display device (Ibukisumi Akira, ) Published in the first year of Heisei) ". The liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Uchida Tatsuo, published by Sakai High School Co., Ltd. in 1994) ". The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the present invention can be applied to various types of liquid crystal display devices described in the "next generation liquid crystal display technology ".

The color filter of the present invention may be used in a color TFT type liquid crystal display device. The color TFT type liquid crystal display device is described in, for example, "Color TFT liquid crystal display (published by Kyoritsu Shootpan Co., Ltd., 1996) ". The present invention can also be applied to a liquid crystal display device such as a transverse electric field driving system such as an IPS or a pixel division system such as an MVA or an STN, TN, VA, OCS, FFS and R-OCB .

The color filter in the present invention can also be provided in a bright, high definition COA (Color-filter On Array) system. In the COA type liquid crystal display device, the required characteristics for the color filter layer may require the characteristics required for the interlayer insulating film, that is, the low dielectric constant and the peel liquid resistance, in addition to the above-mentioned usual required characteristics. The color filter of the present invention is excellent in color purity, light transmittance and the like and excellent in color tone of a colored pattern (pixel) in that a coloring matter multifunctional material excellent in hue is used. Therefore, a COA type liquid crystal display Device can be provided. Further, in order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.

These image display methods are described in, for example, page 43 of "EL, PDP, and LCD display technology and the latest trend in the market" (published by Toray Research Center Research Division, 2001).

The liquid crystal display device provided with the color filter in the present invention is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film in addition to the color filter in the present invention. The color filter of the present invention can be applied to a liquid crystal display device constituted by these known members. These members are described in, for example, "Market of Liquid Crystal Display Materials and Chemicals, 1994 (published by Shimaguchi Co., Ltd., CMC)", "2003 Current Status and Future Prospects of LCD Related Markets Published by Fuji Chimera Soken Co., Ltd., 2003).

Regarding the backlight, it is described in the SID meeting Digest 1380 (2005) (A. Konno et al.) And in the monthly display December 2005, pages 18-24 (Yamazaki Shimaya), 25-30 pages (Yagi Takaaki) .

When the color filter according to the present invention is used for a liquid crystal display device, high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, and LED light sources (RGB-LEDs) of red, As the light, it is possible to provide a liquid crystal display device having high luminance, high color purity, and good color reproducibility.

Example

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless the scope of the invention is exceeded. In addition, "%" and "part" are on a mass basis unless otherwise specified.

<Synthesis Example of Dye Compound A-1>

(80)

(Synthesis of Intermediate 1)

Compound No. of International Publication No. WO2013 / 082409. In the synthesis example 2, the intermediate 1 was obtained by changing iodomethane to iodoethane.

(Synthesis of intermediate 2)

In the acid chloridation of Acid Red 289 of Exemplified Compound 1 of International Publication No. WO2013 / 031838, intermediate 2 was obtained using intermediate 1.

(Synthesis of Intermediate 3)

Intermediate 2 (7.98 g) was dissolved in 40 ml of methylene chloride 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 3 hours, washed with 100 ml of 1N hydrochloric acid, and then washed with saturated brine. The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The residue was dissolved in 50 ml of chloroform and purified by column chromatography (chloroform: ethyl acetate = 7: 3) to obtain 6.65 g of Intermediate 3.

Maximum absorption wavelength: 543 nm (methanol)

(Synthesis of Intermediate 4)

(5 mg), 2-isocyanatoethyl methacrylate (0.96 g), Neostan U-600 (Nitto Kasei), 10 mg of 2,6-diisocyantyl-4-methylphenol Was dissolved in 30 ml of dimethylacetamide, and the mixture was stirred at 60 占 폚 for 4 hours. The reaction solution was added to 100 ml of water and extracted with 100 ml of ethyl acetate. Then, it was dried with sodium sulfate and concentrated under reduced pressure. 100 ml of acetonitrile was added to the residue, and the mixture was stirred for 1 hour and filtered to obtain 4.5 g of Intermediate 4. [

Maximum absorption wavelength: 543 nm (methanol)

(Synthesis of Dye Compound A-1)

Intermediate 4 (4 g) was dissolved in methanol (20 ml), lithium N, N-bis (trifluoromethanesulfonyl) imide (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. To the resulting residue was added 50 ml of acetonitrile, followed by dispersion washing, followed by filtration to obtain dye compound A-1 (4 g).

Maximum absorption wavelength: 543 nm (methanol)

<Synthesis Example of Dye Compound A-2>

In the synthesis example of the dye compound A-1, the lithium N, N-bis (trifluoromethanesulfonyl) imide was changed to potassium N, N-bis (nonafluorobutainesulfonyl) To obtain a dye compound A-2.

Maximum absorption wavelength: 543 nm (methanol)

<Synthesis Example of Dye Compound A-3>

In the synthesis example of the dye compound A-1, the lithium N, N-bis (trifluoromethanesulfonyl) imide was changed to potassium N, N-hexafluoropropane-1,3-disulfonylimide , And the procedure was otherwise carried out to obtain the dye compound A-2.

Maximum absorption wavelength: 543 nm (methanol)

<Synthesis Example of Dye Compound A-4>

In the synthesis example of the dye compound A-1, except that the lithium N, N-bis (trifluoromethanesulfonyl) imide was changed to a lithium tetrakis (pentafluorophenyl) borate ethyl ether complex, , Thereby obtaining the dye compound A-2.

Maximum absorption wavelength: 543 nm (methanol)

<Dye compound A-5 to A-15>

Monomers serving as starting materials for the repeating units A-5 to A-15 described later were synthesized in the same manner as in the foregoing synthesis examples.

<Synthesis Example of Pigment Polymer P-1>

24 g of cyclohexanone was added to the three-necked flask, and the mixture was heated to 90 DEG C under a nitrogen atmosphere. To this solution was added the dye 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'-azobis (Trade name: V601, manufactured by Wako Pure Chemical Industries, Ltd.) (4.31 g, 18.7 mmol) and cyclohexanone (65.9 g) was added dropwise over 1 hour. Thereafter, the mixture was stirred at 90 DEG C for 3 hours, cooled to room temperature, dropped into a mixed solvent of ethyl acetate / acetonitrile = 1156 mL / 144 mL, and re-dissolved. After air-drying at 40 占 폚 for one 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 (molar ratio) was confirmed by ¹ H-NMR, and the coloring matter part: methacrylic acid part was 25:75.

(12.5 g), glycidyl methacrylate (2.68 g), tetraethylammonium bromide (0.5 g), p-methoxyphenol (0.015 g), cyclohexanone 83.3 g), and the mixture was stirred at 105 캜 for 4 hours under air. Thereafter, the mixture was cooled to room temperature, dropped into a mixed solvent of ethyl acetate / acetonitrile = 748 mL / 39 mL, and re-dissolved. After air-drying at 40 占 폚 for one day, 5.52 g of a colorant P-1 was obtained. The colorant oligomer P-1 had an acid value of 0.94 mmol / g, and the composition ratio (molar ratio) was confirmed by ¹ H-NMR, and the coloring matter portion: methacrylic acid portion: polymerizable group-containing portion was 25:40:35.

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

The dyeing compound A-1 and another compound in the dyeing multimer P-1 were synthesized by carrying out the same operations except that the monomers were changed to be the repeating units shown in the following Table 1.

[Table 1]

Each repeating unit constituting the dye multimer is shown below.

[Formula 81]

(82)

(83)

(84)

[Examples and Comparative Examples]

1. Preparation of resist solution

The following composition was mixed and dissolved to prepare a resist solution for the undercoat layer.

&Lt; Composition of resist solution for undercoat layer >

Solvent: propylene glycol monomethyl ether acetate  Section 19.20

Solvent: Ethyl lactate  36.67 parts

Alkali-soluble resin: 40% propylene glycol (weight ratio) of benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer (molar ratio = 60/22/18, weight average molecular weight 15,000, number average molecular weight 9,000) Solution of colmonomethylether acetate (PGMEA)  30.51 part

· Ethylenically unsaturated double bond-containing compound: dipentaerythritol hexaacrylate  12.20 part

Polymerization inhibitor: p-methoxyphenol 0.0061 part

· Fluorochemical surfactant: F-475, manufactured by DIC Co., Ltd.   0.83 part

Photopolymerization initiator: a photopolymerization initiator of the trihalomethyltriazine system 0.586 part

(TAZ-107, manufactured by Midori Kagaku Co., Ltd.)

2. Fabrication of silicon wafer substrate with undercoat layer

A 6-inch silicon wafer was heated in an oven at 200 캜 for 30 minutes. Next, the resist solution was applied onto the silicon wafer so that the dry film thickness became 1.5 占 퐉, and further heated and dried in an oven at 220 占 폚 for 1 hour to form an undercoat layer to obtain a silicon wafer substrate with an undercoat layer .

3. Preparation of coloring composition

3-1. Preparation of blue pigment dispersion

Blue Pigment Dispersion 1 was prepared as follows.

A mixed solution comprising 13.0 parts of CI Pigment Blue 15: 6 (blue pigment, average particle diameter 55 nm), 5.0 parts of Disperbyk 111 as a pigment dispersant and 82.0 parts of PGMEA was dispersed in a bead mill (zirconia beads 0.3 mm diameter) Followed by mixing and dispersing for a time to prepare a pigment dispersion. Thereafter, dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high pressure disperser NANO-3000-10 (manufactured by Nippon Express Co., Ltd.) with a pressure reducing mechanism. This dispersion treatment was repeated ten times to obtain a blue pigment dispersion 1 (CI Pigment Blue 15: 6 dispersion, pigment concentration: 13%) used for the coloring composition of Example or Comparative Example.

The obtained blue pigment dispersion was measured for its particle diameter by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (Nikkiso Co., Ltd.)) to be 24 nm.

3-2. Preparation of coloring composition

The following components were mixed, dispersed and dissolved to obtain each of the colored compositions of Examples and Comparative Examples.

Dye compounds (compounds listed in the following table) 0.04 part as solid content

· Solvent (PGMEA) 1.133 part

Alkali-soluble resin (compound of J12 below)  0.03 part

Dispersant (Sol Spurs 20000: (1% cyclohexane solution, manufactured by Nippon Lubrizol Corporation) 0.125 part

Photopolymerization initiator (compound of the following C-9) 0.012 part

The above pigment dispersion (pigment concentration 13%) 0.615 part

· Curable compound  0.07 part

Surfactant (glycerol propoxide: (1% cyclohexane solution)) 0.048 part

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

(85)

A-DPH-12E (Shin-Nakamura Chemical Co., ethyleneoxy-modified dipentaerythritol hexaacrylate)

&Lt; EMI ID =

[Chemical Formula 87]

[Formula 88]

4. Fabrication of Color Filter by Coloring Composition

&Lt; Pattern formation >

Each of the color compositions of the prepared examples and comparative examples was applied on the undercoat layer of the silicon wafer substrate with the undercoat layer obtained in the above 2. to form a colored composition layer (coating film). Then, a heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 캜 so that the dried film thickness of the coated film became 0.6 탆.

Subsequently, the resist was exposed at various exposure amounts of 50 to 1200 mJ / cm ² through an island pattern mask having a wavelength of 365 nm and a pattern of 1.0 μm square using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.).

Thereafter, the silicon wafer substrate on which the irradiated coated film was formed was placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by KEMITRONICS Co., Ltd.), and a CD-2000 (FUJIFILM ELECTRONIC MATERIALS Ltd.) for 60 seconds at 23 占 폚 to form a colored pattern on a silicon wafer substrate.

A silicon wafer having a colored pattern formed thereon was fixed to the horizontal rotary table by a vacuum chucking method and the silicon wafer substrate was rotated at a rotation speed of 50 rpm by a rotary device while pure water was sprayed from a spray nozzle To perform a rinsing treatment, and thereafter spray-dried.

Thus, a monochromatic color filter having a coloring pattern formed by the coloring composition of Example or Comparative Example was produced.

Thereafter, the size of the colored pattern was measured using a measurement SEM "S-9260A" (manufactured by Hitachi High-Technologies Corporation). The exposure amount at which the pattern size becomes 1.0 mu m was defined as the optimum exposure amount.

5. Performance evaluation

5-1. Heat resistance

The glass substrate coated with the obtained coloring composition was placed on a hot plate at 200 캜 so as to be in contact with the substrate surface and heated for 1 hour and then measured with a color meter MCPD-1000 (manufactured by OTSUKA DENKI CO., LTD.), (? E * ab value) was measured and evaluated as an index for evaluating the fastness of heat fastness according to the following criteria. The value of? E * ab indicates that the smaller the value, the better the heat resistance. The value of? E * ab is a value obtained from the following color difference formula by the CIE 1976 (L *, a *, b *) spatial colorimetric system (Japanese Society for Color Science Handbook of Color Science Handbook ).

ΔE * ab = {(ΔL * ) 2+ (Δa *) 2+ (Δb *) 2} 1/2

Were evaluated according to the following criteria.

A: value of? E * ab is 0 or more and less than 1.0

B: value of? E * ab is 1.0 or more and less than 3.0

C: value of? E * ab is 3.0 or more

5-2. Cyclohexane solubility

Solvent solubility of the obtained coloring composition to PGMEA at 25 캜 was evaluated based on the following criteria.

A: Solubility of 12.5 mass or more

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

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

When D is less than 5% by mass

5-3. Dye assessment

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

A CT-2000L solution (manufactured by FUJIFILM ELECTRONICS, INC., Made by Clearfactory Co., Ltd.) was applied on the colored pattern formation side of the color filter so as to have a dry film thickness of 1 mu m and dried to form a transparent film, For 5 minutes.

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

The ratio [%] of the absorbance A to the value of the absorbance A of the coloring pattern measured before heating was calculated with respect to the absorbance B of the obtained transparent film (the following formula (A)). This was used as an index for evaluating the migration to adjacent pixels.

(Formula A) diatom (%) = absorbance B / absorbance A × 100

A: Value of expression A is 0 or more and less than 2

B: value of formula A is 2 or more and less than 5

C: Value of expression A is 5 or more

5-4. Spectral evaluation before and after development

CT-4000L solution (manufactured by FUJIFILM ELECTRONICS MATERIALS CO., LTD. Made by Transparent Materials Co., Ltd.) was coated on a glass wafer so that the dry film thickness was 0.1 mu m and dried to form a transparent film. Heat treatment was carried out.

The colored composition was applied using a spin coater so that the film thickness became 0.6 mu m, and heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 DEG C.

Subsequently, exposure was performed at an exposure amount of 500 mJ / cm ² at a wavelength of 365 nm using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.).

The color filter thus obtained was measured for its transmittance in a wavelength range of 300 nm to 800 nm with a spectrophotometer (reference: glass substrate) of ultraviolet visible infrared spectrophotometer UV3600 (Shimadzu Corporation).

(Manufactured by Fuji Film Electronics Materials Co., Ltd.) on a horizontal rotating table of a spin shower developing machine (DW-30 type, manufactured by KEMITRONICS Co., Ltd.) Then, the silicon wafer substrate was rotated at a rotation speed of 50 rpm by a rotary device, pure water was supplied from a spray nozzle through a spray nozzle from above the rotation center to a rinse treatment, and spray-dried. After drying, the spectral measurement was carried out again to evaluate the transmittance before and after development (the transmittance before development is T0 and the transmittance after development is T1, the value represented by the formula | T0-T1 | B or more is a practical level.

AA: The transmittance variation before and after the development in the entire region of 300 nm to 800 nm is less than 2%

A: The transmittance variation before and after development in the entire region of 300 nm to 800 nm is 2% or more and less than 5%

B: The transmittance variation before and after development in the entire region of 300 nm to 800 nm is 5% or more and less than 10%

C: transmittance variation before and after development in an entire region of 300 nm to 800 nm is 10% or more

[Table 2]

As is clear from the above table, it was found that the composition of the present invention has high light resistance and can effectively suppress the spectral change at the time of development. In addition, it was found that it was also effective in suppressing the change in heat resistance, solvent solubility, and dye migration.

On the other hand, when the xanthane dye structure was not a multimer (Comparative Examples 1 to 3), the light resistance and / or the spectroscopy at the time of development were likely to change. In addition, evaluation of heat resistance, solvent solubility, and change in dye migration also tended to be poor.

Claims (16)

A dye multimer having at least one of a repeating unit represented by the general formula (A1-1) and a repeating unit represented by the general formula (A1-2)
Curable compound
A coloring composition;
In general formula (A1-1)
[Chemical Formula 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 anionic group or an anionic group substituent 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, R ⁵ ~ R ¹⁰ each independently represent a hydrogen atom, a halogen 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 amino group, an alkylamino group, an arylamino group , Or a sulfonyl group;
In general formula (A1-1-1)
(2)

In the general 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 general formula (A1-2)
(3)

In the general formula (A1-2), one of R ¹ to R ¹⁵ includes a main chain structure represented by the general formula (A1-1-1), 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, a halogen atom, an alkyl group, an aryl group, a carbonyl group, a nitro group, an amino group, an alkylamino group, an arylamino group or a sulfonyl group; X represents an anion which forms an opposite salt to the cation of xanthine. The method according to claim 1,
, The anionic group in the general formula (A1-1) includes a carboxylic acid anion, a sulfonic acid anion, an anion represented by the general formula (A1-1-2), or an anion represented by the general formula (A1-1-3) , A coloring composition wherein X in the general formula (A1-2) is any one of a carboxylic acid anion, a sulfonic acid anion, an imide anion, a methide anion, and a borate anion;
In general formula (A1-1-2)
[Chemical Formula 4]

In the general formula (A1-1-2), L ¹ represents a single bond or a divalent linking group, L ² represents -SO ₂ - or -CO-, G represents a carbon atom or a nitrogen atom, n1 is the case when G is a carbon atom represents a 2, G represents a 1 if the nitrogen atom, R ⁶ is each represents an aryl group containing alkyl group or a fluorine atom containing a fluorine atom, which n1 is 2, 2 Each R &lt; ⁶ &gt; may be the same or different;
In general formula (A1-1-3)
[Chemical Formula 5]

In 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, G Is a carbon atom or a nitrogen atom, n2 is 1 when G is a carbon atom, 0 when G is a nitrogen atom, ^R7A and ^R7B are each independently an alkylene group containing a fluorine atom or An arylene group containing a fluorine atom, and R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group. The method according to claim 1 or 2,
Wherein the dye compound (A) further has an alkali-soluble group. The method according to any one of claims 1 to 3,
Wherein the dye compound (A) further comprises a polymerizable group. The method according to any one of claims 1 to 4,
Wherein the curable compound is a polymerizable compound and further contains a photopolymerization initiator. The method according to any one of claims 1 to 5,
Further comprising a pigment having a phthalocyanine skeleton. The method according to any one of claims 1 to 6,
Wherein one of R ¹¹ to R ¹⁵ in Formula (A1-1) and one of R ¹¹ to R ¹⁵ in Formula (A1-2) is a main chain structure represented by Formula (A1-1-1). The method according to any one of claims 1 to 7,
The R ² and R ⁴ is a phenyl group of the formula (A1-1) R ² and R ⁴ also the formula (A1-2), the coloring composition. The method according to any one of claims 1 to 8,
R ² and R ⁴ in formula (A1-1) and at least one of R ² and R ⁴ in formula (A1-2) are represented by the following formula (A1-1-2);
[Chemical Formula 6]

In the general 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 carbonylamido group, A sulfonyl group, a sulfonyl group, a sulfonyl group, a nitro group, an amino group, an aminocarbonyl group, an aminosulfonyl group, a sulfonylimide group or a carbonylimide group, R ²² and R ²⁶ each independently represent a Alkyl group. The method according to any one of claims 1 to 9,
General formula (A1-1) of the R ¹ and R ³ also general formula (A1-2), R ¹ and R ³ are, each independently, is, the coloring composition of the alkyl group of 1 to 5 carbon atoms. The method according to any one of claims 1 to 10,
A coloring composition used for forming a colored layer of a color filter. A cured film obtained by curing the coloring composition according to any one of claims 1 to 11. A step of forming a coloring composition layer on a support using the coloring composition according to any one of claims 1 to 11; a step of exposing the coloring composition layer in a pattern shape; a step of exposing the unexposed portion of the exposed coloring composition layer to a developing And a step of forming a color filter. A color filter obtained by the color filter having the cured film according to claim 12 or the color filter according to claim 13. A solid-state image pickup device having the color filter according to claim 14. An image display apparatus having the color filter according to claim 14.