KR20160085329A - Coloring composition, cured film using same, color filter, pattern formation method, method for manufacturing color filter, solid-state imaging element, and image display device - Google Patents

Abstract

A coloring composition excellent in discoloration resistance and a cured film, a color filter, a pattern forming method, a color filter manufacturing method, a solid-state image pickup device and an image display device using the same are provided. is a coloring composition comprising a repeating unit having (a) a repeating unit having a dye structure and (b) a repeating unit having a repeating unit of 2 to 20 unsubstituted alkyleneoxy chains on the side chain.

Description

TECHNICAL FIELD [0001] The present invention relates to a color filter, a color filter, a pattern forming method, a color filter manufacturing method, a solid-state image pickup device, and an image display device using the color filter. , SOLID-STATE IMAGING ELEMENT, AND IMAGE DISPLAY DEVICE}

The present invention relates to a coloring composition. Particularly, the present invention relates to a coloring composition which is preferably used for forming a colored layer of a color filter. Further, the present invention relates to a cured film, a color filter, a solid-state image pickup device and an image display device using the coloring composition. The present invention also relates to a pattern forming method using a coloring composition and a manufacturing method of a color filter.

In recent years, with the development of personal computers, particularly large-screen liquid crystal televisions, there is a tendency that the demand of liquid crystal displays (LCDs), especially color liquid crystal displays, increases. And the spread of organic EL displays is also demanded from the demand for further high image quality. On the other hand, demand for solid-state image pickup devices such as CCD image sensors has been greatly increased owing to the spread of digital cameras and mobile phones equipped with cameras.

Color filters are used as key devices for these displays and optical elements, and there is an increasing demand for cost reduction with the demand for further high image quality. Such a color filter has coloring layers (patterns) of three primary colors, typically red (R), green (G), and blue (B). In a display device or an image pickup device, And the like.

In recent years, a pigment multimer has been studied as a coloring agent for forming a colored layer.

Specifically, Patent Document 1 discloses a resin composition containing, as a colorant, a dye multimer having an alkali-soluble group having a weight average molecular weight (Mw) of 5,000 to 20,000 and a dispersion degree of 1.00 to 2.50.

Patent Document 2 discloses a colored curable composition containing a pigment oligomer having a polymerizable group, a pigment, a polymerizable compound, and a photopolymerization initiator.

Patent Document 3 discloses a colored curable composition containing a colorant multimer, a polymerizable compound, a photopolymerization initiator, and an organic solvent that contains a xanthene skeleton as a partial structure of a dye moiety.

Patent Document 4 discloses a coloring radiation sensitive composition comprising a dye polymer and a solvent, which is polymerized using a chain transfer agent having a LogP value of 5 or less, and which contains a structural unit having a dye structure.

Patent Document 1: JP-A No. 2011-213925 Patent Document 2: JP-A-2013-28764 Patent Document 3: JP-A-2012-32754 Patent Document 4: JP-A-2012-215806

There is an increasing demand for coloring compositions containing a dye multimer such as the above, and a coloring composition capable of forming a more precise pattern by recent technological innovations is required. Particularly, there is a demand for a coloring composition having a better discoloration resistance in a coloring curable composition containing a colorant multimer. The present invention aims to provide a coloring composition excellent in discoloration resistance by using an additional dye multimer in view of this situation.

As a result of a study by the inventors of the present invention, it has been found that, by using a dye multimer containing a repeating unit having a repeating unit of 2 to 20 unsubstituted alkyleneoxy chains as a dye multimer, The present inventors have found that excellent coloring compositions can be provided, and the present invention has been accomplished.

Specifically, the above problem has been solved by the following means.

<1> A coloring composition comprising a pigment multimer comprising (a) a repeating unit having a dye structure, and (b) a repeating unit having a repeating unit of 2 to 20 unsubstituted alkyleneoxy chains on the side chain.

<2> The coloring composition according to <1>, wherein the coloring matter structure is derived from a coloring matter selected from a dipyramethane coloring matter, a triarylmethane coloring matter, a xanthine coloring matter, a cyanine coloring matter and a squarylium coloring matter.

&Lt; 3 > The coloring composition according to < 1 > or < 2 >, wherein the dye multimer has an acid group.

&Lt; 4 > The coloring composition according to any one of < 1 > to < 3 >, wherein the coloring composition further comprises a pigment and a pigment dispersant.

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

<6> The coloring composition according to any one of <1> to <5>, wherein the colorant multimer is a (meth) acrylic resin.

<7> The coloring composition according to any one of <1> to <6>, wherein the proportion of the repeating unit having a dye structure (a) is 10 to 35 mol% of the total repeating units constituting the dye multimer.

<8> (b) a repeating unit having a repeating unit of 2 to 20 unsubstituted alkyleneoxy chains in the side chain of 2 to 20 mol% of all repeating units constituting the colorant multimer, Gt; to < 7 >.

<9> The coloring composition according to any one of <1> to <8>, wherein the colorant multimer comprises a polymerizable group.

<10> The coloring composition according to any one of <1> to <9>, which is used for forming a coloring layer of a color filter.

<11> A cured film obtained by curing a colored composition according to any one of <1> to <10>.

&Lt; 12 > A color filter having a cured film according to < 11 >.

&Lt; 13 > A process for producing a colored composition, comprising the steps of: applying a coloring composition according to any one of < 1 > to < 10 > onto a support to form a coloring composition layer; exposing the coloring composition layer in a pattern; And forming a colored pattern.

&Lt; 14 > A method for manufacturing a color filter, comprising the pattern formation method according to < 13 >.

<15> A solid-state image pickup element having a color filter obtained by the method according to <12> or the method of manufacturing a color filter according to <14>.

&Lt; 16 > A color filter according to < 12 > or an image display apparatus having a color filter obtained by the method of manufacturing a color filter according to < 14 >.

According to the present invention, it has become possible to provide a coloring composition having excellent discoloration resistance. In addition, it becomes possible to provide a cured film, a color filter, a pattern forming method, a color filter manufacturing method, a solid-state image pickup device and an image display device using the colored composition.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, "" is used to mean that the numerical values described before and after the lower limit and the upper limit are included. The organic EL element in the present invention refers to an organic electroluminescence element.

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. It also refers to the solid content at 25 占 폚.

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, "(meth) acrylate" represents both or either of acrylate and methacrylate, and "(meth) acrylic" represents both acrylate and methacrylate, "(Meth) acryloyl" represents 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, Me in the formula represents a methyl group, Et represents an ethyl group, Pr indicates a propyl group, Bu indicates a butyl group, and Ph indicates a phenyl group.

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.

The coloring composition of the present invention is a colored composition comprising (a) a repeating unit having a pigment structure, and (b) a pigment multimer comprising a repeating unit having a repeating unit of 2 to 20 unsubstituted alkyleneoxy chains on its side chain do.

By compounding such a repeating group of the alkyleneoxy chain, the discoloration resistance can be improved. The reason for this is presumption. If the number of alkyleneoxy chains exceeds 20, hydrophilicity becomes too high, and it is considered that discoloration tends to occur on the contrary when patterning is developed. In the present invention, by adjusting the number of alkyleneoxy chains, it has succeeded in achieving the decolorizing property appropriately.

Further, by adding a pigment and a pigment dispersant separately from the pigment multimer, the discoloration resistance is remarkably improved. This reason is presumed to be due to the mutual action of the pigment dispersant and the repeating unit of the alkyleneoxy chain.

Hereinafter, the details of the present invention will be described.

&Lt;

The colorant multimer used in the present invention is a polymer having a repeating unit (a) having a dye structure (hereinafter sometimes referred to as a "repeating unit (a)") and (b) a repeating unit having 2 to 20 unsubstituted alkyleneoxy chains (Hereinafter sometimes referred to as "(b) repeating unit") having repeating groups in the side chain. The repeating unit (a) and the repeating unit (b) may each contain only one kind or two or more kinds.

The dye multimer is not particularly limited as long as it contains a dye structure, but it is preferably a (meth) acrylic resin.

Hereinafter, description will be made on the structure that becomes the skeleton of the dye multimer, the dye structure, and the counter anion of the dye structure included as needed.

<< (a) Skeletal structure of repeating unit >>

(A), the general formula (B), and the general formula (C) shown in paragraphs 0276 to 0304 of Japanese Laid-Open Patent Publication No. 2013-28764 It is preferable that at least one of the constituent units appearing is a skeleton, or that a large amount of the dye represented by the formula (D) is preferable. The description of paragraphs 0276 to 0304 of Japanese Laid-Open Patent Publication No. 2013-28764 is incorporated herein by reference.

In the present invention, it is preferable to include a dye multimer represented by the following general formula (A).

The proportion of the repeating unit (a) having a dye structure is preferably 10 to 35 mol%, more preferably 15 to 30 mol%, of the total repeating units constituting the dye multimer.

<<< Constitutional units represented by the general formula (A) >>>

[Chemical Formula 1]

(In the general formula (A), X ₁ represents a linking group formed by polymerization, L ₁ represents a single bond or a divalent linking group, and Dye I represents a pigment structure.)

Hereinafter, general formula (A) will be described in detail.

In the general formula (A), X ₁ represents a linking group formed by polymerization. That is, a part forming a repeating unit corresponding to a main chain formed by a polymerization reaction. In addition, the parts indicated by two * are repeated units. X ₁ is preferably a linking group represented by any one of the following formulas (XX-1) to (X-24), more preferably a linking group represented by any one of formulas (XX-1) Linking chain represented by (XX-10) to (XX-17), (XX-18) and (XX-19) and (XX-24) represented by More preferably a chain selected from the group consisting of a (meth) acrylic linkage chain represented by (XX-1) and (XX-2), a styrene-based chain represented by (XX- More preferably selected from vinyl-based connecting chains represented by (XX-1) and (XX-2), and more preferably the styrene-based connecting chains represented by (meth) acrylic connecting chains and Do.

(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.

(2)

(3)

In the general formula (A), L ₁ represents a single bond or a divalent linking group. Examples of the divalent linking group when L ₁ represents a 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, a butylene group, etc.) A substituted or unsubstituted arylene group having 6 to 30 carbon atoms (e.g., a phenylene group or a naphthalene group), a substituted or unsubstituted heterocyclic linking group, -CH = CH-, -O-, -S-, -C (= O) -, -CO ₂ -, -NR-, -CONR-, -O ₂ C-, -SO-, -SO ₂ -, and a linking group formed by connecting two or more of these. It is also preferable that L ₁ contains an anion. L ₁ is a single bond or an alkylene group, more preferably a single bond or - (CH ₂ ) n- (n is an integer of 1 to 5). Here, R represents, independently of each other, a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. An example in which L ₁ includes an anion will be described later.

In the general formula (A), DyeI represents a dye structure derived from a dye compound described later.

The pigment oligomer having the constitutional unit represented by the general formula (A) is obtained by (1) a method of synthesizing a monomer having a pigment residue by addition polymerization, (2) a method of synthesizing a monomer having a pigment residue such as an isocyanate group, an acid anhydride group, A method of reacting a polymer having a reactive functional group with a dye having a functional group capable of reacting with a highly reactive group (a hydroxyl group, a primary or secondary amino group, a carboxyl group, or the like).

In the addition polymerization, known addition polymerization (radical polymerization, anionic polymerization, cation polymerization) can be applied. Of these, the synthesis by radical polymerization in particular makes it possible to mild the reaction conditions and does not decompose the pigment structure Do. For the radical polymerization, known reaction conditions can be applied. That is, the dye multimer used in the present invention is preferably an addition polymer.

Among them, the pigment multimer having the constituent unit represented by the general formula (A) in the present invention is preferably a radical polymer obtained by radical polymerization using a dye monomer having an ethylenically unsaturated bond from the viewpoint of heat resistance .

<< Color Structure >>

The dye structure used in the present invention is not specifically defined, and a known dye structure can be employed. The dye structure used in the present invention is preferably a dye structure containing a cationic site in the molecule.

Specific examples of the dye include pigments such as a dipyramethine dye, a carbonium dye (diphenylmethane dye, triarylmethane dye, xanthine dye, and acridine dye), a polymethine dye (oxolin dye, Dye structures derived from pigments selected from pigments selected from the group consisting of pyrrolidone dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), subphthalocyanine dyes and their metal complex dyes.

A preferable example of the repeating unit (a) in the present invention is one wherein the dye structure is introduced into the polymer skeleton of the repeating unit (a).

Among these dye structures, from the viewpoint of color characteristics, a dye structure derived from a dye selected from a dipyramethine dye, a carbonium dye, and a polymethine dye is preferable, and a dye structure derived from a dipyramethine dye, a triarylmethane dye, More preferably a dye structure derived from a dye selected from a dye, a cyanine dye and a squarylium dye, more preferably a dye structure derived from a dye selected from a dipyramethine dye and a xanthine dye, The dye structure is particularly preferred. The use of cations having such a pigment structure tends to further improve heat resistance and light resistance.

Specific dye compounds capable of forming a pigment structure can be found in "New Edition Dye Handbook" (edited by Organic Synthetic Chemistry Association, Maruzen, 1970), "Society of Dyers and colourists", " Et al., Kodansha, 1986).

A particularly preferable dye (dye compound) capable of forming a dye structure in a cation having a dye structure is described in detail.

<<< Dipyromethane coloring >>>

One of the aspects of the dye structure according to the present invention is the structure of the dipyramethine dye shown below.

As the dipyrammethene dye in the present invention, a dipyrammethene compound and a dipyrammethene metal complex compound obtained from a dipyrammethene compound and a metal or a metal compound are preferable. And binds to the polymer at one of these dipyramethine dye structures.

Further, in the present invention, a compound containing a dipyrammethenic structure is referred to as a dipyrammethenic compound, and a complex containing a compound containing a dipyrammethenic structure to a metal or a metal compound is referred to as a dipyrammethenic metal complex compound.

As the dipyrammethene metal complex compound, a dipyrammethene metal complex compound obtained from a dipyrammethene compound represented by the following formula (M) and a metal or a metal compound and a tautomer thereof are preferable, and among them, as a preferred embodiment, (7), or a dipyrammethene metal complex compound represented by the following general formula (8), and the dipyrammethene metal complex compound represented by the general formula (8) is more preferable.

(A dipyrammethene metal complex compound obtained from a dipyrammethene compound represented by the formula (M) and a metal or a metal compound, and a tautomer thereof)

One of preferred embodiments of the dye structure is a compound in which a compound represented by the following formula (M) (a dipyrammethene compound) or a tribo-isomer thereof is a complex for embedding in a metal or a metal compound (hereinafter appropriately referred to as "specific complex" Containing pigment structure. In the present invention, the following compounds form a cation structure. For example, a metal such as zinc bonded to the nitrogen atom of the formula (M) may form a cation structure.

[Chemical Formula 4]

(In the formula (M), R ⁴ to R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent, provided that R ⁴ and R ⁹ are not bonded to each other to form a ring.)

The introduction site in the case of introducing the compound represented by the general formula (M) into the structural unit represented by the general formula (A) is not particularly limited, but from the viewpoint of compatibility with synthesis, any one of R ⁴ to R ⁹ Is preferably introduced in any one of R ⁴ , R ⁶ , R ⁷ and R ⁹ , and is more preferably introduced in any one of R ⁴ and R ⁹ .

Examples of the monovalent substituent in the case where R ⁴ to R ⁹ in the general formula (M) represent a monovalent substituent include the substituents in the group of Substituent Group A described later.

When the monovalent substituent represented by R ⁴ to R ⁹ in the general formula (M) is a further substitutable group, it may further have a substituent described for R ⁴ to R ⁹ , and when it contains two or more substituents, These substituents may be the same or different.

R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , and R ⁸ and R ⁹ in the general formula (M) are each independently bonded to form a 5-membered, 6-membered or 7-membered Wreath, or unsaturated ring may be formed. Provided that R ⁴ and R ⁹ are not bonded to each other to form a ring. When the 5-membered, 6-membered, and 7-membered rings to be formed are further substitutable groups, they may be substituted with the substituents described for R ⁴ to R ⁹ , and when they are substituted with two or more substituents, They may be the same or different.

R ⁴ and R ⁵ in the general formula (M), R ⁵ and R ⁶ , R ⁷ and R ⁸ , and R ⁸ and R ⁹ are each independently bonded to form a 5-membered, 6-membered, Examples of the 5-membered, 6-membered or 7-membered ring or unsaturated ring having no substituent when forming a 7-membered ring or an unsaturated ring include a pyrrole ring, a furan ring, a thiophene ring, Pyridine ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexane ring, benzene ring, pyridine ring, pyrazine ring, And preferably a benzene ring or a pyridine ring.

R ¹⁰ in the general formula (M) preferably represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. The halogen atom, the alkyl group, the aryl group, and the heterocyclic group each are the same as the halogen atom, the alkyl group, the aryl group and the heterocyclic group of Substituent Group A described later, and the preferable range thereof is also the same.

When the alkyl group, aryl group and heterocyclic group in the case where R ¹⁰ represents an alkyl group, an aryl group or a heterocyclic group are further substitutable groups, they may be substituted with the substituents described in the Substituent Group A described later , When they are substituted with two or more substituents, the substituents may be the same or different.

~ Metal or metal compound ~

The specific complex in the present invention is a complex in which a dipyrammethenic compound represented by the general formula (M) or a tautomer thereof represented by the above-mentioned general formula (M) is embedded in a metal or a metal compound.

Here, the metal or metal compound may be any metal or metal compound capable of forming a complex, and includes a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. Examples of metals or metal compounds, such as Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, in addition to metals such as Co, Fe, AlCl, InCl, FeCl, TiCl _2, Metal chlorides such as SnCl ₂ , SiCl ₂ and GeCl ₂ , metal oxides such as TiO ₂ and VO, and metal hydroxides such as Si (OH) ₂ .

Among these, preferred are Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO or VO in view of stability of the complex, spectral characteristics, heat resistance, light resistance, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or VO is more preferable, and Zn is particularly preferable.

Next, a more preferable range of the specific complex of the compound represented by the formula (M) in the present invention will be described.

A preferable range of the specific complex in the present invention is that in the general formula (M), R ⁴ and R ⁹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, An acyl group, an alkoxycarbonyl group, a carbamoyl group, an amino group, an anilino group, a heterocyclic amino group, a carbonamido group, an eudate group, an imide group, an acyl group, An alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group; R ⁵ and R ⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, An alkoxycarbonyl group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, An arylsulfonyl group, or a sulfamoyl group; R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, a cyano group, an alkoxy group, An alkoxy group, an alkoxy group, an alkylthio group, an arylthio group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an anilino group, a carbonyl group, An alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or a phosphinoylamino group; R ¹⁰ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group; The metal or metal compound is in the range of Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO or V =

A more preferable range of the specific complex in the present invention is that in the general formula (M), R ⁴ and R ⁹ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, An aryl group, an alkoxycarbonyl group, an aryloxycarbonylamino group, a sulfonamido group, an azo group, an alkylsulfonyl group, an aryloxycarbonyl group, an aryloxycarbonyl group, an aryloxycarbonyl group, an aryloxycarbonyl group, an aryloxycarbonyl group, A sulfonyl group, or a phosphinoylamino group; R ⁵ and R ⁸ are each independently selected from the group consisting of alkyl, alkenyl, aryl, heterocyclic, cyano, nitro, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, A sulfonyl group, an arylsulfonyl group, or a sulfamoyl group; R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, , An alkoxycarbonylamino group, a sulfonamido group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group; R ¹⁰ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group; Wherein the metal or the metal compound is Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or V =

A particularly preferable range of the specific complex in the present invention is that in the general formula (M), R ⁴ and R ⁹ are each independently a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, a heterocyclic amino group, An amido group, an ethylidene group, an imide group, an alkoxycarbonylamino group, a sulfonamido group, an azo group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group; R ⁵ and R ⁸ are each independently an alkyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group or an arylsulfonyl group; R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; R ¹⁰ is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group; The metal or the metal compound is Zn, Cu, Co, or V = O.

The dipyrammethene metal complex compound represented by the general formula (7) or the general formula (8) described below in detail is also a particularly preferable embodiment of the dipyramethine dye.

(The dipyrammethene metal complex compound represented by the general formula (7)

One suitable embodiment of the dye structure in a cation having a dye structure is a dye structure derived from a dipyrammethene metal complex compound represented by the following general formula (7). In the present invention, the following compounds form a cation structure. For example, Ma in formula (7) may form a metal cation structure such as zinc.

[Chemical Formula 5]

(In the general formula (7), R ⁴ to R ⁹ each independently represents a hydrogen atom or a monovalent substituent, and R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group X ¹ represents a group capable of binding to Ma, X ² represents a group for neutralizing the charge of Ma, X ¹ and X ² are bonded to each other to form a bond with Ma A 5-membered, a 6-membered, or a 7-membered ring may be formed, provided that R ⁴ and R ⁹ are not bonded to each other to form a ring.

The dipyrammethene metal complex compound represented by the general formula (7) includes a tautomer.

The introduction site in the case of introducing the dipyrammethene metal complex compound represented by the general formula (7) into the structural unit represented by the general formula (A) is not particularly limited, but from the viewpoint of the synthetic suitability, the R ⁴ to R ⁹ It is preferably introduced into any one of the moieties, more preferably introduced in any one of R ⁴ , R ⁶ , R ⁷ and R ⁹ , more preferably introduced in any one of R ⁴ and R ⁹ .

In the case where the cation having a dye structure has an alkali-soluble group, a method of introducing an alkali-soluble group is not particularly limited as long as at least one of R ⁴ to R ¹⁰ , X ¹ and X ² in Formula (7) A method of allowing the substituent group to have an alkali-soluble group can be used. Among these substituents, any one of R ⁴ to R ⁹ and X ¹ is preferable, and any one of R ⁴ , R ⁶ , R ⁷ and R ⁹ is more preferable, and any one of R ⁴ and R ⁹ is more preferable .

The dipyrammethene metal complex compound represented by the general formula (7) may have a functional group other than the alkali-soluble group as long as the effect of the present invention is not impaired.

The general formula R ⁴ R ⁹ ~ of 7, and R ⁹ and R ~ ⁴ agree in the formula (M), it is also the same preferred embodiment.

In the general formula (7), Ma represents a metal atom or a metal compound. The metal atom or metal compound may be any metal atom or metal compound capable of forming a complex, and includes a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride.

For example, Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe and the like, and AlCl, InCl, FeCl, TiCl _2, SnCl _2, SiCl _2, GeCl ₂ , etc., metal oxides such as TiO ₂ and V = O, and metal hydroxides such as Si (OH) ₂ .

Among them, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co and the like are used as metal atoms or metal compounds from the viewpoints of stability of the complex, spectroscopic characteristics, heat resistance, light resistance, , TiO 2 and V═O are preferable and Zn, Mg, Si, Pt, Pd, Cu, Ni, Co and V═O are more preferable and Zn, Co, V═O and Cu are more preferable , And Zn are particularly preferable.

In the general formula (7), R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom.

In the general formula (7), X ¹ may be any of groups capable of binding to Ma, and specifically concretely includes water, alcohols (e.g., methanol, ethanol, propanol) 1], and compounds described in Sakaguchi, Ueno, Keizo (1995, Nankodo), [2] (1996), [3] (1997), etc.). Among them, water, a carboxylic acid compound and an alcohol are preferable from the viewpoint of production, and water and a carboxylic acid compound are more preferable.

Examples of the "group capable of neutralizing the charge of Ma" represented by X ² in the general formula (7) include a halogen atom, a hydroxyl group, a carboxylic acid group, a phosphoric acid group and a sulfonic acid group. Among them, , A halogen atom, a hydroxyl group, a carboxylic acid group and a sulfonic acid group are preferable, and a hydroxyl group and a carboxylic acid group are more preferable.

In the general formula (7), X ¹ and X ² may combine with each other to form a 5-membered, 6-membered or 7-membered ring together with Ma. The 5-membered, 6-membered, and 7-membered rings to be formed may be a furan ring or an unsaturated ring. The 5-membered, 6-membered and 7-membered rings may be composed of carbon atoms alone or may form a heterocycle having at least one atom selected from a nitrogen atom, an oxygen atom and / or a sulfur atom.

As preferable embodiments of the compound represented by the general formula (7), R ⁴ to R ⁹ are each independently a preferred embodiment described in the description of R ⁴ to R ⁹ and R ¹⁰ is a preferred embodiment described in the description of R ¹⁰ , Ma is Zn, Cu, Co or V = O, X ¹ is water or a carboxylic acid compound, X ² is a hydroxyl group or a carboxylic acid group, X ¹ and X ² are bonded to each other to form a 5-membered or 6-membered ring .

(The dipyrammethene metal complex compound represented by the general formula (8)

One suitable embodiment of the dye structure in the cation having a dye structure is a dye structure derived from a dipyrammethene metal complex compound represented by the following general formula (8). In the present invention, the following compounds form a cation structure. For example, Ma in formula (8) may form a metal cation structure such as zinc.

[Chemical Formula 6]

(In the general formula (8), R ¹¹ and R ¹⁶ each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a heterocyclic amino group. R ¹² ~ R ¹⁵ each independently represent a hydrogen atom or a substituent. R ¹⁷ is a hydrogen atom, a halogen atom, an alkyl group, a represents an aryl group, or a heterocyclic group. Ma is a metal atom or a metal compound X ² and X ³ are each independently NR (wherein R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group) Y ¹ and Y ² are each independently NR ^{c wherein} R ^c is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group A nitrogen atom or a carbon atom, R ¹¹ And Y ¹ may combine with each other to form a 5-membered, 6-membered or 7-membered ring, and R ¹⁶ and Y ² may combine with each other to form a 5-membered, 6-membered or 7-membered ring X ¹ represents a group capable of bonding with Ma, and a represents 0, 1, or 2.

Further, the dipyrammethene metal complex compound represented by the general formula (8) includes a tautomer.

The site for introducing the dipyrammethene metal complex compound represented by the general formula (8) into the structural unit represented by the general formula (A) is not particularly limited as long as the effect of the present invention is not impaired, but R ¹¹ to R ¹⁷ , X ¹ , And Y ¹ to Y ² . Among these, from the viewpoint of synthesis suitability, R ¹¹ ~ R ¹⁶ and X ¹ of preferably introduced in any one, more preferably, R ^11, R ^13, R ¹⁴ and R ¹⁶ Insert according to any one of the , And more preferably, it is inserted in any one of R ¹¹ and R ¹⁶ .

When the cation having a dye structure has an alkali-soluble group, it is preferable that the alkali-soluble group be present in any one or two or more substituents of R ¹¹ to R ¹⁷ , X ¹ , and Y ¹ to Y ² in the general formula (8) Method can be used. Among these substituents, any one of R ¹¹ to R ¹⁶ and X ¹ is preferable, and any one of R ¹¹ , R ¹³ , R ^14, and R ¹⁶ is more preferable, and any one of R ¹¹ and R ¹⁶ is more preferable .

The dipyrammethene metal complex compound represented by the general formula (8) may have a functional group other than the alkali-soluble group as long as the effect of the present invention is not impaired.

In the general formula (8), R ¹² to R ¹⁵ are the same as R ⁵ to R ⁸ in the general formula (M), and preferred embodiments are also the same. R ¹⁷ is the same as R ¹⁰ in formula (M), and preferred embodiments are also the same. Ma agrees with Ma in the general formula (7), and the preferable range is also the same.

More specifically, among R ¹² to R ¹⁵ in the general formula (8), R ¹² and R ^{15 are preferably an} alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, An imido group or a carbamoyl sulfonyl group is preferable and an alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, nitryl group, imide group and carbamoylsulfonyl group are more preferable, and alkoxycarbonyl group, aryloxycarbonyl group, An oxycarbonyl group, a carbamoyl group, a nitrile group, an imide group and a carbamoylsulfonyl group are more preferable, and an alkoxycarbonyl group, an aryloxycarbonyl group and a carbamoyl group are particularly preferable.

R ¹³ and R ¹⁴ are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, more preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl . Specific examples of the more preferable alkyl group, aryl group and heterocyclic group are the same as those of R ⁶ and R ⁷ in formula (M).

In the general formula (8), R ¹¹ and R ¹⁶ are preferably an alkyl group (preferably a straight chain, branched chain or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, An isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group, a dodecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, (Preferably an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, such as a vinyl group, an allyl group, a 3-buten-1-yl group), an aryl group (Preferably an aryl group having 6 to 36 carbon atoms, more preferably a carbon number 6 to 18 carbon atoms such as a phenyl group or a naphthyl group), a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, For example, a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, a 2-pyrimidinyl group, a 2-pyridyl group, a 2-benzothiazolyl group, (Preferably an alkoxy group having 1 to 36 carbon atoms, more preferably an alkoxy group having 1 to 18 carbon atoms, such as a methoxy group, an isopropoxy group, an isopropoxy group, an isopropoxy group, (Preferably having from 6 to 24 carbon atoms, more preferably from 1 to 20 carbon atoms, more preferably from 1 to 20 carbon atoms, more preferably from 1 to 20 carbon atoms, An aryloxy group having 1 to 18 carbon atoms such as a phenoxy group and a naphthyloxy group), an alkylamino group (preferably an alkylamino group having 1 to 36 carbon atoms, more preferably a carbon number of 1 to 18, such as a methylamino group, , N, N-diethylamino group, N, N-diethylamino group, N, N-diethylamino group, N, N-diethylamino group, N, N-dibutylamino group, N- Ethylamino group), an arylamino group (preferably an arylamino group having 6 to 36 carbon atoms, and more preferably 6 to 18 carbon atoms, such as a phenylamino group, a naphthylamino group, an N, N-diphenylamino group, N-ethyl-N-phenylamino group), or a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as 2-aminopyrrole group, Sol, 2-aminopyridine group, 3-aminopyridine group).

R ¹¹ and R ¹⁶ are preferably an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylamino group, an arylamino group or a heterocyclic amino group, more preferably an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, , An alkenyl group, and an aryl group are more preferable, and an alkyl group is particularly preferable.

In the general formula (8), when the alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylamino group, arylamino group or heterocyclic amino group represented by R ¹¹ and R ¹⁶ are further substitutable groups May be substituted with a substituent described in the section of Substituent Group A described later, and when they are substituted with two or more substituents, the substituents may be the same or different.

In the general formula (8), X ² and X ³ each independently represent NR, a nitrogen atom, an oxygen atom, or a sulfur atom. Here, R represents a hydrogen atom, an alkyl group (preferably a straight chain, branched chain, or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such as a methyl group, Ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group), an alkenyl group (preferably a phenyl group) An alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, such as a vinyl group, an allyl group and a 3-buten-1-yl group), an aryl group (preferably having 6 to 36 carbon atoms (Preferably an aryl group having 6 to 18 carbon atoms, such as a phenyl group or a naphthyl group), a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably a heterocyclic group having 1 to 12 carbon atoms, A 2-furyl group, a 2-pyrimidinyl group, a 1-pyridyl group, a 2-benzothiazolyl group, a 1- (Preferably an acyl group having 1 to 24 carbon atoms, more preferably an acyl group having 2 to 18 carbon atoms, such as an acetyl group, a cyano group, an acetyl group, An alkylsulfonyl group (preferably having 1 to 24 carbon atoms, more preferably an alkylsulfonyl group having 1 to 18 carbon atoms, such as methylsulfonyl group , An ethylsulfonyl group, an isopropylsulfonyl group, a cyclohexylsulfonyl group), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 24 carbon atoms, and more preferably a carbon number of 6 to 18, such as phenylsulfonyl group, T-butyl sulfonyl group).

In the general formula (8), Y ¹ and Y ² each independently represent NR ^C , a nitrogen atom or a carbon atom, R ^C is synonymous with R of X ² and X ³ , and preferable embodiments thereof are also the same .

In formula (8), R ¹¹ and Y ¹ are bonded to each other to form a 5-membered ring (for example, a cyclopentane ring, a pyrrolidine ring, a tetrahydrofuran ring, a dioxolane ring, a tetrahydrothiophene ring, A benzofuran ring, a benzothiophene ring), a 6-membered ring (for example, a cyclohexane ring, a piperidine ring, a piperazine ring, a morpholine ring, a tetrazole ring, A pyridazine ring, a quinoline ring, a quinazoline ring), or a 7-membered ring (for example, a cyclohexane ring, a cyclopentadienyl ring, a cyclopentadienyl ring, Tetramine, tetramine, hexamethyleneimine).

In formula (8), R ¹⁶ and Y ² are bonded to each other to form a 5-membered ring (for example, a cyclopentane ring, a pyrrolidine ring, a tetrahydrofuran ring, a dioxolane ring, a tetrahydrothiophene ring, A benzofuran ring, a benzothiophene ring), a 6-membered ring (for example, a cyclohexane ring, a piperidine ring, a piperazine ring, a morpholine ring, a tetrazole ring, A pyridazine ring, a quinoline ring, a quinazoline ring), or a 7-membered ring (for example, a cyclohexane ring, a cyclopentadienyl ring, a cyclopentadienyl ring, Tetramine, tetramine, hexamethyleneimine).

In the case of 5-membered, 6-membered, and 7-membered rings formed by combining R ¹¹ and Y ¹ and R ¹⁶ and Y ² in the general formula (8) And the substituents may be the same or different when two or more substituents are substituted.

In the general formula (8), R ¹¹ and R ¹⁶ are each preferably a monovalent substituent having a steric parameter -Es' value of 1.5 or more, more preferably 2.0 or more, still more preferably 3.5 or more, And particularly preferably at least 5.0.

Here, the value of the three-dimensional parameter -Es 'is a parameter indicating the three-dimensional bulky property of the substituent, and the value of the three-dimensional parameter -Es' (Design of Drug, issued Feb. 20, 1986 (Kagakudojin)).

In the general formula (8), X ¹ represents a group capable of binding to Ma, specifically, a group similar to X ¹ in the general formula (7), and preferred embodiments are also the same.

a represents 0, 1 or 2;

As preferable embodiments of the compound represented by the general formula (8), R ¹² to R ¹⁵ are each independently a preferred embodiment described in the description of R ⁵ to R ^{8 in} the general formula (M), and R ¹⁷ is a group represented by the general formula M), and a preferred embodiment described in the R ¹⁰ of the description, Ma is Zn, Cu, Co, or V = O, and, X ² is NR (R is a hydrogen atom, an alkyl group), a nitrogen atom, or oxygen atom, X ³ is NR (R is a hydrogen atom, an alkyl group) or an oxygen atom, Y ¹ is NR ^C (R ^C is a hydrogen atom, an alkyl group), a nitrogen atom or a carbon atom and Y ² is a nitrogen atom or a carbon atom , R ¹¹ and R ¹⁶ are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, X ¹ is a group bonded through an oxygen atom, and a is 0 or 1. R ¹¹ and Y ¹ may be bonded to each other to form a 5-membered or 6-membered ring, or R ¹⁶ and Y ² may be bonded to each other to form a 5-membered or 6-membered ring.

As a more preferred embodiment of the compound represented by the general formula (8), R ¹² to R ¹⁵ are each independently a preferred embodiment described in the description of R ⁵ to R ⁸ in the compound represented by the general formula (M), and R ¹⁷ is a preferred embodiment described in the description of R ^{10 in} the general formula (M), Ma is Zn, X ² and X ³ are oxygen atoms, Y ¹ is NH, Y ² is a nitrogen atom and R ¹¹ And R ¹⁶ are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, X ¹ is a group bonded through an oxygen atom, and a is 0 or 1. R ¹¹ and Y ¹ may be bonded to each other to form a 5-membered or 6-membered ring, or R ¹⁶ and Y ² may be bonded to each other to form a 5-membered or 6-membered ring.

The molar extinction coefficient of the dipyrammethene metal complex compound represented by the general formula (7) and the general formula (8) is preferably as high as possible from the viewpoint of tinting power. The maximum absorption wavelength? Max is preferably from 520 nm to 580 nm, more preferably from 530 nm to 570 nm, from the viewpoint of improving the color purity. By using the coloring composition of the present invention in this region, a color filter having good color reproducibility can be produced.

Further, the dye having a dye structure derived from a dipyramethine dye preferably has an absorbance of 1,000 times or more, more preferably 10,000 times or more, and more preferably 100,000 times or more of the absorbance at a maximum absorption wavelength (? Max) Or more. When the ratio is within this range, a color filter having a higher transmittance can be formed by using the coloring composition of the present invention, particularly when a blue color filter is produced. Further, the maximum absorption wavelength and the molar extinction coefficient are those measured by a spectrophotometer cary5 (manufactured by Varian).

The melting point of the dipyrammethene metal complex compound represented by the general formula (7) and the general formula (8) should not be too high in view of solubility.

The dipyrammethene metal complex compound represented by the general formula (7) and the general formula (8) is disclosed in U.S. Patent Nos. 4,774,339, 5,433,896, JP-A 2001-240761, 2002-155052, Publication No. 3614586, Aust. J. Chem., 1965, 11, 1835-1845, J.H. Boger et al., Heteroatom Chemistry, Vol. 1, No. 5, 389 (1990), and the like. Specifically, the method described in paragraphs 0131 to 0157 of Japanese Laid-Open Patent Publication No. 2008-292970 can be applied.

Specific examples of the dipyramethane coloring matter are shown below, but the present invention is not limited thereto. In the formulas, X represents an anion. In the present invention, any one hydrogen atom of the following dye structures is bonded to the polymer skeleton.

(7)

Among these embodiments, (PM-4), (PM-7) and (PM-8) are preferable and (PM-8) is more preferable from the viewpoint of color characteristics and heat resistance.

<<< Carbonium coloring >>>

Among the carbonium dyes, triarylmethane dyes and xanthine dyes are preferred.

(Triarylmethane dye)

One of the aspects of the cation having a dye structure according to the present invention is one having a partial structure derived from a triarylmethane dye (triarylmethane compound). The dye has, as a dye structure, a partial structure derived from a compound (triarylmethane compound) represented by the following general formula (TP). In the present invention, the term "triarylmethane compound" refers to a compound having a dye structure including a triarylmethane skeleton in its molecule.

The general formula (TP)

[Chemical Formula 8]

(Formula (TP) of, Rtp ¹ ~ Rtp ⁴ are, each independently, represent a hydrogen atom, alkyl group or aryl group. Rtp ⁵ is a hydrogen atom, an alkyl group, an aryl group or NRtp ⁹ Rtp ¹⁰ (Rtp ⁹ and Rtp ¹⁰ represents a represents a hydrogen atom, an alkyl group or an aryl group). Rtp ^6, Rtp ⁷ and Rtp ⁸ shows a substituent. a, b and c represents an integer of 0 ~ 4. a, b and c is 2 or more Rtp ⁶ , Rtp ⁷ and Rtp ⁸ may be connected to form a ring, X ^- represents an anion structure, and when X ^- is not present, at least one of Rtp ¹ to Rtp ⁸ contains an anion do.)

For a preferable range and specific examples of the compound represented by the formula (TP), reference can be made to the description of paragraphs 0170 to 0178 of JP-A-2013-28764, the contents of which are incorporated herein by reference.

The introduction site in the case of introducing a compound represented by formula (TP) into the structural unit represented by formula (A) is not particularly limited, but is preferably introduced into any one of Rtp ¹ to Rtp ¹⁰ .

(Xanthan)

A preferred embodiment of the cation having a dye structure in the present invention is one having a partial structure derived from a xanthine dye (xanthine compound). The dye has, as a dye structure, a partial structure derived from a xanthene compound represented by the following general formula (J).

[Chemical Formula 9]

(In the formula (J), R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represents a hydrogen atom or a monovalent substituent, R ⁸⁵ independently represents a monovalent substituent, And X ^- represents an anion structure, and when X ^- is absent, at least one of R ⁸¹ to R ⁸⁵ includes an anion.

The introduction site in the case of introducing the compound represented by formula (J) into the structural unit represented by formula (A) is not particularly limited, but is preferably introduced into any one of R ⁸¹ to R ⁸⁵ .

The substituent groups R ⁸¹ to R ⁸⁴ and R ⁸⁵ in the general formula (J) can take are the same as the substituents in the group of the substituent group A described later.

R ⁸¹ and R ⁸² in the general formula (J), R ⁸³ and R ⁸⁴ , and R ⁸⁵ when m is 2 or more are each independently bonded to form a 5-membered, 6-membered or 7-membered ring or 5 A 6-membered or 7-membered unsaturated ring. When the 5-membered, 6-membered or 7-membered ring to be formed is a further substitutable group, the substituent may be substituted with the substituent described in R ⁸¹ to R ⁸⁵ , and when the substituent is substituted with two or more substituents, May be different or different.

R ⁸¹ and R ⁸² in the general formula (J), R ⁸³ and R ⁸⁴ , and R ⁸⁵ when m is 2 or more are each independently bonded to form a 5-membered, 6-membered or 7-membered 6-membered and 7-membered unsaturated rings which do not have a substituent or 5-membered, 6-membered and 7-membered unsaturated rings when forming a 5-membered, 6-membered or 7-membered unsaturated ring A thiazole ring, an oxazole ring, a thiazole ring, a pyrrole ring, a piperidine ring, a cyclopentane ring, a cyclohexane ring, a benzene ring, a pyridine ring, a pyridine ring, A furan ring, a pyrazine ring, and a pyridazin ring, preferably a benzene ring and a pyridine ring.

In particular, it is preferable that R ⁸² and R ⁸³ are a hydrogen atom or a substituted or unsubstituted alkyl group, and R ⁸¹ and R ⁸⁴ are a substituted or unsubstituted alkyl group or a phenyl group. R ⁸⁵ is preferably a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamido group, a carboxyl group or an amido group, and more preferably a sulfo group, a sulfonamido group, a carboxyl group or an amido group desirable. It is preferred that R &lt; ^{85 &gt;} is bonded to the adjacent portion of the carbon linked to the polycyclic ring. The substituent of the phenyl group of R ⁸¹ and R ⁸⁴ is particularly preferably a hydrogen atom, a halogen atom, a straight-chain or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamido group or a carboxyl group.

The compound having a xanthane skeleton represented by the general formula (J) can be synthesized by a method described in the literature. Specifically, Tetrahedron Letters, 2003, vol. 44, No. 23, pp. 4355-4360, Tetrahedron, 2005, vol. 61, No. 12, pp. 3097-3106, and the like can be applied.

Specific examples of the xanthene compound are shown below, but the present invention is not limited thereto. In the present invention, any one hydrogen atom of the following dye structures is bonded to the polymer skeleton.

[Chemical formula 10]

(11)

[Chemical Formula 12]

<<< Cyanine color >>>

One of the aspects of the cation having a dye structure according to the present invention is one having a partial structure derived from a cyanine dye (a cyanide compound). For details of these, reference can be made to the description of paragraphs 0191 to 0201 of Japanese Laid-Open Patent Publication No. 2013-28764, the contents of which are incorporated herein by reference.

<<< Subphthalocyanine pigment >>>

One aspect of the cation having a dye structure according to the present invention is one having a subphthalocyanine pigment structure. For details of these, reference can be made to the description of paragraphs 0242 to 0250 of Japanese Laid-Open Patent Publication No. 2013-28764, the contents of which are incorporated herein by reference.

<< Squarylium pigment >>

The cation having a dye structure used in the present invention may have a squarylium dye structure. For details of these, reference can be made to the description of paragraphs 0202 to 0223 of Japanese Laid-Open Patent Publication No. 2013-28764, the contents of which are incorporated herein by reference.

The dye of the present invention may be substituted with a substituent selected from Substituent Group A below in the dye structure as long as it does not deviate from the object of the present invention.

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, Cyclohexyl [2, 2] octan-3-yl) or tricycloalkyl group, and the like can be mentioned , Preferably monocyclic cycloalkyl groups, bicycloal Group, and that the cycloalkyl group of monocyclic 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 substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or polycyclic heterocyclic group of 5 to 7 members, 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 the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2- Pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), a cyano group, a hydroxyl group, a nitro group, a carboxyl 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, and the heterocyclic moiety is preferably a heterocyclic moiety described in 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), or a cyano group, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy,

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 in the above 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, an ethylsulfonyl 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 Substituted or non-substituted 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 heterocyclic portion is preferably the heterocyclic moiety described in the above heterocyclic group), for example, phenylazo, p-chlorophenyl azo, 5-ethylthio-1,3,4-thiadiazol- (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 phosphine group 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 include methylsulfonylaminocarbonyl , p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

<<< counter negative ion >>>

When the dye structure used in the present invention has a cation structure, the counter anion may be present in the same repeating unit of the dye multimer or may be other than the same repeating unit. The presence of the counter anion in the same repeating unit refers to a case in which a cation and an anion are bonded through a covalent bond in a repeating unit having a pigment structure. On the other hand, the term "other than the same repeating unit" means the case other than the above. For example, the case where the cation and the anion are not bonded through a covalent bond but exists as a separate compound, and the case where the cation and the anion are included as independent repeating units of the dye multimer, respectively.

(When the counter anion is in the same repeating unit)

The first embodiment of the anion in the present invention is a case where the opposite anion is present in the same repeating unit, specifically, a case in which a cation and an anion are bonded through a covalent bond in a repeating unit having a dye structure .

As the anion part of the _{^{case, -SO 3 -, -COO -,}} -PO 4 -, it is preferably at least one member selected from the following formula structure represented by the structure and the following general formula (A2) represented by (A1).

In formula (A1)

[Chemical Formula 13]

(In the general formula (A1), R ¹ and R ² each independently represent -SO ₂ - or -CO-.)

In the general formula (A1), at least one of R ¹ and R ² is -SO ₂ -, and it is preferable that indicates, both the R ¹ and R ² -SO ₂ - and more preferably indicating.

The above general formula (A1) is more preferably represented by the following general formula (A1-1).

In general formula (A1-1)

[Chemical Formula 14]

(In the general formula (A1-1), R ¹ and R ² each independently represent -SO ₂ - or -CO-, and X ¹ and X ² each independently represent an alkylene group or an arylene group.)

In the general formula (A1-1), R ¹ and R ² are the same as those of R ¹ and R ² in the general formula (A1), and their preferable ranges are also the same.

When X ¹ represents an alkylene group, the number of carbon atoms of the alkylene group is preferably from 1 to 8, more preferably from 1 to 6. When X ¹ represents an arylene group, the number of carbon atoms of the arylene group is preferably 6 to 18, more preferably 6 to 12, and even more preferably 6. When X ¹ has a substituent, it is preferably substituted with a fluorine atom.

X ² represents an alkyl group or an aryl group, and an alkyl group is preferable. The number of carbon atoms in the alkyl group is preferably from 1 to 8, more preferably from 1 to 6, still more preferably from 1 to 3, and particularly preferably 1. When X ² has a substituent, it is preferably substituted with a fluorine atom.

In general formula (A2)

[Chemical Formula 15]

(In the general formula (A2), R ³ represents -SO ₂ - or -CO-, R ⁴ and R ⁵ each independently represent -SO ₂ -, -CO- or -CN.)

In the general formula (A2), R ³ ~ R ⁵ is at least one of -SO ₂ -, and it is preferable that indicates, at least two of R ³ ~ R ⁵ -SO ₂ - and more preferably indicating.

In the present embodiment, particularly, when the skeleton of the dye multimer is represented by the structural unit represented by the general formula (A), a case where a part of L ₁ includes a moiety represented by the general formula (A1) is a preferable example . Specific examples of such a case include (a-xt-1), (a-xt-5) and (a-xt-6) in the examples of repeating units having a dye structure described below.

Also in this embodiment, the case where the skeleton of the dye multimer used in the present invention includes the structural unit represented by the general formula (B) shown in paragraphs 0276 to 0304 of Japanese Laid-Open Patent Publication No. 2013-28764 is also an example . (B-dp-1), (B-mp-1), (B-xt-1) and (B-xt-2) in the examples of the repeating units having a dye structure .

(If the counter anion is a separate molecule)

The second embodiment of the anion in the present invention is a case where the opposite anion is out of the same repeating unit and the cation and the anion are not bonded through a covalent bond but exist as separate molecules.

Examples of the anion in this case include a fluorine anion, a chlorine anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, a borate anion (BF ⁴ -y), PF ^6- and SbF ^6- , Borate anions and PF &lt; ⁶ &gt; are preferred.

The borate anion is a group represented by B (R ¹⁰ ) ^4- , and R ¹⁰ is a fluorine atom, a cyano group, an alkyl fluoride group, an alkoxy group, or an aryloxy group.

The anion may be contained in a part of the compound as an anion part. As the anion part of the _{^{case, -SO 3 -, -COO -,}} -PO 4 -, the at least one structure selected from structures represented by the general formula and general formula (A2) represented by (A1) described in the first embodiment of paper desirable.

Specific examples of the anion of the second embodiment include the following, but the present invention is not limited thereto.

[Chemical Formula 16]

[Chemical Formula 17]

In the second embodiment, the anion may be a mass of anion. As the multimer in this case, a multimer containing a repeating unit containing an anion and containing no repeating unit derived from a dye structure containing a cation is exemplified. Here, as the repeating unit containing an anion, a repeating unit containing an anion described in the third embodiment to be described later may be mentioned as a preferable example. Further, the multimer containing an anion may have a repeating unit other than the repeating unit containing an anion. As such a repeating unit, other repeating units which may be contained in the dye multimer used in the present invention to be described later are exemplified as preferable examples.

(In the case where the cation and the anion are included in the respective other repeating units of the dye multimer)

The third embodiment of the present invention refers to a case where cations and anions are included in independent repeating units of a dye multimer.

In the case of the present embodiment, the anion may be present in the side chain of the dye multimer, may be contained in the main chain, or may have a counter anion in both the main chain and the side chain. Preferably, it is a side chain.

Preferable examples of the repeating unit containing an anion include repeating units represented by the formula (C) and repeating units represented by the formula (D).

In the general formula (C)

[Chemical Formula 18]

(In the general formula (C), X ¹ represents a main chain of the repeating unit, L ¹ represents a single bond or a divalent linking group, and anion represents the above counter anion.

In the general formula (C), X ¹ represents a main chain of a repeating unit, and usually represents a linking group formed by a polymerization reaction. For example, a (meth) acrylic, styrene, Acrylic type is more preferable. In addition, the parts indicated by two * are repeated units.

When L ¹ represents a divalent linking group, an 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), an arylene group having 6 to 30 carbon atoms (a phenylene group, ), A heterocyclic linking group, -CH = CH-, -O-, -S-, -C (= O) -, -CO-, -NR-, -CONR-, -OC-, -SO-, -SO ₂ -, and a linking group combining two or more of them. Here, R represents, independently of each other, a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

In particular, L ¹ represents a single bond or an alkylene group having 1 to 10 carbon atoms (preferably - (CH ₂ ) n - (n is an integer of 5 to 10) and an arylene group having 6 to 12 carbon atoms A phenylene group, a naphthalene group), -NH-, -CO ₂ -, -O- and -SO ₂ -.

Specific examples of X ^1, examples of X ¹ in the general formula (A) may be mentioned as a preferable example.

In general formula (D)

[Chemical Formula 19]

(In the general formula (D), L ² and L ³ each independently represent a single bond or a divalent linking group.) Anion represents the above counter anion.

In the formula (D), when L ² and L ³ represent a divalent linking group, an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, -CH═CH-, -O-, -S-, -C (= O) -, -CO ₂ -, -NR-, -CONR-, -O ₂ C-, -SO-, -SO ₂ - and a linking group combining two or more thereof. Here, R represents, independently of each other, a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

L ² is preferably an arylene group having 6 to 12 carbon atoms (particularly a phenylene group). The arylene group having 6 to 30 carbon atoms is preferably substituted with a fluorine atom.

L ³ is preferably a group formed by a combination of an arylene group (particularly a phenylene group) having 6 to 12 carbon atoms and -O-, and at least one arylene group having 6 to 12 carbon atoms is preferably substituted with a fluorine atom.

Specific examples of the repeating unit containing an anion in the present embodiment are shown below, but the present invention is not limited thereto.

[Chemical Formula 20]

The following specific examples show a state in which the anion structure is not dissociated, but it is needless to say that the state in which the anion structure is dissociated is also within the scope of the present invention.

[Chemical Formula 21]

[Chemical Formula 22]

(23)

&Lt; EMI ID =

(25)

Examples of the repeating unit (a) preferably used in the present invention are shown below. It is needless to say that the present invention is not limited to these. X ^- represents a counter anion. It is to be noted that some Xs are shown in a state in which the anion structure is not disassociated, but it is needless to say that the disassociated state is also included in the present invention.

(26)

(27)

(28)

[Chemical Formula 29]

(30)

(31)

(32)

(33)

<< (b) Repeating unit having a group consisting of repeating of 2 to 20 unsubstituted alkyleneoxy chains on the side chain >>

The dye multimer used in the present invention is a repeating unit (b) having repeating units of 2 to 20 unsubstituted alkyleneoxy chains in the side chain (hereinafter sometimes referred to as "(b) repeating unit") .

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- and n is an integer, and 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)

(34)

(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, and more preferably a group consisting of a group-terminal atom or a terminal group consisting of repeating -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) the repeating unit having a repeating unit of 2 to 20 unsubstituted alkyleneoxy chains in the side chain is preferably 2 to 20 mol% of the total repeating units constituting the colorant multimer, And more preferably 15 mol%.

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.

(35)

<< Other functional groups or other repeating units >>

The dye multimer of the present invention may have a functional group other than the above and another repeating unit.

The other functional group may be contained in the repeating unit (a) and / or the repeating unit (b), and may be contained as another repeating unit containing a functional group separately from these repeating units.

Examples of other functional groups include polymerizable groups, acid groups, and other alkali-soluble groups. More specifically, in the general formula (P), a repeating unit in which P is a polymerizable group, an acid group and other alkali-soluble groups is preferable. As other repeating units, repeating units containing at least one of a polymerizable group and an acid group are exemplified.

The details of these will be described below.

<<< Polymeric group >>>>>

The polymerizable group is preferably included in the embodiment contained in the repeating unit (a) and in the other repeating unit. is contained in the dye structure in the repeating unit (a), heat resistance tends to be further improved. The polymerizable group may be contained only in one kind or in two or more kinds.

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.

More specifically, in the general formula (P), a repeating unit in which P is a polymerizable group is preferable.

Examples of the method of introducing the polymerizable group include: (1) a method of modifying and introducing a polymerizable group-containing compound into a repeating unit into which a polymerizable group is to be introduced, such as (a) a repeating unit, (2) a method of copolymerizing and introducing a polymerizable group- .

The amount of the polymerizable group contained in the dye structure in the repeating unit (a) is preferably 0.1 to 2.0 mmol, more preferably 0.2 to 1.5 mmol, and more preferably 0.3 to 1.0 mmol based on 1 g of the pigment structure Particularly preferred.

When the other repeating units contain a polymerizable group, the amount thereof is preferably 10 to 40 moles, more preferably 15 to 35 moles, per 100 moles of the total repeating units.

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

(36)

(37)

(38)

<<< Mountains >>>

Examples of the acid group which may be contained in the dye multimer in the present invention include a carboxylic acid group, a sulfonic acid group and a phosphoric acid group. In the present invention, the acid group is preferably a repeating unit having an acid group and contained in the colorant multimer. The acid group may be contained only in one kind or in two or more kinds.

The acid value of the colorant multimer used in the present invention is preferably from 0.3 to 1.5 mmol / g, more preferably from 0.5 to 1.2 mmol / g, more preferably from 0.5 to 1.0 mmol / g, Do.

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, it is possible to obtain a resin having a desired acid value by changing the content of the monomer unit containing an acid group, which is a raw material for the dye multimer.

More specifically, in the general formula (P), a repeating unit in which P is an acid group is preferable.

When the dye multimer contains repeating units having an acid group, the proportion of repeating units containing an acid group-containing repeating unit is, for example, 20 to 80 moles per 100 moles of repeating units containing a pigment multimer More preferably 20 to 65 moles.

<<< Other alkali soluble groups >>>

The dye multimer in the present invention may contain an alkali-soluble group other than the above-mentioned groups. Examples of the alkali-soluble group which may be contained in the pigment multimer used in the present invention include a phenolic hydroxyl group and the like.

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

As a method of introducing an alkali-soluble group into a dye-form mass, a method of introducing an alkali-soluble group into the dye monomer in advance may be mentioned. Examples of the method for introducing an alkali-soluble group into a dye multimer include a monomer other than the dye monomer having an alkali-soluble group (caprolactone-modified product of (meth) acrylic acid and acrylic acid, modified product of 2-hydroxyethyl (meth) , Modified phthalic anhydride of 2-hydroxyethyl (meth) acrylate, modified 1,2-cyclohexanedicarboxylic anhydride of 2-hydroxyethyl (meth) acrylate, styrene carboxylic acid, itaconic acid, maleic acid, A monomer containing a carboxylic acid such as stearic acid, a stearic acid, a stearic acid, a stearic acid, a stearic acid, a stearic acid, a stearic acid, a stearic acid, a stearic acid, a stearic acid, .

More specifically, in the general formula (P), a repeating unit in which P is an alkali-soluble group is preferable.

When the alkali-soluble group is contained in the dye oligomer, the amount of the alkali-soluble group is preferably 0.3 mmol to 2.0 mmol, more preferably 0.4 mmol to 1.5 mmol, and more preferably 0.5 mmol to 1.0 mmol based on 1 g of the colorant multimer Particularly preferred.

When the dye multimer contains a repeating unit having an alkali-soluble group, the proportion of the repeating unit containing a repeating unit having an alkali-soluble group is preferably from 1 to 100 moles per 100 moles of the repeating unit containing a dye multimer, 10 mols is preferred.

<<< Other Functionalities >>>

In addition to the above-mentioned other functional groups, as the functional group which may be contained in the pigment multimer used in the present invention, a development promoter such as lactone, acid anhydride, amide, -COCH ₂ CO- and cyano group, long chain and cyclic alkyl group, , An aryl group, a polyalkylene oxide group, a hydroxyl group, a maleimide group, and an amino group, and the like, and they can be suitably introduced. These may be contained only in one kind or in two or more kinds.

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

<<< Example >>>

Specific examples of other repeating units are shown, but the present invention is not limited thereto.

[Chemical Formula 39]

<< Characteristic of pigment multimers >>

In the dye multimer of the present invention, the maximum absorption wavelength is preferably 400 to 650 nm, more preferably 450 to 600 nm.

The weight average molecular weight 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.

In particular, in the case of a colorant multimer containing a xanthine coloring matter, 8,000 to 20,000 is preferable, and 10,000 to 18,000 is more preferable.

In the case of a dye multimer containing a dipyramethane dye, 5,000 to 20,000 is preferable, and 9,000 to 15,000 is more preferable.

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 3.0, more preferably 1.0 to 2.5, Particularly preferably 2.0 to 2.0.

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. The 5% weight reduction temperature by thermogravimetric analysis (TGA measurement) is preferably 120 ° C or higher, more preferably 150 ° C or higher, and even more preferably 200 ° C or higher. 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.

The absorption coefficient per unit weight of the colorant multimer according to the present invention (hereinafter referred to as? '=? / Average molecular weight, unit: L / g? Cm) is preferably 30 or more, 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 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 0.40 to 1.00, more preferably 0.45 to 0.80, and even more preferably 0.50 to 0.75.

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 from 50 to 70 mass%, more preferably from 55 to 65 mass%, of the total solid content of the coloring composition desirable.

&Lt; Other components of coloring composition >

The coloring composition of the present invention may contain other components in addition to the colorant multimer. For example, for the purpose of controlling the color value, etc., the coloring composition used in the present invention preferably contains a pigment and a pigment dispersant in addition to the above-mentioned pigment oligomer.

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 including a polymerizable group) is exemplified and appropriately selected according to the application and the production method. 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.

<< Pigment >>

The coloring composition of the present invention preferably further contains 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 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;

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

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. For example, as the red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone, or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone A yellowish pigment or a mixture with a perylene-based red pigment may 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 it is preferable to mix with CI Pigment Yellow 139 in terms of color degradability. 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. 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 halophthalic phthalocyanine pigment alone or in combination with the pigment of a disazo yellow pigment, a quinophthalone yellow pigment, an azomethan yellow pigment or an isophorone yellow pigment Mixing 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 ID = 0.0 &gt; 185 &lt; / RTI &gt; 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 black matrix pigment, 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 a pigment other than black, and more preferably blended with a blue pigment.

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, still more 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.

When the pigment is incorporated into the composition of the present invention, the content of the pigment is preferably from 20 to 50% by mass, more preferably from 25 to 50% by mass, relative to the total components excluding the solvent contained in the coloring composition, And preferably 30 to 45% by mass.

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

<< 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 from the structure.

Examples of the end-modified polymer having an anchor site on the surface of the pigment include a polymer 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. Furthermore, a polymer having an anchor site (an acid group, a basic group, a partial skeleton of an organic dye, a heterocycle, etc.) introduced into two or more pigment surfaces at the polymer terminal end described 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 the like can be mentioned acid group-containing copolymer of the monomer. Particularly, the amphoteric dispersion 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.

A known macromonomer can be used as the macromonomer used when the graft polymer having an anchor site on 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 particularly excellent in flexibility and hydrophilicity 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 on 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 (Copolymers containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166 and 170 (polymeric copolymers) "," BYK-P104, P105 Unsaturated polycarboxylic acid "), EFKA 4047, 4050 to 4010 to 4165 (polyurethane resin), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (High molecular weight polycarboxylic acid salt), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ", Ajisper PB821, PB822, PB880, PB881" manufactured by Ajinomoto Fine Techno Co., 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, P-123 "manufactured by Sanyo Chemical Industries, "And the like.

Further, a block copolymer obtained by radical-polymerizing a polymerizable unsaturated compound in the presence of a reversible addition-fragmentation chain transfer (RAFT agent) such as a dithiocarbonyl compound or the like and a radical initiator, or a block copolymer having a narrow molecular weight distribution May be used in combination as a pigment dispersant. Specific examples of such resins include resins described in Japanese Patent Laid-Open Publication No. 2008-242081, paragraphs 0053 to 0129 and Japanese Patent Laid-Open Publication No. 2008-176218, paragraphs 0049 to 0117, do. Such a block copolymer or a copolymer having a narrow molecular weight distribution may be used as an alkali-soluble resin.

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.

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 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.

<< Dye >>

The coloring composition of the present invention may contain a known dye other than a colorant multimer. 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 group, a pyromethene group, an anilino group, a triphenylmethane group, an anthraquinone group, a benzylidene group, an oxolane group, a pyrazolotriazole group, a pyridazo group, And pyrrolopyrazole azo methane phosphoric acid, can be used.

The dye may be contained in only one kind or in two or more kinds.

When the dye is contained in the coloring composition of the present invention, it may be, for example, 0.1 to 5% by mass of the total coloring agent.

<< 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 it 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.

The photopolymerization initiator preferably 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, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, An oxime compound such as an oxazole compound, an oxazole compound such as an oxazole compound, an oxazole compound such as an oxazole derivative, an organic peroxide, a thio compound, a ketone compound, an aromatic onium salt, a ketoximeether, an aminoacetophenone compound and 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.

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As the trihalomethyltriazine compound, a commercially available product may be used, and 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 the photopolymerization initiator (D) in order to form a fine pattern such as a solid-state image sensor.

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 type initiator, commercial products IRGACURE-819 and DAROCUR-TPO (trade names, all of which are manufactured by BASF) and Midori Kagaku TAZ series (such as TAZ-107, TAZ-110 and TAZ- , TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123).

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.) .

As oxime compounds other than the above-mentioned materials, compounds described in Japanese 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 where nitro groups are introduced, ketoxime compounds described in International Patent Publication No. 2009-131189, triazine skeleton and oxime skeleton in the same molecule The compound described in U.S. Patent Publication No. 7556910, the 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 covalently bound to the carbazole dyes described in JP-A-2010-32985 and JP-A-2010-185072 are preferred from the viewpoint of high sensitivity due to their high light absorption.

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 specific substituents as shown in Japanese Patent Application Laid-Open No. 2007-269779 and oxime compounds having thioaryl groups as disclosed in Japanese Patent 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).

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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 nonmetal 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.

The alkyl group is preferably an alkyl group having from 1 to 30 carbon atoms and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, , a sec-butyl group, a tert-butyl group, a 1-ethylpentyl group, a cyclopentyl group, a cyclohexyl group, a trifluoromethyl group, a 2-ethylhexyl group, a phenacyl group, , 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group , 3-trifluoromethylphenacyl group, and 3-nitrophenacyl group.

As the aryl group, an aryl group having 6 to 30 carbon atoms is preferable, and specific examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, Naphthacenylene group, a 5-naphthacenylene group, a 1-indenyl group, a 2-azulenyl group, a 9-fluorenyl group, a terphenyl group, a quaterphenyl group, an o- tolyl group, Dienes, m-cumene dienes and p-cumene dienes, mesityl groups, pentalene dienes, binaphthalenylene dienes, terenaphthalene dienes, quaternaphthalenylene dienes, heptalenylene dienes, biphenylene dienes, indacene dienes, A phenanthryl group, a pyrenyl group, a pyrenyl group, a pyrenyl group, a pyrenyl group, a pyrenyl group, a pyrenyl group, a pyrenyl group, a pyrenyl group, a pyrenyl group, a pyrenyl group, A naphthacene group, a pheenadien group, a picenyl group, a perylene group, a pentaphenyl group, a pentacene group, a tetraphenylene group A heptylphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalvenyl group can be exemplified as the alkylene group, the alkylene group, and the alkylene group.

As the acyl group, an acyl group having 2 to 20 carbon atoms is preferable, and specific examples thereof include an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, a 1-naphthoyl group, A 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2- Trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-fluorobenzoyl group, 4-chlorobenzoyl group, A cyano group, a cyano group, a cyano group, a cyanobenzoyl group, and a 4-methoxybenzoyl group.

The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and specific examples thereof include a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group , A decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

Specific examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylsulfanylphenyloxycarbonyl group, a 4-phenylsulfanylphenyloxycarbonyl group, A 4-dimethylaminophenyloxycarbonyl group, a 2-chlorophenyloxycarbonyl group, a 2-methylphenyloxycarbonyl group, a 2-methoxyphenyloxycarbonyl group, a 2-butoxyphenyloxy 3-chlorophenyloxycarbonyl, 3-chlorophenyloxycarbonyl, 3-trifluoromethylphenyloxycarbonyl, 3-cyanophenyloxycarbonyl, 3-nitrophenyloxycarbonyl, 4-fluorophenyloxycarbonyl, 4- Cyanophenyloxycarbonyl group, and 4-methoxyphenyloxycarbonyl group.

As the heterocyclic group, an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom is preferable.

Specific examples thereof include a cyano group, a benzo [b] thienyl group, a naphtho [2,3-b] thienyl group, a thianthrenyl group, a furyl group, a pyranyl group, an isobenzofuranyl group, A pyrazolyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an indolizine group, an isoindolyl group, a 3H-indolyl group, a pyrazolyl group, a pyrazolyl group, , Indolyl group, 1H-indazolyl group, purine group, 4H-quinolyl group, isoquinolyl group, quinolyl group, phthalazine group, naphthyridyl group, quinoxalinyl group, quinazolinyl group, A pyranyl group, a phenanthryl group, a phenarazyl group, an isothiazole group, an imidazolyl group, an imidazolyl group, an imidazolyl group, a pyrimidinyl group, A diazonium, a phenothiazine diazonium, an isoxazoline diazonium, a furazanil diazonium, a phenoxazoi diazonium, an isochroman diazonium, , Pyrrolidinyl, pyrrolinyl, imidazolinyl, imidazolinyl, pyrazolidinyl, pyrazolyl, piperidyl, piperazinyl, indolinyl, isoindolinyl, quinuclidine, A diazo group, a morpholine diazo group, and a thioxantholyl group.

Specific examples of the alkylthiocarbonyl group include methylthiocarbonyl group, propylthiocarbonyl group, butylthiocarbonyl group, hexylthiocarbonyl group, octylthiocarbonyl group, decylthiocarbonyl group, octadecylthiocarbonyl group, A trifluoromethylthiocarbonyl group, a trifluoromethylthiocarbonyl group, and a trifluoromethylthiocarbonyl group.

Specific examples of the arylthiocarbonyl group include a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonyl group, a 4-phenylsulfanylphenylthiocarbonyl group, 4-dimethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2 3-chlorophenylthiocarbonyl group, 3-chlorophenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-chlorophenylthiocarbonyl group, 4-chlorophenylthiocarbonyl group, -Fluorophenylthiocarbonyl group, a 4-cyanophenylthiocarbonyl group, and a 4-methoxyphenylthiocarbonyl group.

In the general formula (OX-1), the monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. These groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified. In addition, the substituent described above may be further substituted with another substituent.

Among them, particularly preferred is the structure shown below.

Y, X, and n in the following structures are each the same as Y, X, and n in the general formula (OX-2) to be described later, and preferred examples are also the same.

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Examples of the divalent organic group represented by A in formula (OX-1) include an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, and an alkynylene group. These groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified. In addition, the substituent described above may be further substituted with another substituent.

Among them, A in the formula (OX-1) is preferably an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group An alkylene group substituted with an alkenyl group (e.g., a vinyl group or an allyl group), an aryl group (e.g., a phenyl group, a p-tolyl group, a xylyl group, a cumene group, Anthryl group, phenanthryl group, styryl group) is preferable.

In the formula (OX-1), the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent. As the substituent, the same substituent as the substituent introduced into the substituted aryl group as the specific example of the aryl group which may have a substituent first can be mentioned.

Of these, a substituted or unsubstituted phenyl group is preferable in that the sensitivity is increased and coloring due to heating and aging is suppressed.

In the formula (OX-1), from the viewpoint of sensitivity, it is preferable that the structure of "SAr" formed from Ar in the formula (OX-1) and S adjacent thereto is a structure shown below. Me represents a methyl group, and Et represents an ethyl group.

(44)

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

[Chemical Formula 45]

In the general formula (OX-2), each of R and X independently represents a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents an integer of 0 to 5. R, A, and Ar in formula (OX-2) are synonymous with R, A, and Ar in formula (OX-1), and preferred examples are also the same.

Examples of the monovalent substituent represented by X in formula (OX-2) include an alkyl group, aryl group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, amino group, heterocyclic group, . These groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified. In addition, the substituent described above may be further substituted with another substituent.

Among them, an alkyl group is preferable as X in the general formula (OX-2) in view of solubility in solvents and improvement of absorption efficiency in a long wavelength region.

In the formula (2), n represents an integer of 0 to 5, preferably an integer of 0 to 2.

Examples of the divalent organic group represented by Y in the general formula (OX-2) include the following structures. In the groups shown below, "*" represents a bonding position of Y and adjacent carbon atoms in formula (OX-2).

(46)

Among them, from the viewpoint of high sensitivity, the following structure is preferable.

(47)

The oxime compound is preferably a compound represented by the following general formula (OX-3) or (OX-4).

(48)

In the general formula (OX-3) or (OX-4), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n represents an integer of 0 to 5 .

R, X, A, Ar and n in the general formula (OX-3) or (OX-4) Agreement, and the preferred example is the same.

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

(49)

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) and 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 type of photopolymerization initiator or two or more types of photopolymerization initiators. When two or more kinds are included, the total amount is preferably in the above range.

<< Curing compound >>

<<< Polymerizable compound >>>

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

Known polymerizable compounds that can be crosslinked 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 is widely known in the industrial field, and they can be used without any particular limitation in the present invention. These may be, for example, monomers, prepolymers, i.e., dimers, trimer and oligomers or mixtures thereof and their chemical forms such as their 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 and the like), esters thereof, amides, And amides of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound, and a multimer thereof, preferably an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound. 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, a compound group substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an ally ether or the like may be used in place of the above unsaturated carboxylic acid.

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.

As the polymerizable compound, a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and having a boiling point of 100 캜 or higher at normal pressure is also preferable. 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-B-48-64183, JP-A-49-43191, JP-A-52-30490, epoxies which are reaction products of epoxy resins 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.

(50)

(51)

In the 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 plurality of 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 (═O) represents a group represented by _{C (CH 3) = CH 2} .

As specific examples of the polymerizable compounds represented by formulas (MO-1) to (MO-5), compounds described in paragraphs 0248 to 0251 of Japanese Laid-Open Patent Publication No. 2007-269779 are suitably used in the present invention .

Further, in JP-A No. 10-62986, a compound obtained by adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in the specific examples of the general formulas (1) and (2) and then adding (meth) Can also be used as a polymerizable compound.

Among them, dipentaerythritol triacrylate (KAYARAD D-330, manufactured by Nippon Kayaku Kabushiki Kaisha) and dipentaerythritol tetraacrylate (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) NK Ester A-DPH-12E manufactured by Shin-Nakamura Kagaku Co., Ltd.), and a structure in which these (meth) acryloyl groups are interposed between ethylene glycol and propylene glycol moieties SR454, SR494, SR499, etc., which are commercially available from Satomaru Co., Ltd.) are preferable. These oligomer types can also be used. Alternatively, tris (2-hydroxyethyl) isocyanurate triacrylate (commercially available SR368 from Satoromer) may be used.

The polymerizable compound is a polyfunctional monomer and may have an acid group such as a carboxyl group, a sulfonic acid group, or 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.

(52)

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

(53)

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.

(54)

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) (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 a compound), DPCA-60 (the same formula, m = 1, equation (2), both the number of = 6, R ¹ in the group represented by in the compound), DPCA-120 (the same expression hydrogen atoms m = 2, formula 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).

(55)

In the general formulas (Z-4) and (Z-5), E is each independently - ((CH ₂ ) _y CH ₂ O) - or - ((CH ₂ ) _y CH (CH ₃ ) -, y represents an integer independently from 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 an integer of 0 to 40 to be. Provided that when the sum of each m is 0, any one of X is a carboxyl group.

In the general formula (Z-5), 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 to be. 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.

- ((CH ₂ ) _y CH ₂ O) - or - ((CH ₂ ) _y CH (CH ₃ ) O) - in the general formula (Z-4) or the general formula (Z- Side 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 (Z-5), 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 a ring opening skeleton And a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride on the terminal hydroxyl group of the ring-opening skeleton. Each process is a well-known process, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).

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

Specifically, the compounds (a) to (f) below (hereinafter also referred to as "exemplified compounds (a) to (f)") , (e) and (f) are preferable.

(56)

(57)

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.).

As the cyclic ether (epoxy, oxetane), for example, as the compound having an epoxy group, a bisphenol A type epoxy resin such as JER-827, JER-828, JER-834, JER-1001, JER- (Manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 840, EPICLON 860, EPICLON 1050, EPICLON1051, EPICLON1055 (manufactured by DIC Corporation), etc., and bisphenol F type (Manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 (manufactured by DIC Co., Ltd.) (trade name, manufactured by DIC Corporation) as the epoxy resin, and JER-806, JER-807, JER-4004, JER-4005, JER- JER-152, JER-157, JER-157S70 and JER-157S65 (above, Japan) as the phenol novolak type epoxy resin, EPICLON N-660 (trade name, manufactured by DIC Corporation), EPICLON N-740, EPICLON N-770 and EPICLON N-775 EPICLON N-670, EPICLON N-680, EPICLON N-690, EPICLON N-695, , ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by Nippon Kayaku Co., Ltd.) and ADEKA RESIN as an aliphatic epoxy resin (2-epoxy-4- (2-hydroxyethyl) -1-butanol), Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE- EX-214L, EX-216L, EX-216L, EX-216L, EX-216L, and EX-216L), EPOLEAD PB 3600 and PB 4700 (manufactured by Daicel Chemical Industries, Ltd.) ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S and EP-4011S (manufactured by ADEKA Corporation), NC (Manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON HP7200 (DIC (registered trademark), manufactured by Nippon Polyurethane Industry Co., Ltd.) Ltd.), and the like. The epoxy compound is suitable for forming a pattern by a dry etching method.

Details of the structure, the use of the polymerizable compound, whether it is used singly or in combination, and the amount of the polymerizable compound 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 amount of unsaturated groups per molecule is preferable, and in many 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. In addition, it is preferable that the developing ability of the coloring composition can be controlled by using a polymerizable compound having three or more functional groups and having different ethylene oxide chain lengths, so that 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.

When the polymerizable compound is compounded in the coloring composition of the present invention, the content of the polymerizable compound is preferably from 0.1% by mass to 90% by mass, more preferably from 1.0% by mass to 60% by mass relative to the total solid content in the coloring composition , And 2.0% by mass to 40% by mass.

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

<<< Alkali-soluble resin >>>

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

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

As the alkali-soluble resin, a linear organic polymer may 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 molecule having 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 an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, and the like, preferably soluble in an organic solvent and capable of being developed by a weakly alkaline aqueous solution , And (meth) acrylic acid are particularly preferable. These acid groups may be only one kind, or two or more kinds.

Examples of the monomer capable of giving an acid group after polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, monomers having an epoxy group such as glycidyl (meth) acrylate, And monoisomers having an isocyanate group such as anisatoethyl (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 "monomer for introducing an acid group") is polymerized .

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 other monomers 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 either one type alone or two or more types.

As the alkali-soluble resin, it is also preferable that the alkali-soluble resin includes a polymer (a) obtained by polymerizing a monomer component essentially containing a compound represented by the following formula (ED) (hereinafter may be referred to as "ether dimer"

(58)

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.

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 (ED) 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, A linear or branched alkyl group such as methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl or 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)] - propenoate, di (n-propyl) -2,2' - [oxybis Di (isobutyl) -2,2 '- [oxybis (2-methoxyphenyl) -2,2'- 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 (meth) 2-propenoate, dibenzyl-2, 2 '- [oxy (2-methoxyphenyl) Bis (methylene)] bis-2-propenoate, diphenyl-2,2 '- [oxybis (methylene)] bis-2-propenoate, dicyclohexyl- )] Bis-2-propenoate, dicyclohexylcyclohexyl) -2,2 '- [oxybis (methylene)] bis- , 2 '- [oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) -2,2' Bis (2-propenyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, diadamantyl- 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 either 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 the ethylenically unsaturated monomer (a) represented by the following formula (X).

[Chemical Formula 59]

(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, an alkali-soluble resin having a polymerizable group may be used. 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 K.K.), 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 An unsaturated group-containing acrylic resin obtained by reaction of an urethane-modified polymerizable double bond-containing acrylic resin obtained by the reaction of an acrylic resin, an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule, 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? In addition, ARC Liqueur RD-F8 (manufactured by Nippon Shokubai Co., Ltd.) is also preferable.

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 / methacrylic Acid copolymers and the like, and particularly preferred are copolymers of benzyl methacrylate / methacrylic acid and the like.

As the alkali-soluble resin, reference can be made to Japanese Patent Application 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.

(60)

The acid value of the alkali-soluble resin is preferably from 30 mgKOH / g to 200 mgKOH / g, more preferably from 50 mgKOH / g to 150 mgKOH / g, and particularly preferably from 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 the solubility, coating ability, and safety of an ultraviolet absorber, an alkali-soluble resin or a dispersant . 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, cyclohexyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate , Butyl butyrate, methyl lactate, ethyl lactate, alkyloxyacetate (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (for example, methyl methoxyacetate, methoxyacetate, methoxyacetate, ethoxy Ethoxyacetic acid and the like), 3-oxypropionic acid alkyl esters (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate (e.g., methyl 3-methoxypropionate, 3-methoxypropionate Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate and the like), 2-oxypropionic acid alkyl esters such as 2-oxypropyl Propyl methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2- (2-methoxypropionate), 2- Methyl 2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methyl Ethyl propionate and the like), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like, and ethers such as diethylene glycol Diethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, di Ethylene glycol mono Ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate And ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like, and aromatic hydrocarbon such as toluene and xylene, .

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.

In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmmpl / L or less, and more preferably substantially no peroxide.

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 type of organic solvent or two or more types 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 in addition to the coloring composition of the present invention, it is possible to further increase the hardness of the cured film obtained by curing the coloring composition.

The crosslinking agent is not particularly limited as long as it can perform film curing by a crosslinking reaction, and examples thereof 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 coloring 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, (Manufactured by Asahi Glass Co., Ltd.), PF636, PF656 (manufactured by Asahi Glass Co., Ltd.), SC-103, SC-104, SC-105, SC1068, SC-381, SC- , PF6320, PF6520, PF7002 (manufactured by OMNOVA), and the like.

As the fluorine-based surfactant, a block polymer may be used. Specific examples thereof include the compounds described in Japanese Laid-Open Patent Publication No. 2011-89090.

Specific examples of the nonionic surfactant include glycerol, trimethylol propane, trimethylol ethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerine 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, Tertronic 304, 71, 704, 901, 904 and 150R1 of BASF) Lubrizol Corporation) 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 anhydride 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 anhydride, respectively, or may contain two or more kinds. 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 may 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 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-mentioned components.

Further, at the time of preparing the coloring composition, each component constituting the coloring composition may be blended at one time, or 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 of the present invention is preferably filtered with a filter for the purpose of removing foreign matters or reducing defects. So long as it is conventionally used for filtration applications and the like. For example, a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon-6 or nylon-6,6, a polyolefin resin such as polyethylene or polypropylene (PP) And the like). Of these materials, polypropylene (including high-density polypropylene) is preferable.

The pore diameter of the filter is preferably about 0.01 to 7.0 mu m, preferably about 0.01 to 3.0 mu m, and more preferably about 0.05 to 0.5 mu m. This range makes it possible to reliably remove fine foreign matter which inhibits the preparation of a uniform and smooth colored composition in a subsequent step.

When using a filter, different filters may be combined. At this time, the filtering in the first filter may be performed once or two or more times.

It is also possible to combine the first filters having different pore sizes within the above-mentioned range. Here, the hole diameter can refer to the nominal value of the filter maker. As a commercially available filter, there may be selected, for example, various filters provided by Nippon Oil Corporation, Advantech Toyokawa Co., Ltd., Nippon Integrity Corporation (formerly Nihon Micro-Roller Corporation) or Kitsch Microfilter .

The second filter may be formed of the same material as the first filter described above.

For example, the filtering in the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing the other components.

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 is suitably used for forming a coloring pattern of a solid-state imaging element (for example, a CCD, a CMOS or the like) or a color filter used for an image display apparatus such as a liquid crystal display . In addition, it can be suitably used for producing printing ink, inkjet ink, and paint. Among them, color filters for solid-state image pickup devices 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. A method of manufacturing a color filter using the pattern forming method of the present invention will be described.

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.

In the composition of the present invention, a color filter may be formed by pattern formation by the so-called photolithography method, or a pattern may be formed by a dry etching method.

That is, as a first embodiment of the pattern forming method of the present invention, there is provided a method for forming a pattern, comprising the steps of: applying a coloring composition onto a support to form a coloring composition layer; exposing the coloring composition layer in a pattern; A pattern forming method including a step of forming a colored pattern is exemplified.

As a second embodiment of the pattern forming method of the present invention, a step of applying a coloring composition onto 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.

Such a pattern formation method is used in the production of a colored layer of a color filter. That is, the present invention also discloses a method of manufacturing a color filter including the pattern forming method of the present invention.

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 in order to improve adhesion with the upper layer, prevent diffusion of the substance, or planarize 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, and these components may be appropriately selected from the components to be incorporated in the composition of the present invention desirable.

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 at a temperature of 50 ° C to 140 ° C for 10 seconds to 300 seconds in a hot plate, an oven or the like.

&Lt; Case 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 the present 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 development processing in a pattern forming step described later to improve the developability, surface roughness , And a colored pattern excellent in the pattern shape can be obtained.

<< Development Process >>

Subsequently, by performing the alkali development treatment, the colored composition layer in the unexposed area in the exposure step is eluted into the aqueous alkaline solution, leaving only the photo-cured portion.

As the developer, an organic alkali developing solution which does not cause damage to the underlying imaging element or circuit 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 developing solution every 60 seconds and newly supplying the developing solution may be repeated several 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. As the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate and the like are preferable.

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 coloring pattern of multiple colors is to be formed, a cured coating can be produced by repeating the above steps for each color in order. 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.

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 necessary, as the other process. For example, the coloring composition layer forming step, the exposure step, and the pattern forming step described above may be performed, and then, if necessary, a curing step of curing the formed colored pattern by heating and / or exposure.

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 for cleaning and removing 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 colored pattern (colored pixel) formed is excellent in pattern shape, The color characteristic is excellent because the residue in the developing portion is suppressed.

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

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 the configuration includes the color filter of 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 only a photodiode light- And a silicon nitride film or the like formed on the light-shielding film so as to cover the entire light-shielding film surface and the photodiode light-receiving portion. The color filter for a solid-state imaging device of the present invention .

It is also possible to use a configuration having a condensing means (for example, a microlens or the like) on the device protective layer and below the color filter (near the support), or a configuration having the condensing means on the color filter.

<Image Display Device>

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

In addition, the color filter in the present invention can be provided in a COA (Color-filter On Array) method which is bright and high definition. 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. In the color filter of the present invention, since a color pigment having excellent color is good, color purity, light transmittance and the like are good and coloring pattern (pixel) is excellent in color tone, a COA type liquid crystal display device having high resolution and long- . 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 assurance 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

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 it departs from the spirit thereof. In addition, "%" and "part" are on a mass basis unless otherwise specified.

&Lt; Synthesis Example 1: Synthesis of dye oligomers used in Example 1 >

(61)

31.2 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 Monomer 1 (35.0 g, 32.3 mmol), methacrylic acid (9.64 g, 112 mmol), dodecylmercaptan (2.75 g, 13.6 mmol), polyethylene glycol monomethacrylate (Trade name: V601, manufactured by Wako Pure Chemical Industries, Ltd.) (6.25 g, 27.1 mmol), 2.52 g of 2,2'-azobis (isobutyrate) Cyclohexanone (81.2 g) was added dropwise over 1 hour. Thereafter, the mixture was stirred at 90 ° C for 3 hours, cooled to room temperature, dropped into a mixed solvent of ethyl acetate / acetonitrile = 1530 mL / 170 mL, and re-dissolved. After air-drying at 40 占 폚 for one day, 25.3 g of the dye-sensitized body 2 was obtained. The coloring matter mass: methacrylic acid part: PE-90 part = 20: 68: 12 was confirmed by ¹ H-NMR, and the composition ratio (molar ratio) was confirmed to be 2.23 mmol / g.

(12.5 g), glycidyl methacrylate (2.19 g), tetraethylammonium bromide (0.40 g), p-methoxyphenol (0.015 g) and cyclohexanone 83.3 g), and the mixture was stirred at 105 캜 for 4 hours under air. Thereafter, the solution 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, 6.52 g of the pigment mass 3 was obtained. The coloring matter unit: methacrylic acid part: polymerizable group-containing part: PE-90 part = 20:36:32:12 was confirmed by ¹ H-NMR, and the composition ratio (molar ratio) was found to be 1.01 mmol / .

&Lt; Synthesis of dye multimer used in other examples and comparative examples >

<Synthesis of pigment multimer (Examples 2 to 42 and Comparative Examples 1 to 11>

Monomer 1 in Synthesis Example 1 and methacrylic acid and polyethylene glycol monomethacrylate were synthesized by carrying out the same operations except that the monomers were changed to be the repeating units shown in Table 1 below.

&Lt; Synthesis Example 2: Synthesis of dye oligomers used in Example 43 >

(62)

39.2 g of N-ethylpyrrolidone was added to a three-necked flask, and the mixture was heated to 90 占 폚 under a nitrogen atmosphere. To this solution was added monomer 4 (40.0 g, 35.4 mmol), methacrylic acid (MAA, 4.62 g, 53.7 mmol), dodecyl mercaptan (2.79 g, 13.8 mmol), polyethylene glycol monomethacrylate (BBEM, 12.5 g, 44.8 mmol), 2,2'-azobis (3-aminophenol) (PE-90 manufactured by Nichiyu K.K.) (3.38 g), ethylene glycol mono 2-bromoisobutylate monomethacrylate (6.25 g, 27.1 mmol) and N-ethylpyrrolidone (91.4 g) was added dropwise over 1 hour. After that, 10.54 g of N-ethylpyrrolidone was added and stirred at 90 占 폚 for 3 hours and then cooled to room temperature. After cooling to room temperature, 253 g of N-ethylpyrrolidone and 0.279 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical were added to the reaction solution, and diazabicyclic Undecene (DBU) (47.6 g) was added slowly, and the mixture was stirred at room temperature for 14 hours. Thereafter, the solution was cooled to 5 degrees or less with an ice bath, and 30.1 g of methanesulfonic acid and 16.9 g of N-ethylpyrrolidone were added slowly. After the reaction, the reaction solution was added dropwise to 4800 mL of 1 mol / l hydrochloric acid and re-dissolved. The solid obtained by filtration was suspended in 250 parts of acetonitrile, washed with water again and filtered to obtain 50.0 g of the dye 6 of the present invention .

The dye 6 had a weight average molecular weight (in terms of polystyrene) of 8000 and an acid value of 0.74 mmol / g by titration using a 0.1 mol / l aqueous solution of sodium hydroxide. The composition ratio (molar ratio) was confirmed by ¹ H-NMR, and the coloring matter part: methacrylic acid part: polymerizable group-containing part: PE-90 part = 28: 31: 27:

&Lt; Colorant multimers (Synthesis of Examples 44 to 75)

Monomer 4 and methacrylic acid and polyethylene glycol monomethacrylate in Synthesis Example 2 were synthesized by carrying out the same operations except that the monomers were changed to be the repeating units shown in Table 3 below.

1. Preparation of resist solution

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

Composition of resist solution for undercoat layer

Solvent: propylene glycol monomethyl ether acetate Section 19.20

Solvent: Ethyl lactate 36.67 parts

40% PGMEA solution of alkali soluble resin: 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) 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 a trihalomethyltriazine type

(TAZ-107, manufactured by Midori Kagaku Co., Ltd.) 0.586 part

2. Fabrication of silicon wafer substrate with undercoat layer

The silicon wafer with undercoat layer used for the evaluation was produced as follows.

CT-4000L (manufactured by Fuji Film Electronics Materials Co., Ltd.) was uniformly coated on a 200 mm (8 inch) silicon wafer by spin coating to form a coating film. The coating film was cured to form an undercoat layer. The spinning speed of the spin coat was adjusted so that the film thickness of the coated film after the heat treatment became about 0.1 mu m.

3. Preparation of coloring composition

3-1. Preparation of blue pigment dispersion

(Preparation of Pigment Dispersion P1 (C.I. Pigment Blue 15: 6 Dispersion)

A pigment dispersion P4 (C.I. Pigment Blue 15: 6 dispersion) was prepared in the following manner.

19.4 parts by mass (average primary particle diameter: 55 nm) of CI Pigment Blue 15: 6 (hereinafter, also referred to as "PB 15: 6") and 2.95 parts by mass of pigment dispersant BY- 2.95 parts by mass of the alkali-soluble resin 1 and 172.3 parts by mass of PGMEA were mixed and dispersed for 3 hours by a beads mill (zirconia beads 0.3 mm in diameter) for 3 hours. Thereafter, dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high pressure disperser NANO-3000-10 (manufactured by Nippon Express Co., Ltd.) with a pressure reducing mechanism. This dispersion treatment was repeated 10 times to obtain a CI Pigment Blue 15: 6 dispersion as a pigment dispersion. The average primary particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (Nikkiso Co., Ltd.)) relative to the obtained CI Pigment Blue 15: 6 dispersion.

(Preparation of pigment dispersion P2 (C.I. Pigment Blue 15: 6 dispersion)

Pigment dispersion P2 was prepared in the same manner as P1 except that the following dispersant D1 was used as the pigment dispersant.

(63)

(Preparation of Pigment Dispersion P3 (C.I. Pigment Blue 15: 6 Dispersion)

A pigment dispersion P3 was prepared in the same manner as in the preparation of P1 except that the following dispersant D2 was used as the pigment dispersant.

&Lt; EMI ID =

3-2. Preparation of coloring composition

(Preparation of colored composition 1) (Examples 1 to 40 and Comparative Examples 1 to 11)

The following components were mixed, dispersed and dissolved to obtain a colored composition.

Organic solvent (cyclohexanone): 17.12 parts

Alkali-soluble resin 1 (copolymer of benzyl methacrylate (BzMA) and methacrylic acid (MAA), 30% PGMEA solution): 1.23 parts

Alkali-soluble resin 2 (ARCICURE RD-F8 (manufactured by Nippon Shokubai Co., Ltd.)): 0.23 parts

Photopolymerization initiator I-2 (IRGACURE OXE-02): 0.975 parts

· Cyclohexanone solution of the colorant multimer (solid content concentration 12.3%): 24.57 parts

Pigment dispersion (C.I. Pigment Blue 15: 6 dispersion, PGMEA solution, solid concentration 12.8%): 51.40 parts

Polymerizable compound (ethyleneoxy-modified dipentaerythritol hexaacrylate, NK ester A-DPH-12E (Shin-Nakamura Kagaku)): 1.96 parts

Polymerization inhibitor (p-methoxyphenol): 0.0007 part

Fluorine-based surfactant (F475, 1% PGMEA solution, manufactured by DIC): 2.50 parts

(Preparation of Coloring Composition 2) (Examples 41 and 42)

The following components were mixed, dispersed and dissolved to obtain a colored composition.

Organic solvent (cyclohexanone): 17.12 parts

Epoxy Compound JER1031S (manufactured by Mitsubishi Chemical Corp., epoxy equivalent: 180-220 (g / eq.)): 4.395 parts

· Cyclohexanone solution of the colorant multimer (solid content concentration 12.3%): 24.57 parts

Pigment dispersion (C.I. Pigment Blue 15: 6 dispersion, PGMEA solution, solid concentration 12.8%): 51.40 parts

Polymerization inhibitor (p-methoxyphenol): 0.0007 part

Fluorine-based surfactant (F475, 1% PGMEA solution, manufactured by DIC): 2.50 parts

(Preparation of Coloring Composition 3) (Examples 43 to 46, 49 to 72)

The following components were mixed to obtain Coloring Composition 3.

· Organic solvent (cyclohexanone): 14.69 parts

Alkali-soluble resin 1: 0.29 parts (solid 0.09 part, solid content 30%)

Alkali-soluble resin 2 (ARC Liqueur RD-F8 (manufactured by Nippon Shokubai Co., Ltd.)): 0.05 part

Photopolymerization initiator: 0.78 part

· Cyclohexanone solution of colorant multimer (solid concentration 12.3%): 28.45 parts

Pigment dispersion (C. I. Pigment Blue 15: 6 dispersion, PGMEA solution, solid concentration 12.8%): 51.23 parts

Polymerizable compound: 1.61 parts

Epoxy compound: 0.39 part

Polymerization inhibitor (p-methoxyphenol): 0.0007 part

Fluorine-based surfactant (F475, 1% PGMEA solution, manufactured by DIC): 2.50 parts

(Preparation of coloring composition 4) (Examples 47 and 48)

The following components were mixed, dispersed and dissolved to obtain Coloring Composition 4.

Organic solvent (cyclohexanone): 17.12 parts

Epoxy compound (E1): 4.395 parts

· Cyclohexanone solution of the colorant multimer (solid content concentration 12.3%): 24.57 parts

Pigment dispersion (C.I. Pigment Blue 15: 6 dispersion, PGMEA solution, solid concentration 12.8%): 51.40 parts

Polymerization inhibitor (p-methoxyphenol): 0.0007 part

Fluorine-based surfactant (F475, 1% PGMEA solution, manufactured by DIC): 2.50 parts

4. Fabrication of color filter (coloring pattern)

4-1: Fabrication of color filter by photolithography

The colored compositions 1 and 3 prepared above were coated on the undercoat layer of the silicon wafer with the undercoat layer prepared above to form a colored 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 1 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 ° C to form a colored pattern on the undercoat layer of the silicon wafer with the undercoat layer.

The silicon wafer on which the coloring pattern was formed was fixed to a horizontal rotary table by a vacuum chucking method and purified water was supplied from a spray nozzle through a nozzle in a shower shape while rotating the silicon wafer at a rotation speed of 50 rpm by a rotary device, And thereafter spray-dried, and post-baked at 200 캜 for 300 seconds on a hot plate to obtain a transparent pattern (cured film) having a thickness of 1 탆 on a silicon wafer.

Thus, a silicon wafer with a coloring pattern having a coloring pattern (color filter) provided on an undercoat layer of a silicon wafer with an undercoat layer was obtained.

Thereafter, the size of the colored pattern was measured using a measurement SEM "S-9260A" (manufactured by Hitachi High-Technologies Corporation).

Evaluation of pattern formability, development residue, and roughness (color unevenness) was carried out by using a colored pattern having an exposure amount of 1.0 mu m in pattern size.

4-2: Fabrication of color filter by dry etching method

The colored compositions 2 and 4 obtained above were applied on a glass substrate of 7.5 cm x 7.5 cm using a spin coater so that the film thickness became 0.5 m and heated at 200 캜 for 5 minutes using a hot plate , And the coating film was cured to prepare a colored layer. The film thickness of this colored layer was 0.5 mu m.

Subsequently, a positive type photoresist "FHi622BC" (manufactured by Fuji Film Electronics Materials Co., Ltd.) was applied and prebaked at 90 DEG C for 1 minute to form a photoresist layer having a thickness of 0.8 mu m.

Subsequently, the photoresist layer was subjected to pattern exposure at an exposure amount of 350 mJ / cm ² using an i-line stepper (manufactured by Canon Inc.), and the photoresist layer was exposed at a temperature of 90 ° C for 1 minute, Heat treatment was carried out. Thereafter, development processing was performed for one minute with a developing solution "FHD-5" (manufactured by FUJIFILM ELECTRONIC MATERIALS), and further post-baked at 110 DEG C for one minute to form a resist pattern. The size of the resist pattern was formed to be 1.0 μm on one side in consideration of the etching conversion difference (reduction in pattern width due to etching).

Next, the obtained glass substrate was attached to a 200 mm (8 inch) silicon wafer. RF power: 800 W, antenna bias: 400 W, wafer bias: 200 W, The etching was carried out for 80 seconds in the first step of etching at a pressure of 4.0 Pa and a substrate temperature of 50 DEG C under the conditions of CF ₄ : 80 mL / min, O ₂ : 40 mL / min, Ar: 800 mL / Treatment.

Then, in the same etching chamber, the gas species and the flow rate of the mixed gas were set to 500 mL / min (N _{2) in an} RF power of 600 W, an antenna bias of 100 W, a wafer bias of 250 W, an inner pressure of the chamber of 2.0 Pa, (N ₂ / O ₂ / Ar = 10/1/10), O _{2 was} 50 mL / min, and Ar was 500 mL / min, and the second stage etching treatment and overetching treatment were performed for 28 seconds.

After performing the dry etching under the above conditions, the photoresist stripping solution "MS230C" (manufactured by FUJIFILM ELECTRONICS MATERIALS CO., LTD.) Was subjected to peeling treatment at 50 ° C for 120 seconds to remove the resist, thereby forming a green coloring pattern . Further, washing with pure water and spin drying were performed, and dehydration baking treatment was then performed at 100 ° C for 2 minutes. Thus, a color filter was obtained.

5. Evaluation

5-1. Pattern forming property

The obtained color filter was cut out with a glass knife, and its cross-section was observed at a magnification of 15,000 times using a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.) and evaluated according to the following evaluation criteria.

A: A pattern with a line width of 1.0 mu m was formed with good linearity.

B: The pattern with a line width of 1.0 mu m was slightly uneven, but there was no practical problem.

C: Linearity of a pattern with a line width of 1.0 mu m was remarkably bad.

5-2. Development residue

The outside of the formation area (unexposed area) of the colored pattern in the silicon wafer was observed at a magnification of 30,000 times using a scanning electron microscope and evaluated according to the following evaluation criteria.

A: Residues were not observed at all outside the coloring pattern forming area (unexposed area).

B: Residues were slightly observed outside the coloring pattern forming area (unexposed area), but there was no problem in practical use.

C: Residues were remarkably confirmed outside the coloring pattern forming area (unexposed area).

5-3. asperity

The obtained monochromatic color filter (coloring pattern) was provided between the observation lens of the optical microscope and the light source, the light was irradiated toward the observation lens, and the state of the transmitted light was observed by an optical microscope equipped with a digital camera with a magnification of 1000 times . The digital camera installed in the optical microscope was equipped with a CCD of 128 megapixels, and the surface of the film in the transmitted light state was photographed. The photographed image was saved as data (digital image) digitally converted into an 8-bit bitmap format.

In addition, the photographing of the surface of the coating film of the colored pattern was carried out for arbitrarily selected 20 regions. The digitally converted data was obtained by digitizing the captured image as the density distribution of 256 gradations ranging from 0 to 255,

Then, with respect to the stored digital image, the lattice size was divided into lattice shapes so that one lattice size corresponded to 2 mu m square on the actual substrate, and the luminance in one compartment was averaged. In this embodiment, since an image of 1000 times of optical is photographed with a digital camera of 128 million pixels, 2 mu m on the actual substrate is 2 mm on the photographed image, and the image size on the display is 452 mm x 352 mm, The total number of compartments in one area was 39776.

The average luminance of one arbitrary section and all adjacent sections adjacent thereto was measured for the whole section of each area. The average number of significant subdivisions of the total area and the average total number of the significant subdivisions of the total area are 39957 total areas (39776) in each area, (Hereinafter, simply referred to as "ratio"). The smaller the value, the less the color unevenness (roughness) is judged. If the number of significant subdivisions is 800 or less and the ratio is 3% or less, it is judged that there is no problem in practical use.

Evaluation criteria of color unevenness (roughness)

A: Excellent level with a significant subdivision number of less than 500 and less than 2%

B: The number of significant subdivisions is 800 or less, and the ratio is 3% or less (except for the case of A above)

C: at least one of a significant number of divisions greater than 800 and a ratio exceeding 3%, and a level

5-4. Bleaching resistance

The coloring composition was coated on a glass substrate using a spin coater so as to have a film thickness of 0.6 mu m and subjected to heat treatment (prebaking) for 120 seconds using a hot plate at 100 DEG C. [ Subsequently, a heat treatment (post-baking) was performed using a hot plate at 220 캜 for 300 seconds to produce a cured film.

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). Further, differential interference images were observed on a reflection observation (magnification: 50 times) using an OLYMPUS optical microscope BX60.

Subsequently, the film was immersed in an alkali developing solution FHD-5 (manufactured by Fuji Film Electronics Materials Co., Ltd.) for 5 minutes, dried and then subjected to spectroscopic measurement again to determine the transmittance variation before and after the solvent immersion T0-T1 | when the transmittance after immersion was T1) and the film surface were evaluated and evaluated according to the following criteria.

AA: Good When the transmittance variation before and after solvent immersion in the entire region of 300 nm to 800 nm is less than 2%

A: Slightly Good When the transmittance variation before and after solvent immersion in the entire region of 300 nm to 800 nm is 2% or more and less than 5%

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

C: In the entire region of insufficient 300 nm to 800 nm, the transmittance variation before and after the solvent immersion is 10% or more

Hereinafter, the repeating unit of the dye multimer used in the present embodiment is shown.

<Repeating unit 1>

(65)

In the above, X ^- is an anion shown in Tables 1 and 2.

(66)

In the above, X represents the state before the dissociation of the anions shown in Tables 1 and 2.

(67)

In the above, X ^- is an anion shown in Tables 1 and 2.

(68)

In the above, X ^- is an anion shown in Tables 1 and 2.

(69)

In the above, X ^- is an anion shown in Tables 1 and 2.

<Repeating units 2 to 4>

(70)

Anion X

(71)

Photopolymerization initiator:

(72)

Alkali-soluble resin 1: The following structure

(73)

Polymerizable compound

Z1: Ethyleneoxy-modified dipentaerythritol hexaacrylate, NK ester A-DPH-12E (Shin-Nakamura Kagaku)

Z2: dipentaerythritol hexaacrylate, KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

Z3: ethoxylated (4) pentaerythritol tetraacrylate, SR494 (manufactured by Satomar)

Z4: ethoxylated (3) trimethylol propyl acrylate, SR454 (manufactured by Satoromer)

Z5: ethoxylated (6) trimethylol propyl acrylate, SR499 (manufactured by Satomar)

Z6: KAYARAD DPCA-60 (manufactured by Nippon Kayaku Co.)

Z7: tris (2-hydroxyethyl) isocyanurate triacrylate, SR368 (manufactured by Satomar)

Epoxy compound

E1: EHPE 3150, manufactured by Daicel Co., Ltd.

E2: EPICLON 840 (made by DIC)

E3: EPICLON N660 (made by DIC)

[Table 1]

[Table 2]

[Table 3]

[Table 4]

As is clear from the above results, it was found that the coloring composition of the present invention was excellent in discoloration resistance. In addition, it was found that pattern formation property, development residue, and roughness were also excellent. In particular, it was found that the discoloration resistance was remarkably improved in the formulations containing the pigment and the dispersing agent.

Claims (16)

A coloring composition comprising a colorant multimer comprising (a) a repeating unit having a dye structure, and (b) a repeating unit having a repeating unit of 2 to 20 unsubstituted alkyleneoxy chains on the side chain. The method according to claim 1,
Wherein the dye structure is derived from a dye selected from a dipyramethine dye, a triarylmethane dye, a xanthine dye, a cyanine dye and a squarylium dye. The method according to claim 1 or 2,
Wherein the dye multimer further comprises an acid group. The method according to any one of claims 1 to 3,
Wherein the coloring composition further comprises a pigment and a pigment dispersant. The method according to any one of claims 1 to 4,
Wherein the coloring composition further comprises a polymerizable compound and a photopolymerization initiator. The method according to any one of claims 1 to 5,
Wherein the dye multimer is a (meth) acrylic resin. The method according to any one of claims 1 to 6,
(a) the proportion of repeating units having a dye structure is 10 to 35 mol% of the total repeating units constituting the dye multimer. The method according to any one of claims 1 to 7,
(b) the repeating unit having a group consisting of repeating of 2 to 20 unsubstituted alkyleneoxy chains in the side chain is 2 to 20 mol% of the total repeating units constituting the dye multimer. The method according to any one of claims 1 to 8,
Wherein the dye multimer comprises a polymerizable group. The method according to any one of claims 1 to 9,
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 10. A color filter having the cured film according to claim 11. A method for producing a coloring composition, comprising the steps of: applying a coloring composition according to any one of claims 1 to 10 on a support to form a coloring composition layer; exposing the coloring composition layer to a pattern; To form a pattern. A method of manufacturing a color filter, comprising the pattern forming method according to claim 13. A solid-state image pickup element having the color filter obtained by the color filter according to claim 12 or the method for manufacturing a color filter according to claim 14. An image display apparatus having the color filter obtained by the color filter according to claim 12 or the method for manufacturing a color filter according to claim 14.