TW201529754A - Colored composition, cured film using colored composition, color filter, method for forming pattern, method for manufacturing color filter, solid-state image sensing device, and image display device - Google Patents

Abstract

A colored composition, a cured film using the colored composition, a color filter, a method for forming a pattern, a method for manufacturing a color filter, a solid-state image sensing device and an image display device are provided, wherein the colored composition has an excellent discoloration resistance. The colored composition contains a pigment polymer, and the pigment polymer contains a repeating unit (a) having a pigment structure and a repeating unit (b) having a group obtained by repeating 2 to 20 numbers of unsubstituted alkyleneoxy chains at a side chain.

Description

Colored composition and cured film, color filter, and pattern using the same Forming method, method of manufacturing color filter, solid-state image sensor, and image display device

The present invention is directed to a colored composition. More particularly, it relates to a colored composition that is preferably used to form a colored layer of a color filter. Further, there is a cured film, a color filter, a solid-state image sensor, and an image display device using a coloring composition. Further, the present invention relates to a pattern forming method using a coloring composition and a method of producing a color filter.

In recent years, with the development of personal computers, especially large-screen liquid crystal televisions, there has been a tendency for the demand for liquid crystal displays (LCDs), particularly color liquid crystal displays, to increase. In view of the demand for further high image quality, the popularity of organic electroluminescence (EL) displays is also expected. On the other hand, due to the spread of digital cameras and mobile phones with cameras, solid-state imaging devices such as charge-coupled devices (CCD) image sensors Demand has also expanded significantly.

As key elements of such displays or optical components, the use of color filters further increases the requirements for higher image quality and cost down. Such a color filter usually has a coloring layer (pattern) of three primary colors of red (R), green (G), and blue (B), and functions to divide the passed light into three primary colors in a display element or an imaging element. .

Here, in recent years, a dye polymer has been studied as a coloring agent for forming a coloring layer.

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

Patent Document 2 discloses a color-curable composition containing a dye-polymerizable polymer, a pigment, a polymerizable compound, and a photopolymerization initiator.

Patent Document 3 discloses a coloring curable composition containing a dye polymer including a xanthene skeleton as a partial structure of a dye site, a polymerizable compound, a photopolymerization initiator, and an organic solvent.

Patent Document 4 discloses a colored radiation composition comprising a dye polymer and a solvent, which comprises a structural unit obtained by polymerizing a chain transfer agent having a LogP value of 5 or less and having a dye structure.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-213925

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2013-28764

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

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2012-215806

The demand for a coloring composition containing a dye multimer as described above is increasing, and a coloring composition capable of forming a pattern with higher precision is required by recent technological innovation. In particular, in a color hardening composition containing a dye polymer, a coloring composition having more excellent fading resistance is required. The present invention has been made in view of the above circumstances, and an object thereof is to provide a coloring composition which is excellent in fading resistance by using a novel dye polymer.

The inventors of the present invention conducted research based on the above problems, and as a result, found that a coloring composition excellent in fading resistance can be provided by using a dye polymer containing a repeating unit, and the repeating unit has two to 20 repeats. The group of the unsubstituted alkylene oxide chain is completed to complete the present invention.

Specifically, the problem is solved by the following means.

<1> A coloring composition comprising a dye multimer comprising: (a) a repeating unit having a dye structure; (b) having 2 to 20 unsubstituted stretches in a side chain a repeating unit of a group formed by an alkoxy group.

<2> The colored composition according to <1>, wherein the dye structure is derived from a dipyrromethane dye, triarylmethane, or a triarylmethane. Pigments in pigments, xanthene pigments, cyanine pigments, and squarylium pigments.

<3> The colored composition according to <1> or <2>, wherein the dye polymer further has an acid group.

The colored composition according to any one of <1> to <3> wherein the colored composition further comprises a pigment and a pigment dispersant.

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

The colored composition according to any one of <1> to <5> wherein the dye polymer is a (meth)acrylic resin.

The colored composition according to any one of <1> to <6> wherein (a) the ratio of the repeating unit having a dye structure is 10 mol% of all repeating units constituting the dye polymer. 35 moles %.

The colored composition according to any one of <1> to <7> wherein (b) has a group in which 2 to 20 unsubstituted alkylene oxide chains are repeated in the side chain. The ratio of the repeating units is from 2 mol% to 20 mol% of all the repeating units constituting the dye polymer.

The colored composition according to any one of <1> to <8> wherein the dye multipolymer comprises a polymerizable group.

<10> The colored 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 which is recorded in any one of <1> to <10> The colored composition of the load is hardened.

<12> A color filter comprising the cured film according to <11>.

<13> A pattern forming method comprising the steps of: applying the coloring composition according to any one of <1> to <10> to a support to form a colored composition layer; and coloring the composition The step of exposing the layer in a pattern; and developing the unexposed portion to form a colored pattern.

<14> A method of producing a color filter, comprising the pattern forming method according to <13>.

<15> A solid-state imaging device comprising the color filter according to <12> or a color filter obtained by the method for producing a color filter according to <14>.

<16> An image display device comprising the color filter according to <12> or a color filter obtained by the method for producing a color filter according to <14>.

According to the present invention, a coloring composition excellent in fading resistance can be provided. Further, a cured film using a colored composition, a color filter, a pattern forming method, a method of producing a color filter, a solid-state image sensor, and an image display device can be provided.

Hereinafter, the contents of the present invention will be described in detail. In the specification of the present application, "~" is used in the sense that the numerical values described before and after are included as the lower limit and the upper limit. Further, the term "organic EL element" as used in the present invention means an organic electroluminescence element.

In the present specification, the term "total solid content" means the total mass of the components obtained by removing the solvent from the total composition of the coloring composition. Moreover, it means a solid component at 25 °C.

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

In addition, the term "radiation" in the present specification means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (Extreme Uitraviolet (EUV) light), an X-ray, an electron beam, or the like. Further, the term "light" as used in the present invention means actinic ray or radiation. In the present specification, the term "exposure" is used to describe not only the ultraviolet light, the X-ray, the EUV light, etc., which are represented by mercury lamps or excimer lasers, but also the use of particle beams such as electron beams and ion beams. Also included in the exposure.

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

In addition, in this specification, "monomer" and "monomer" have the same meaning. The monomer in the present specification means a compound which is distinguished from an oligomer and a polymer and has 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 that participates in a polymerization reaction.

In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.

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

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

In the present specification, the weight average molecular weight and the number average molecular weight are defined by polystyrene-converted values obtained by GPC measurement. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, by using HLC-8220 (manufactured by Tosoh Corporation) and using TSKgel Super AWM-H (Dongcao) Manufactured, 6.0 mm ID × 15.0 cm) As a column, a solution of 10 mmol/L of lithium bromide N-methylpyrrolidone (NMP) was used as a solution.

The colored composition of the present invention contains a dye multimer comprising: (a) a repeating unit having a dye structure, and (b) having 2 to 20 unsubstituted alkylene oxides in the side chain. A repeating unit of a group formed by a base chain.

The fading resistance can be improved by blending such a group of a repeating alkoxy chain. The reason is presumed to be that if the number of alkoxy chains exceeds 20, the hydrophilicity is too high, and when pattern development is performed, fading is likely to occur. In the present invention, appropriate fading resistance can be successfully achieved by adjusting the number of alkylene oxide chains.

Further, unlike the dye polymer, the fading resistance is remarkably improved by blending the pigment and the pigment dispersant. Although the reason is presumed, it is presumed that the reason is that the pigment dispersant interacts with a group obtained by repeating an alkoxy chain.

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

<Pigment Polymer>

The dye multimer used in the present invention includes (a) a repeating unit having a dye structure (hereinafter sometimes referred to as "(a) repeating unit") and (b) having 2 to 20 unsubstituted in the side chain. A repeating unit of a group derived from an alkoxy group (hereinafter sometimes referred to as "(b) repeating unit"). (a) the repeating unit and (b) the repeating unit may be contained alone or in combination of two or more.

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

Hereinafter, the structure of the skeleton of the dye polymer, the dye structure, and the counter anion of the dye structure contained as needed will be described.

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

The skeleton structure of the (a) repeating unit is not particularly limited, and the general formula (A) and the general formula (B) which are shown in Paragraph No. 0276 to Paragraph No. 0304 of Japanese Patent Laid-Open No. 2013-28764 and At least one of the constituent units represented by the general formula (C) Each of them is a skeleton, and is preferably a dye polymer represented by the formula (D). The description of Paragraph No. 0276 to Paragraph No. 0304 of Japanese Patent Laid-Open No. 2013-28764 is incorporated into the specification of the present application.

In the present invention, it is preferred to include a dye polymer represented by the following formula (A).

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

<<<Composition unit represented by the general formula (A)>>>

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

The general formula (A) will be described in detail below.

In the formula (A), X ₁ represents a linking group formed by polymerization. That is, it means a part which forms a repeating unit corresponding to the main chain formed by the polymerization reaction. Furthermore, the part indicated by two * is a repeating unit. X _{1 is} a linking group formed of a known polymerizable monomer, and is not particularly limited, and particularly preferably a linking group represented by the following (XX-1) to (X-24). More preferably, it is selected from the (meth)acrylic connecting chain represented by (XX-1) and (XX-2), and the styrene-based connecting chain represented by (XX-10) to (XX-17), (XX) Further, the ethylene-based linking chain represented by -18) and (XX-19) and (XX-24) is more preferably selected from (meth)acrylic linkages represented by (XX-1) and (XX-2). The chain, the styrene-based linking chain represented by (XX-10) to (XX-17), and the ethylene-based linking chain represented by (XX-24) are particularly preferably (XX-1) and (XX-2). The (meth)acrylic linking chain represented by the above and the styrene-based linking chain represented by (XX-11).

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

[Chemical 2]

[Chemical 3]

In the formula (A), L ₁ represents a single bond or a divalent linking group. The divalent linking group in the case where L ₁ represents a divalent linking group, and represents a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (for example, a methylene group, an exoethyl group, a trimethylene group, a propyl group, a butyl group or the like, a substituted or unsubstituted extended aryl group having 6 to 30 carbon atoms (e.g., a phenyl group, a naphthyl group, etc.), a substituted or unsubstituted heterocyclic linker, -CH=CH -, -O-, -S-, -C(=O)-, -CO ₂ -, -NR-, -CONR-, -O ₂ C-, -SO-, -SO ₂ - and these Two or more linking groups formed by joining. Further, L _{1 is} also preferably a structure including an anion. L _{1 is more} preferably a single bond or an alkyl group, and further preferably a single bond or -(CH ₂ )n- (n is an integer of 1 to 5). Here, R each independently represents 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), Dyel represents a dye structure derived from a dye compound described later.

The dye multipolymer having a structural unit represented by the general formula (A) can be synthesized by the following method: (1) a method of synthesizing a monomer having a dye residue by addition polymerization; (2) by a method of (2) A polymer having a highly reactive functional group such as an isocyanate group, an acid anhydride group or an epoxy group, and a dye having a functional group (hydroxyl group, primary amino group or secondary amine group, carboxyl group, etc.) capable of reacting with a highly reactive group The method of reaction.

A well-known addition polymerization (radical polymerization, anionic polymerization, cationic polymerization) can be applied to the addition polymerization, and in particular, in the case of synthesis by radical polymerization, the reaction conditions can be made stable without decomposing the dye structure. Therefore, it is better. Well-known reaction conditions can be applied to the radical polymerization. That is, the dye polymer used in the present invention is preferably an addition polymer.

In the present invention, the dye polymer having the constituent unit represented by the formula (A) in the present invention is preferably obtained by radical polymerization using a dye monomer having an ethylenically unsaturated bond. Free radical polymer.

<<Pigment structure>>

The dye structure used in the present invention is not particularly limited, and a known dye structure can be employed. The dye structure used in the present invention is preferably a dye structure which usually contains a cationic moiety in the molecule.

Specific examples thereof include a dye structure derived from a dye selected from the group consisting of dipyrromethene dye, carbonium dye (diphenylmethane dye, triarylmethane dye, xanthene dye, acridine dye, etc.), polymethine Base pigment (oxyquinone pigment, merocyanine pigment, Avon) a pigment in a base dye, a styrene-based dye, a cyanine dye, a squaraine sputum dye, a ketoxime dye, or the like, a phthalocyanine dye, and a metal complex dye.

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

Among these dye structures, a dye structure derived from a pigment selected from the group consisting of a dipyrromethene dye, a carbonium dye, and a polymethine dye is preferred from the viewpoint of color characteristics, and more preferably selected from the viewpoint of color characteristics. The pigment structure of the pigment in the dipyrromethene dye, the triarylmethane dye, the xanthene pigment, the cyanine pigment, and the squaraine sputum pigment is preferably derived from a dipyrromethene pigment and an oxygen The pigment structure of the pigment in the anthraquinone pigment is particularly preferably a pigment structure derived from a xanthene pigment. When such a cation having a dye structure is used, heat resistance and light resistance tend to be further improved.

Specific pigment compounds that can form a pigment structure are described in "New Dye Handbook" (Organic Synthetic Chemistry Association; Maruzen, 1970), "Color Index" (The Society of Dyers) And colourists)), "Pigment Handbook" (Dahe Yuan Hebian; Lecture Society, 1986).

A particularly preferred coloring matter (pigment compound) in which a dye structure can be formed in a cation having a dye structure is described in detail.

<<<Dipyrromethene pigment>>>

One of the aspects of the dye structure of the present invention is a dipyrromethene dye structure shown below.

The dipyrromethene dye of the present invention is preferably a dipyrromethene compound, and a dipyrromethene obtained from a dipyrromethene compound and a metal or metal compound. Metal complex compound. A site of the dipyrromethene dye structure is bonded to the polymer.

Further, in the present invention, a compound containing a dipyrromethene structure is referred to as a dipyrromethene compound, and a compound containing a dipyrromethene structure is compounded on a metal or a metal compound. It is a dipyrromethene metal complex compound.

The dipyrromethene metal complex compound is preferably a dipyrromethene metal complex compound obtained from a dipyrromethene compound represented by the following formula (M) and a metal or a metal compound, and the mutual In the preferred embodiment, the dipyrromethene metal complex compound represented by the following formula (7) or the dipyrromethene metal represented by the following formula (8) The complex compound is more preferably a dipyrromethene metal complex compound represented by the formula (8).

(a dipyrromethene metal complex compound obtained by a dipyrromethene compound represented by the general formula (M) and a metal or a metal compound, and a tautomer thereof)

One of the preferable aspects of the pigment structure is a complex containing a compound represented by the following formula (M) (dipyrromethene compound) or a tautomer thereof, which is coordinated to a metal or a metal compound ( Hereinafter, the dye structure is appropriately referred to as "specific complex". In the present invention, the following compound forms a cationic structure, and a metal such as zinc bonded to a nitrogen atom of the formula (M) may form a cationic structure.

[Chemical 4]

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

The introduction site when the compound represented by the formula (M) is introduced into the structural unit represented by the formula (A) is not particularly limited, and in terms of the suitability for synthesis, it is preferably R ⁴ ~. introducing either a portion of R ^9, more preferably in R ^4, R ^6, R ⁷ and R ⁹ according to any one of the introduction, and further is excellent in any one of R ⁴ and R ⁹ is introduced into one.

In the case where R ⁴ to R ⁹ in the formula (M) represent a monovalent substituent, the substituents listed in the item of the substituent group A to be described later may be mentioned.

A price of the general formula (M) R ⁴ ~ R ⁹ substituent represented over time as the case may be further substituted with a group, can have more R ~ R ^{9 4} described substituent having 2 In the case of more than one substituent, the 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 formula (M) may be independently bonded to each other to form a saturation of 5 members, 6 members or 7 members. Ring or unsaturated ring. Wherein R ⁴ and R ^{9 are} not bonded to each other to form a ring. In the case where the ring of the 5, 6 and 7 members formed is a group which may be further substituted, it may be substituted with a substituent described in R ⁴ to R ⁹ , and may have two or more substituents. In the case of substitution, the 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 formula (M) are each independently bonded to each other to form a 5-member or a 6-member having no substituent or In the case of a saturated or unsaturated ring of 7 members, the saturated or unsaturated ring of 5, 6 or 7 members having no substituent may, for example, be a pyrrole ring, a furan ring, a thiophene ring or a pyrazole ring. The imidazole ring, the triazole ring, the oxazole ring, the thiazole ring, the pyrrolidine ring, the piperidine ring, the cyclopentene ring, the cyclohexene ring, the benzene ring, the pyridine ring, the pyrazine ring and the pyridazine ring are preferably exemplified. Benzene ring or pyridine ring.

R ¹⁰ in the 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 have the same meanings as those of the halogen atom, the alkyl group, the aryl group and the heterocyclic group of the substituent group A described later, and the preferred range thereof is also the same.

In the case where the alkyl group, the aryl group and the heterocyclic group in the case where R ¹⁰ represents an alkyl group, an aryl group or a heterocyclic group is a group which may be further substituted, it may also be in the group of the substituent group A described later. The substituents described are substituted, and when substituted with two or more substituents, the substituents may be the same or different.

~Metal or metal compound~

The specific complex of the present invention is a complex compound in which the dipyrromethene compound represented by the above formula (M) or a tautomer thereof is coordinated to a metal or a metal compound.

Here, the metal or the metal compound may be any one as long as it is a metal or a metal compound capable of forming a complex, including a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide or a divalent. Metal chloride. Metal or metal compounds such as zinc (Zn), magnesium (Mg), bismuth (Si), tin (Sn), rhodium (Rh), platinum (Pt), palladium (Pd), molybdenum (Mo), manganese (Mn) Metals such as lead (Pb), copper (Cu), nickel (Ni), cobalt (Co), and iron (Fe) include metals such as AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ , and GeCl ₂ . Chloride, metal oxide such as TiO or VO, metal hydroxide such as Si(OH) ₂ .

Among these, from the viewpoints of stability, spectral characteristics, heat resistance, light resistance, and workability of the complex, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, and preferably, Co, TiO or VO, and more preferably Zn, Mg, Si, Pt, Pd, Cu, Ni, Co or VO, particularly preferably Zn.

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

A preferred range of the specific complex of the present invention is in the range wherein, in the 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 or a decyl group. , hydroxy, cyano, alkoxy, aryloxy, heterocyclic oxy, fluorenyl, alkoxycarbonyl, aminecarbamyl, amine, anilino, heterocyclic amine, carboguanamine, guanidine Base, oximine, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, azo, alkylthio, arylthio, heterocyclic thio, alkylsulfonyl, aryl a sulfoyl group or a phosphinoyl amino group; R ⁵ and R ⁸ are each independently 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 nitrate Alkoxy group, alkoxy group, aryloxy group, heterocyclic oxy group, fluorenyl group, alkoxycarbonyl group, aryloxycarbonyl group, amine mercapto group, quinone imine group, alkoxycarbonylamino group, sulfonylamino group, An azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group or an aminesulfonyl group; and R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom or an alkane Base, alkenyl, aryl, heterocyclic group , decyl, hydroxy, cyano, alkoxy, aryloxy, heterocyclooxy, decyl, alkoxycarbonyl, amine carbaryl, anilino, carbamide, ureido, ruthenium Alkyloxycarbonylamino, sulfonylamino, azo, alkylthio, arylthio, heterocyclic thio, alkylsulfonyl, arylsulfonyl, sulfonyl or phosphine a mercaptoamine group; R ¹⁰ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group; and the metal or metal compound is Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO Or V=O.

A more preferred range of the specific complex of the present invention is the following range: in the 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 or a cyano group. , mercapto, alkoxycarbonyl, amine carbhydryl, amine, heterocyclic amine, carboguanamine, guanidinosyl, oximine, alkoxycarbonylamino, aryloxycarbonylamino, a sulfonylamino group, an azo group, an alkylsulfonyl group, an arylsulfonyl group or a phosphoniumphosphonium group; and R ⁵ and R ⁸ are each independently an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, Cyano, nitro, fluorenyl, alkoxycarbonyl, aryloxycarbonyl, aminemethanyl, quinone imine, alkylsulfonyl, arylsulfonyl or aminesulfonyl; R ⁶ and R ^{7 is} independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a decyl group, an alkoxycarbonyl group, an amine carbaryl group, a carboguanamine group, a guanidino group, a quinone group. , alkoxycarbonylamino, sulfonylamino, alkylthio, arylthio, heterocyclic thio, alkylsulfonyl, arylsulfonyl or sulfonyl; R ¹⁰ is a hydrogen atom, halogen Atom, alkyl, aryl or heterocyclic group; metal or metal compound The substance is Zn, Mg, Si, Pt, Pd, Cu, Ni, Co or V=O.

A particularly preferred range of the specific complex of the present invention is the following range: in the formula (M), R ⁴ and R ⁹ are each independently a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amine group, or a heterocyclic ring. Amino, carboguanamine, guanidinosyl, oxime imido, alkoxycarbonylamino, sulfonylamino, azo, alkylsulfonyl, arylsulfonyl or phosphinium decylamine R ⁵ and R ⁸ are each independently alkyl, aryl, heterocyclyl, cyano, fluorenyl, alkoxycarbonyl, aminemethanyl, alkylsulfonyl or arylsulfonyl; 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; and the metal or metal compound is Zn, Cu, Co, or V. =O.

Further, the dipyrromethene metal complex compound represented by the general formula (7) or the general formula (8) which will be described in detail below is also a particularly preferable aspect of the dipyrromethene dye.

(dipyrromethene metal complex compound represented by the formula (7))

One of preferable aspects of the dye structure in the cation having a dye structure is a dye structure derived from a dipyrromethene metal complex compound represented by the following formula (7). In the present invention, the following compound forms a cationic structure, and for example, Ma of the general formula (7) forms a metal cation structure such as zinc.

(In the formula (7), R ⁴ to R ⁹ each independently represent 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. Ma represents a metal atom or a metal. a compound. X ¹ represents a group which may be bonded to Ma, and X ² represents a group which neutralizes the charge of Ma, and X ¹ and X ² may be bonded to each other and form a 5 member, 6 member or 7 member with Ma. Ring, wherein R ⁴ and R ^{9 are} not bonded to each other to form a ring)

Further, the dipyrromethene metal complex compound represented by the formula (7) includes a tautomer.

When the dipyrromethene metal complex compound represented by the formula (7) is introduced into the structural unit represented by the formula (A), the introduction site is not particularly limited, and the aspect of suitability is synthesized. In particular, it is preferably introduced at any one of R ⁴ to R ⁹ , more preferably introduced on any of R ⁴ , R ⁶ , R ⁷ and R ⁹ , and more preferably any of R ⁴ and R ⁹ . Import on one.

When the cation having a dye structure has an alkali-soluble group, a method of introducing an alkali-soluble group can be used: one or two or more of R ⁴ to R ¹⁰ , X ¹ and X ² in the formula (7). A method having an alkali-soluble group in a substituent. 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 further preferably any of R ⁴ and R ⁹ . .

The dipyrromethene metal complex compound represented by the formula (7) may have a functional group other than the alkali-soluble group, as long as the effects of the present invention are not impaired.

Formula (7) R ⁴ ~ R ⁹ in the general formula R ⁴ ~ R ⁹ are the same meaning (M) of the, preferred aspects are also the same.

In the formula (7), Ma represents a metal atom or a metal compound. The metal atom or the metal compound may be any one, including a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide or a divalent, as long as it is a metal atom or a metal compound capable of forming a complex. Metal chloride.

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

Among these, the metal atom or the metal compound is preferably Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn from the viewpoints of stability, spectral characteristics, heat resistance, light resistance, and workability of the complex. , Cu, Ni, Co, TiO and V=O, more preferably Zn, Mg, Si, Pt, Pd, Cu, Ni, Co and V=O, and further preferably Zn, Co, V=O and Cu, especially Good for Zn.

Further, in the 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 one as long as it is a group which can be bonded to Ma, and specific examples thereof include water, alcohol (for example, methanol, ethanol, propanol), and the like. The compound described in [1] Sakaguchi Takeshi, Ueno Jingping (1995, Nanjiangtang), [2] (1996), [3] (1997), etc.). Among them, in terms of production, water, a carboxylic acid compound, and an alcohol are preferable, and water or a carboxylic acid compound is more preferable.

In the general formula (7), the "group neutralizing the charge of Ma" represented by X ² may, for example, be a halogen atom, a hydroxyl group, a carboxylic acid group, a phosphoric acid group or a sulfonic acid group. In general, a halogen atom, a hydroxyl group, a carboxylic acid group, or a sulfonic acid group is preferred, and a hydroxyl group or a carboxylic acid group is more preferred.

In the formula (7), X ¹ and X ² may be bonded to each other and form a ring of 5 members, 6 members or 7 members together with Ma. The formed ring of 5 members, 6 members and 7 members may be a saturated ring or an unsaturated ring. Further, the rings of 5 members, 6 members, and 7 members may be composed only of carbon atoms, and may form a hetero ring containing at least one atom selected from a nitrogen atom, an oxygen atom or/and a sulfur atom.

In a preferred embodiment of the compound represented by the 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 as described in the description of R ¹⁰ . In a preferred embodiment, 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, and X ¹ and X ² may be bonded to each other to form a 5-member or 6-member ring.

(dipyrromethene metal complex compound represented by the formula (8))

One of the preferable aspects of the dye structure in the cation having a dye structure is a dye structure derived from a dipyrromethene metal complex compound represented by the following formula (8). In the present invention, the following compound forms a cationic structure, and for example, Ma of the general formula (8) forms a metal cation structure such as zinc.

[Chemical 6]

(In the 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 ring. Amino groups: R ¹² to R ¹⁵ each independently represent a hydrogen atom or a substituent. R ¹⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. Ma represents a metal atom or a metal compound. X ² and X ³ Each independently represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group or an arylsulfonyl group), a nitrogen atom, an oxygen atom or a sulfur atom. ¹ and Y ² each independently represent NR ^c (R ^c represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group or an arylsulfonyl group), a nitrogen atom or a carbon. Atom. R ¹¹ and Y ¹ may also be bonded to each other to form a ring of 5 members, 6 members or 7 members, and R ¹⁶ and Y ² may be bonded to each other to form a ring of 5 members, 6 members or 7 members. X ¹ Represents a group that can be bonded to Ma, and a represents 0, 1, or 2)

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

The site in which the dipyrromethene metal complex compound represented by the formula (8) is introduced into the structural unit represented by the formula (A) is not particularly limited as long as the effects of the present invention are not impaired. Preferably, it is any one of R ¹¹ to R ¹⁷ , X ¹ and Y ¹ to Y ² . In the above, in terms of the suitability for synthesis, it is preferably introduced on any of R ¹¹ to R ¹⁶ and X ¹ , more preferably on any of R ¹¹ , R ¹³ , R ¹⁴ and R ¹⁶ . The inserted aspect is preferably a pattern inserted on either of R ¹¹ and R ¹⁶ .

When the cation having a dye structure has an alkali-soluble group, one or two or more substituents of R ¹¹ to R ¹⁷ , X ¹ and Y ¹ to Y ² in the formula (8) may be used. A method of alkali soluble groups. 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 further preferably any of R ¹¹ and R ¹⁶ . .

The dipyrromethene metal complex compound represented by the formula (8) may have a functional group other than the alkali-soluble group, as long as the effects of the present invention are not impaired.

In the formula (8), R ¹² to R ¹⁵ have the same meanings as R ⁵ to R ⁸ in the formula (M), and preferred embodiments are also the same. R ¹⁷ has the same meaning as R ¹⁰ in the formula (M), and the preferred embodiment is also the same. Ma has the same meaning as Ma in the general formula (7), and the preferred range is also the same.

More specifically, in R ¹² to R ¹⁵ in the formula (8), R ¹² and R ^{15 are} preferably an alkoxycarbonyl group, an aryloxycarbonyl group, an aminomethyl group, an alkylsulfonyl group or an aryl group. Sulfonyl, nitrile, oxime imido or amine carbaryl sulfonyl, more preferably alkoxycarbonyl, aryloxycarbonyl, amine carbaryl, alkyl sulfonyl, nitrile, quinone Alkyl sulfonyl sulfhydryl, and more preferably alkoxycarbonyl, aryloxycarbonyl, aminemethanyl, nitrile, oxime imido, amine carbaryl sulfonyl, especially alkoxy Carbonyl group, aryloxycarbonyl group, amine carbenyl group.

R ¹³ and R ^{14 are} preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and more preferably a substituted or unsubstituted alkane. A substituted, unsubstituted or unsubstituted aryl group. Here, specific examples of the more preferable alkyl group, aryl group and heterocyclic group are similarly exemplified by R ⁶ and R ⁷ of the formula (M).

In the formula (8), R ¹¹ and R ¹⁶ represent an alkyl group (preferably a linear, branched or cyclic alkyl group having a carbon number of 1 to 36, more preferably a carbon number of 1 to 12, such as a methyl group, Ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantane a base group, an alkenyl group (preferably a carbon number of 2 to 24, more preferably an alkenyl group having 2 to 12 carbon atoms, such as a vinyl group, an allyl group, a 3-buten-1-yl group) or an aryl group. An aryl group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms, such as a phenyl group or a naphthyl group, or a heterocyclic group (preferably having a carbon number of 1 to 24, more preferably a carbon number of 1 to 12) a cyclic group such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 2-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotrienyl Zin-1-yl), alkoxy (preferably alkoxy having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, a hexyloxy group, a 2-ethylhexyloxy group, a dodecyloxy group, a cyclohexyloxy group, an aryloxy group (preferably an aryloxy group having a carbon number of 6 to 24, more preferably a carbon number of 1 to 18). For example, phenoxy, naphthyloxy), alkylamino ( Preferred are alkylamino groups having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms, such as methylamino, ethylamino, propylamino, butylamino, hexylamino, 2-B Hexylamino group, isopropylamino group, tert-butylamino group, third octylamino group, cyclohexylamino group, N,N-diethylamino group, N,N-dipropylamino group, N,N-dibutylamino, N-methyl-N-ethylamino), arylamine (preferably an arylamino group having a carbon number of 6 to 36, more preferably a carbon number of 6 to 18) , for example, a phenylamino group, a naphthylamino group, an N,N-diphenylamino group, an N-ethyl-N-phenylamino group, or a heterocyclic amine group (preferably having a carbon number of 1 to 24, More preferably, it is a heterocyclic amino group having 1 to 12 carbon atoms, such as 2-aminopyrrolyl, 3-aminopyrazolyl, 2-aminopyridyl, or 3-aminopyridyl.

In the above, 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 or an aromatic group. The group or the heterocyclic group is more preferably an alkyl group, an alkenyl group or an aryl group, and particularly preferably an alkyl group.

In the formula (8), 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 amine represented by R ¹¹ and R ¹⁶ When the group is a group which may be further substituted, it may be substituted with a substituent described in the section of the substituent group A to be described later, and when substituted with two or more substituents, the substituents may be the same. It can also be different.

In the formula (8), X ² and X ³ each independently represent an NR, a nitrogen atom, an oxygen atom or a sulfur atom. Here, R represents a hydrogen atom or an alkyl group (preferably a linear, branched or cyclic alkyl group having a carbon number of 1 to 36, more preferably a carbon number of 1 to 12, such as a methyl group, an ethyl group, or a propyl group. , isopropyl, butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), alkenyl (preferably a carbon number of 2 to 24, more preferably an alkenyl group having 2 to 12 carbon atoms, such as a vinyl group, an allyl group, a 3-buten-1-yl group) or an aryl group (preferably a carbon number of 6~) 36. More preferably, it is an aryl group having 6 to 18 carbon atoms, such as a phenyl group or a naphthyl group, and a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, for example, 2) -thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl a sulfhydryl group (preferably a fluorenyl group having a carbon number of 1 to 24, more preferably a carbon number of 2 to 18, such as an ethyl fluorenyl group, a trimethyl ethane group, a 2-ethylhexyl group, a benzamidine group, or a ring. Alkyl sulfonyl group, preferably an alkylsulfonyl group having a carbon number of 1 to 24, more preferably a carbon number of 1 to 18, such as methylsulfonyl, ethylsulfonyl, or isopropyl Sulfonyl, cyclohexylsulfonate Anthracenyl) or arylsulfonyl (preferably, an arylsulfonyl group having a carbon number of 6 to 24, more preferably a carbon number of 6 to 18, such as a phenylsulfonyl group or a naphthylsulfonyl group).

In the formula (8), Y ¹ and Y ² each independently represent NR ^c , a nitrogen atom or a carbon atom, and R ^c has the same meaning as R ² and X ³ , and the preferred embodiment is also the same.

In the formula (8), R ¹¹ and Y ¹ may be bonded to each other and form a 5-membered ring together with a carbon atom (for example, a cyclopentane ring, a pyrrolidine ring, a tetrahydrofuran ring, a dioxolane ring, or a tetrahydrogen group). Thiophene ring, pyrrole ring, furan ring, thiophene ring, anthracene ring, benzofuran ring, benzothiophene ring), 6-membered ring (eg cyclohexane ring, piperidine ring, piperazine ring, morpholine ring, four) Hydropyran ring, dioxane ring, pentamethylene sulfide ring, dithiane ring, benzene ring, piperidine ring, piperazine ring, pyridazine ring, quinoline ring, quinazoline ring), or 7 Member ring (eg cycloheptane ring, hexamethyleneimine ring).

In the formula (8), R ¹⁶ and Y ² may be bonded to each other and form a 5-membered ring together with a carbon atom (for example, a cyclopentane ring, a pyrrolidine ring, a tetrahydrofuran ring, a dioxolane ring, or a tetrahydrogen group). Thiophene ring, pyrrole ring, furan ring, thiophene ring, anthracene ring, benzofuran ring, benzothiophene ring), 6-membered ring (eg cyclohexane ring, piperidine ring, piperazine ring, morpholine ring, four) Hydropyran ring, dioxane ring, pentamethylene sulfide ring, dithiane ring, benzene ring, piperidine ring, piperazine ring, azine ring, quinoline ring, quinazoline ring), or 7 Member ring (eg cycloheptane ring, hexamethyleneimine ring).

In the general formula (8), when the ring of 5 members, 6 members, and 7 members formed by bonding R ¹¹ and Y ¹ and R ¹⁶ and Y ^{2 is} a ring which may be substituted, it may be substituted as described later. The substituents described in the subgroup A are substituted, and when substituted with two or more substituents, the substituents may be the same or different.

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

Here, the stereo parameter -Es' value is a parameter indicating the stereoscopic expansion of the substituent, and the literature is used (JA Macphee et al., "Tetrahedron", Vol. 34, pp3553 to pp3562, Fujita The -Es' value revealed in the cod, ed., 107, Structural Activity Correlation and Drug Design, issued February 20, 1986 (Chemical Fellow).

In the formula (8), X ¹ represents a group which may be bonded to Ma, and specific examples thereof are the same as those of X ¹ in the formula (7), and preferred embodiments are also the same.

a represents 0, 1, or 2.

In a preferred embodiment of the compound represented by the 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 formula (M), and R ¹⁷ is In a preferred embodiment described in the description of R ¹⁰ in the formula (M), Ma is Zn, Cu, Co or V=O, X ² is NR (R is a hydrogen atom, an alkyl group), a nitrogen atom or an 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, and X ¹ is a group bonded via an oxygen atom, and a is 0 or 1. R ¹¹ and Y ¹ may also be bonded to each other to form a 5- 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.

In a more preferable aspect of the compound represented by the formula (8), R ¹² to R ¹⁵ are each independently a preferred aspect described in the description of R ⁵ to R ⁸ in the compound represented by the formula (M). R ¹⁷ is a preferred embodiment described in the description of R ¹⁰ in the formula (M), wherein 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 is} independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group or an alkylamino group, and X ¹ is a group bonded via an oxygen atom, and a is 0 or 1. R ¹¹ and Y ¹ may also be bonded to each other to form a 5- 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.

From the viewpoint of the coloring power, the molar absorption coefficient of the dipyrromethene metal complex compound represented by the general formula (7) and the general formula (8) is preferably as high as possible. Further, from the viewpoint of improvement in color purity, the maximum absorption wavelength λmax is preferably 520 nm to 580 nm, and more preferably 530 nm to 570 nm. Within this range, a color filter having good color reproducibility can be produced using the colored composition of the present invention.

Further, with respect to the absorbance at 450 nm, the dye having a dye structure derived from a dipyrromethene dye preferably has an absorbance at a maximum absorption wavelength (λmax) of 1,000 or more, more preferably 10,000 or more, and still more preferably 100,000 or more. . When the ratio is within this range, when a blue color filter is specifically produced using the colored composition of the present invention, a color filter having a higher transmittance can be formed. Furthermore, the maximum absorption wavelength and the Mohr absorption coefficient are by the spectrophotometer card (Cary) 5 (Watt) It is manufactured by Varian).

From the viewpoint of solubility, the melting point of the dipyrromethene metal complex compound represented by the general formula (7) and the general formula (8) is preferably not too high.

The dipyrromethene metal complex compound represented by the formula (7) and the formula (8) can be used in the specification of U.S. Patent No. 4,774,339, the specification of U.S. Patent No. 5,433,896, and the Japanese Patent Laid-Open No. 2001-240761. Japanese Patent Laid-Open Publication No. 2002-155052, Japanese Patent No. 3614586, "Aust.J. Chem" (1965, 11, 1835-1845), JH Boger, etc. It is synthesized by a method described in Heteroatom Chemistry (Vol. 1, No. 5, 389 (1990)). Specifically, the method described in paragraphs 0131 to 0157 of JP-A-2008-292970 can be applied.

Specific examples of the dipyrromethene dye are shown below, but the present invention is not limited thereto. Further, in the formula, X represents an anion. In the present invention, any hydrogen atom of the following dye structure is bonded to the polymer skeleton.

[Chemistry 7]

In the specific examples, from the viewpoints of color characteristics and heat resistance, (PM-4), (PM-7), and (PM-8) are preferable, and (PM-8) is more preferable.

<<<Carbon pigment>>>

Among the carbonium pigments, a triarylmethane dye or a xanthene pigment is preferred.

(triarylmethane pigment)

One of the aspects of the cation having a dye structure of the present invention is a partial structure derived from a triarylmethane pigment (triarylmethane compound). The dye has a partial structure derived from a compound represented by the following formula (TP) (triarylmethane compound) as a dye structure. The triarylmethane compound in the present invention is a generic term for a compound having a dye structure containing a triarylmethane skeleton in a molecule.

General formula (TP)

(In the formula (TP), Rtp ¹ to Rtp ⁴ each independently represent a hydrogen atom, an alkyl group or an aryl group. Rtp ⁵ represents a hydrogen atom, an alkyl group, an aryl group or NRtp ⁹ Rtp ¹⁰ (Rtp ⁹ and Rtp ¹⁰ represent hydrogen) Atom, an alkyl group or an aryl group. Rtp ⁶ , Rtp ⁷ and Rtp ⁸ represent a substituent. a, b and c represent an integer of 0 to 4. When a, b and c are 2 or more, Rtp ⁶ , Rtp ⁷ and Rtp ⁸ may also be bonded to each other to form a ring. X ^- represents an anionic structure. In the absence of X ^- , at least one of Rtp ¹ to Rtp ⁸ contains an anion)

For the preferred range and specific examples of the compound represented by the formula (TP), reference is made to the description of Paragraph No. 0170 - Paragraph No. 0178 of JP-A-2013-28764, the contents of which are incorporated herein by reference. In the manual.

The introduction site when the compound represented by the formula (TP) is introduced into the structural unit represented by the formula (A) is not particularly limited, and it is preferably introduced at any of Rtp ¹ to Rtp ¹⁰ .

(xanthene pigment)

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

(In the general formula (J), R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represent a hydrogen atom or a monovalent substituent, R ⁸⁵ each independently represents a monovalent substituent, and m represents an integer of 0 to 5. X ^- represents an anionic structure. In the absence of X ^- , at least one of R ⁸¹ to R ⁸⁵ contains an anion)

The introduction site when the compound represented by the formula (J) is introduced into the structural unit represented by the formula (A) is not particularly limited, and it is preferred to introduce it at any of R ⁸¹ to R ⁸⁵ .

The substituents which may be taken from R ⁸¹ to R ⁸⁴ and R ⁸⁵ in the formula (J) are the same as those exemplified in the item of the substituent group A to be described later.

In the general formula (J), R ⁸¹ and R ⁸² , R ⁸³ and R ⁸⁴ , and R ⁸⁵ in the case where m is 2 or more may be independently bonded to each other to form a saturation of 5 members, 6 members or 7 members. Ring or unsaturated ring of 5, 6 or 7 members. In the case where the ring of 5, 6 or 7 members formed is a group which may be further substituted, it may be substituted with a substituent described in R ⁸¹ to R ⁸⁵ , and may have two or more substituents. In the case of substitution, the substituents may be the same or different.

In the general formula (J), R ⁸¹ and R ⁸² , R ⁸³ and R ⁸⁴ , and R ⁸⁵ in the case where m is 2 or more are each independently bonded to each other to form a 5-member, 6 having no substituent. In the case of a saturated ring of 5 or 6 members, or an unsaturated ring of 5 members, 6 members, and 7 members, a saturated ring of 5 members, 6 members, and 7 members without a substituent or 5 members, 6 members, and 7 members. Examples of the unsaturated ring include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, a piperidine ring, a cyclopentene ring, and a cyclohexene. The ring, the benzene ring, the pyridine ring, the pyrazine ring, and the azine ring preferably include a benzene ring and a pyridine ring.

Particularly preferably, 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. Further, R ^{85 is} preferably a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonylamino group, a carboxyl group or a decylamino group, more preferably a sulfo group, a sulfonylamino group or a carboxyl group. , amidino group. R ^{85 is} preferably an abutting portion bonded to carbon bonded to the xanthene ring. The substituent of the phenyl group of R ⁸¹ and R ⁸⁴ is particularly preferably a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonylamino group or a carboxyl group.

The compound having a xanthene skeleton represented by the formula (J) can be synthesized by a method described in the literature. Specifically, "Tetrahedron Letters" (2003, vol. 44, No. 23, pages 4355 to 4360) and "tetrahedron" can be applied (2005, vol. 61, No. 12, 3097 pages ~ The method described in 3106).

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

[11]

<<<花青色素>>>

One of the aspects of the cation having a pigment structure of the present invention is a moiety having a structure derived from a cyanine pigment (cyanine compound). For details of the above, refer to the description of Paragraph No. 0191 to Paragraph No. 0201 of Japanese Patent Laid-Open No. 2013-28764, the contents of which are hereby incorporated herein.

<<<Subphthalocyanine pigment>>>

One of the aspects of the cation having a pigment structure of the present invention is one having a phthalocyanine dye structure. For details of the above, refer to the description of Paragraph No. 0242 to Paragraph No. 0250 of Japanese Patent Laid-Open No. 2013-28764, the contents of which are hereby incorporated herein.

<<<Squaric acid indole pigment>>>

The cation having a pigment structure used in the present invention may also have a squaraine indole dye structure. For details of these, refer to the description of Paragraph No. 0202 to Paragraph No. 0223 of Japanese Patent Laid-Open Publication No. 2013-28764, which is incorporated herein by reference.

The hydrogen atom in the dye structure may be substituted with a substituent selected from the following substituent group A, as long as the dye of the present invention does not deviate from the gist of the present invention.

Substituent group A:

Examples of the substituent which the dye may have include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, and the like. Aryloxy, nonyloxy, heterocyclooxy, decyloxy, amine methoxycarbonyl, amine (including alkylamino, anilino), mercaptoamine, aminocarbonylamino, alkoxy Carbonylamino, aryloxycarbonylamino, aminesulfonylamino, alkylsulfonylamino or arylsulfonylamino, fluorenyl, alkylthio, arylthio, heterocyclic thio, amine Sulfonyl, sulfo, alkylsulfinyl or arylsulfinyl, alkylsulfonyl or arylsulfonyl, anthracenyl, aryloxycarbonyl, alkoxycarbonyl, aminemethanyl An arylazo or heterocyclic azo group, a quinone imine group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a decyl group, and the like. The details are described below.

The halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), a linear or branched alkyl group (linear or branched substituted or unsubstituted alkyl group, preferably a carbon number of 1~) An alkyl group of 30, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), The cycloalkyl group (preferably, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as a cyclohexyl group or a cyclopentyl group, and a polycycloalkyl group such as a bicycloalkyl group (preferably carbon) is exemplified. a substituted or unsubstituted bicycloalkyl group of 5 to 30, such as bicyclo[1,2,2]heptan-2-yl, bicyclo[2,2,2]octane-3-yl) or tricyclic a group having a polycyclic structure such as an alkyl group. Preferred is a monocyclic cycloalkyl group, a bicycloalkyl group, particularly preferably a monocyclic cycloalkyl group), a linear or branched alkenyl group (linear or branched substituted). Or an unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as a vinyl group, an allyl group, a prenyl group, a geranyl group, an oleyl group, or a cycloalkenyl group (preferably The substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms may, for example, be 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, polycycloalkenyl, for example, bicycloalkenyl ( Preferred are substituted or unsubstituted bicycloalkenyl groups having 5 to 30 carbon atoms, such as bicyclo[2,2,1]hept-2-en-1-yl, bicyclo[2,2,2]octane-2 -alkenyl-4-yl) or tricycloalkenyl, particularly preferably monocyclic cycloalkenyl), alkynyl (preferably substituted or unsubstituted alkynyl having 2 to 30 carbon atoms, such as ethynyl, Propargyl, trimethyldecyl ethynyl), aryl (preferably substituted or unsubstituted aryl having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl) , ortho-hexadecanoylaminophenyl), heterocyclic (preferably substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed ring of 5 to 7 members) More preferably, the heterocyclic group is a heterocyclic group selected from a carbon atom, a nitrogen atom and a sulfur atom and having at least one of a nitrogen atom, an oxygen atom and a sulfur atom, and more preferably a carbon number. 5 to 30 of 6 or 6 membered aromatic heterocyclic groups, such as 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl) , cyano group, hydroxyl group, nitro group, carboxyl group, Alkoxy (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2 -methoxyethoxy), aryloxy (preferably substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 2,4- Di-t-pentylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecylideneaminophenoxy), decyloxy (preferably carbon) a decyloxy group having 3 to 20, for example, a trimethyldecyloxy group, a tert-butyldimethylsilyloxy group, a heterocyclic oxy group (preferably a substituted or unsubstituted carbon number of 2 to 30) The heterocyclic oxy group, the heterocyclic ring portion is preferably a heterocyclic ring described in the above heterocyclic group, for example, 1-phenyltetrazole-5-oxyl, 2-tetrahydropyranyloxy), fluorene An oxy group (preferably a methyl methoxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example Methoxycarbonyl, ethoxylated, trimethylethoxyoxy, stearyloxy, benzhydryloxy, p-methoxyphenylcarbonyloxy), amine formazan a base (preferably a substituted or unsubstituted amine methyl methoxy group having 1 to 30 carbon atoms, such as N,N-dimethylamine methyl methoxy, N,N-diethylamine methyl methoxy group , morpholinylcarbonyloxy, N,N-di-n-octylaminocarbonyloxy, N-n-octylaminemethyloxy), alkoxycarbonyloxy (preferably carbon 2 to 30) Substituted or unsubstituted alkoxycarbonyloxy group, such as methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxy a carbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, ortho. Alkoxyphenoxycarbonyloxy), an amine group (preferably an amine group, a substituted or unsubstituted carbon number of 1 to 30) Alkylamino group, substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, heterocyclic amino group having 0 to 30 carbon atoms, such as an amine group, a methylamino group, a dimethylamino group, an aniline , N-methyl-anilino, diphenylamino, N-1,3,5-triazin-2-ylamino), mercaptoamine (preferably formazanyl, carbon number) a substituted or unsubstituted alkylcarbonylamino group of 1 to 30, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as a decylamino group, an ethyl decylamino group, Methylacetamidoamine, laurylamino, benzhydrylamino, 3,4,5-tri-n-octyloxycarbonylcarbonyl, aminocarbonylamino (preferably carbon) a substituted or unsubstituted aminocarbonylamino group of 1 to 30, such as an amine, a mercaptoamine group, an N,N-dimethylaminocarbonylamino group, an N,N-diethylaminocarbonylamine a morpholinocarbonylamino group, an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as a methoxycarbonylamino group, an ethoxy group) Carbocarbonylamino group, tert-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group, An oxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, a meta-octyloxy group) a phenoxycarbonylamino group, an amine sulfonylamino group (preferably a substituted or unsubstituted sulfonylamino group having a carbon number of 0 to 30, such as an amine sulfonylamino group, N, N - dimethylaminosulfonylamino, N-n-octylaminosulfonylamino), alkylsulfonylamino or arylsulfonylamino (preferably from 1 to 30 carbon atoms) Substituted or unsubstituted alkylsulfonylamino group, substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonate Amino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group, a mercapto group, an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group, an n-hexadecylthio group), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, such as a phenylthio group, a p-chlorophenylthio group, a m-methoxyphenylthio group, or a heterocyclic thio group (preferably having a carbon number of 2 to 30) The substituted or unsubstituted heterocyclic thio group, preferably the heterocyclic moiety described in the above heterocyclic group, such as 2-benzothiazolylthio, 1-phenyltetrazole- 5-thio), aminsulfonyl (preferably substituted or unsubstituted sulfonyl group having a carbon number of 0 to 30, such as N-ethylamine sulfonyl, N-(3-dodecane) Oxypropyl)amine sulfonyl, N,N-dimethylamine sulfonyl, N-acetamimidoxime, N-benzamidesulfonyl, N-(N'-benzene a sulfhydryl group, a sulfo group, an alkylsulfinyl group or an arylsulfinyl group (preferably a substituted or unsubstituted alkyl sulfinium having a carbon number of 1 to 30) a substituted or unsubstituted arylsulfinyl group of 6 to 30, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfin Alkylsulfonyl or arylsulfonyl (preferably substituted or unsubstituted alkylsulfonyl having 1 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30) a sulfonyl group, for example, a methylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group, a p-methylphenylsulfonyl group, a fluorenyl group (preferably a fluorenyl group, a carbon number of 2 to 30) a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as an ethyl fluorenyl group, a trimethylethenyl group, a 2-chloroethyl group, a stearyl group , benzylidene, p-octyloxyphenylcarbonyl), aryloxycarbonyl (preferably substituted or unsubstituted aryloxycarbonyl having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chloro Phenoxy a carbonyl group, a m-nitrophenoxycarbonyl group, a p-tert-butylphenoxycarbonyl group, an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as a An oxycarbonyl group, an ethoxycarbonyl group, a third butoxycarbonyl group, an n-octadecyloxycarbonyl group, an amine carbenyl group (preferably a substituted or unsubstituted amine carbenyl group having 1 to 30 carbon atoms) For example, aminomethyl sulfhydryl, N-methylamine, fluorenyl, N,N-dimethylamine, fluorenyl, N,N-di-n-octylamine, fluorenyl, N-(methylsulfonyl) a carbamoyl group, an aryl azo group or a heterocyclic azo group (preferably a substituted or unsubstituted aryl azo group having a carbon number of 6 to 30, a substituted carbon number of 3 to 30 or Unsubstituted heterocyclic azo group (the heterocyclic moiety is preferably the heterocyclic moiety described in the above heterocyclic group), for example, phenylazo, p-chlorophenylazo, 5-B Thio-1,3,4-thiadiazol-2-ylazo), quinone imine (preferably a substituted or unsubstituted quinone group having a carbon number of 2 to 30, such as N- Amber quinone imine, N-phthalimine), phosphino group (preferably substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino group) , diphenylphosphino, methylphenoxyphosphino), phosphinyl (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxy a phosphino group, a diethoxyphosphinyl group, a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as a diphenoxyphosphinyloxy group) , dioctyloxyphosphinyloxy), phosphinylamino (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as dimethoxyphosphinylamino group , dimethylaminophosphinylamino), decylalkyl (preferably substituted or unsubstituted alkylene group having a carbon number of 3 to 30, such as trimethyldecyl, tert-butyldimethylsilane Base, phenyldimethylmethylalkyl).

a portion of a hydrogen atom in a functional group having a hydrogen atom in the functional group It can also be substituted by any of the above groups. Examples of the functional group which can be introduced as a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an ethenylaminosulfonyl group, and a benzhydrylaminosulfonyl group.

<<<counter anion>>>

The counter anion when the dye structure used in the present invention has a cationic structure may be located in the same repeating unit of the dye polymer or may be located outside the same repeating unit. The fact that the counter anion is located in the same repeating unit means that the cation and the anion are bonded via a covalent bond in a repeating unit having a dye structure. On the other hand, the term "the same repeating unit" means a case other than the above. For example, it means a case where a cation and an anion are not bonded by a covalent bond, but exist as a different compound, or a case where a cation and an anion are each contained as a separate repeating unit of a dye-polymer.

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

In the first embodiment of the anion in the present invention, the counter anion is located in the same repeating unit, and specifically, in the case of a repeating unit having a dye structure, the cation and the anion are bonded via a covalent bond.

The anion portion in this case is preferably selected from the group consisting of -SO ₃ ^- , -COO ^- , -PO ₄ ^- , a structure represented by the following formula (A1), and a structure represented by the following formula (A2). At least one of them.

General formula (A1)

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

In the general formula (A1), preferably R ¹ and R ² represents at least one of -SO ₂ -, more preferably both R ¹ and indicated as R _² -SO ² -.

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

General formula (A1-1)

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

In the formula (A1-1), R ¹ and R ² have the same meanings as R ¹ and R ² in the formula (A1), and the preferred ranges are also the same.

When X ¹ represents an alkylene group, the carbon number of the alkyl group is preferably from 1 to 8, more preferably from 1 to 6. When X ¹ represents an aryl group, the carbon number of the aryl group is preferably from 6 to 18, more preferably from 6 to 12, and still 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, preferably an alkyl group. The carbon number of the alkyl group is preferably from 1 to 8, more preferably from 1 to 6, more preferably from 1 to 3, particularly preferably 1. When X ² has a substituent, it is preferably substituted with a fluorine atom.

General formula (A2)

(In the 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), preferably R ³ ~ R ⁵ represents at least one of -SO ₂ -, more preferably represents at least two of R ³ ~ R ⁵ -SO ₂ -.

In the present embodiment, in particular, when the skeleton of the dye polymer is represented by the constituent unit represented by the above formula (A), a case where a part of L ₁ includes a moiety represented by the formula (A1) is exemplified. A good example. As a specific example in the above case, (a-xt-1), (a-xt-5), and (a-xt-6) in the illustration of the repeating unit having a dye structure described later can be exemplified.

In addition, in the present embodiment, the skeleton of the dye polymer used in the present invention includes the general formula shown in Paragraph No. 0276 to Paragraph No. 0304 of JP-A-2013-28764. (B) The constituent unit represented. (B-dp-1), (B-mp-1), (B-xt-1), (B-xt) in the example of the repeating unit which has a dye structure mentioned later as a specific example in this case. -2).

(When the counter anion is a different molecule)

The second embodiment of the anion in the present invention is a case where the counter anion is outside the same repeating unit, and the cation and the anion are not bonded by a covalent bond but exist as a different molecule.

Examples of the anion in this case include a fluoride anion, a chloride anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, a borate anion (BF ^4-, etc.), PF ^6- and SbF ^6-, etc. It is preferably a borate anion and PF ^6- .

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

Further, the anion may be contained in a part of the compound as an anion portion. The anion portion in the above case is preferably selected from the group consisting of -SO ₃ ^- , -COO ^- , -PO ₄ ^- , and the structure and formula represented by the formula (A1) described in the first embodiment ( A2) at least one of the structures represented.

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

[Chemistry 16]

[化17]

Further, in the second embodiment, the anion may be a polymer. The polymer in this case may, for example, be a polymer comprising a repeating unit having an anion and not including a repeating unit derived from a dye structure having a cation. Here, examples of the repeating unit containing an anion include a repeating unit containing an anion described in the third embodiment to be described later. Further, the anion-containing polymer may have a repeating unit other than the repeating unit containing an anion. As such a repeating unit, other repeating units which can be contained in the dye polymer used in the present invention to be described later are exemplified as preferred examples.

(In the case where the cation and the anion are contained in different repeating units of the dye polymer)

The third embodiment in the present invention refers to a case where the cation and the anion are contained in separate repeating units of the dye polymer.

In the present embodiment, the anion may be contained in the side chain of the dye polymer, or may be contained in the main chain, and may have a counter anion in both the main chain and the side chain. It is preferably a side chain.

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

General formula (C)

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

In the general formula (C), X ¹ represents a main chain of a repeating unit, and generally represents a linking group formed by a polymerization reaction, and is preferably, for example, a (meth)acrylic acid, a styrene-based or a vinyl-based one, and more preferably. It is a (meth)acrylic system. Furthermore, the part indicated by two * is a repeating unit.

When L ¹ represents a divalent linking group, it is preferably an alkylene group having 1 to 30 carbon atoms (methylene group, ethylidene group, trimethylene group, propyl group, butyl group, etc.), and carbon number 6 to 30. Aryl group (phenyl, naphthyl, etc.), heterocyclic linkage, -CH=CH-, -O-, -S-, -C(=O)-, -CO-, -NR-, - CONR-, -OC-, -SO-, -SO ₂ - and a linking group of two or more of these. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

In particular, L ^{1 is} preferably a single bond or an alkylene group having a carbon number of 1 to 10 (preferably -(CH ₂ )n- (n is an integer of 5 to 10)), and a carbon number of 6 to 12 A divalent linking group in which two or more of a group (preferably a phenyl group, an anthranyl group), -NH-, -CO ₂ -, -O-, and -SO ₂ - are combined.

Specific examples of X ^1, can be exemplified by the general formula X ₁ in the example (A) as a preferred embodiment.

General formula (D)

(In the formula (D), L ² and L ³ each independently represent a single bond or a divalent linking group. Anion represents the 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 extended aryl group having 6 to 30 carbon atoms, a heterocyclic linking group, and -CH= are preferably used. CH-, -O-, -S-, -C(=O)-, -CO ₂ -, -NR-, -CONR-, -O ₂ C-, -SO-, -SO ₂ - and these A combination of two or more of them. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

L ^{2 is} preferably a aryl group having 6 to 12 carbon atoms (especially a phenyl group). The aryl group having 6 to 30 carbon atoms is preferably substituted by a fluorine atom.

L ^{3 is} preferably a group containing a combination of a aryl group (particularly a phenyl group) having a carbon number of 6 to 12 and -O-, and preferably at least one exoaryl group having a carbon number of 6 to 12 is substituted by 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.

[Chemistry 20]

The following specific examples show a state in which the anion structure is not dissociated, but the state in which the anion structure is dissociated is of course within the scope of the invention.

[Chem. 21]

[化22]

[化23]

[Chem. 24]

The following is an example of (a) a repeating unit which is preferably used in the present invention. The invention is of course not limited to these. X ^- represents a counter anion. Further, a part of X is shown in a state in which the anion structure is not dissociated, but the dissociated state is of course also included in the present invention.

[化27]

[化28]

[化29]

[化30]

[化31]

[化32]

[化33]

<<(b) Repeating unit having a group in which 2 to 20 unsubstituted alkylene oxide chains are repeated in the side chain>>

The dye multimer used in the present invention contains (b) a repeating unit having a group in which two to 20 unsubstituted alkylene oxide chains are repeated in the side chain (hereinafter sometimes referred to as "(b)). Repeat unit").

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

The 1 alkoxy chain is represented by -(CH ₂ ) _n O-, 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 group obtained by repeating 2 to 20 unsubstituted alkylene oxide chains may contain only one alkylene oxide chain, or may contain two or more types.

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

General formula (P)

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

₁ are the same as the general formula (P) in the meaning of ₁ and ₁ X L with the formula (A) and X ₁ is L, the preferred range is also the same.

P represents a group having a group in which a repeating alkoxy chain is repeated, and more preferably a group containing a "- repeating alkoxy chain" or a terminal group.

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, and further preferably a hydrogen atom or a methyl group. A phenyl group and a hydroxyl group are particularly preferably a hydrogen atom.

(b) having 2 to 20 unsubstituted alkylene oxide chains in the side chain The proportion of the repeating unit of the group is preferably from 2 mol% to 20 mol%, more preferably from 5 mol% to 15 mol%, of all the repeating units constituting the dye polymer.

Examples of the (b) repeating unit which can be used in the present invention are shown below, but the present invention is of course not limited thereto.

<<Other functional groups or other repeating units>>

The dye polymer of the present invention may have other functional groups or other repeating units than those described above.

Other functional groups may be contained in the (a) repeating unit and/or (b) repeating unit, or may be contained in a manner other than the repeating unit, including other repeating units containing a functional group.

Examples of the other functional group include a polymerizable group, an acid group, and other alkali-soluble groups.

More specifically, in the above formula (P), P is preferably a repeating unit of a polymerizable group, an acid group, and another alkali-soluble group.

Further, as another repeating unit, a repeating unit containing at least one of a polymerizable group and an acid group can be exemplified.

The details of these will be described below.

<<<Polymerization base>

The polymerizable group is preferably contained in the (a) repeating unit and contained in other repeating units. When it is contained in the dye structure in the (a) repeating unit, heat resistance tends to be further improved. The polymerizable group may be contained alone or in combination of two or more.

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

More specifically, it is preferred that in the above formula (P), P is a repeating of a polymerizable group unit.

(1) A method of introducing a polymerizable group by (a) a repeating unit to be introduced into a polymerizable group, such as a repeating unit, and introducing a polymerizable group by using a polymerizable group-containing compound, and (2) A method in which a polymerizable group is copolymerized to introduce a polymerizable group.

When the polymerizable group is contained in the dye structure in the (a) repeating unit, the amount of the polymerizable group to be contained is preferably 0.1 mmol to 2.0 mmol, more preferably 0.2 mmol to 1.5 mmol, per 1 g of the dye structure. Particularly preferred is 0.3 mmol to 1.0 mmol.

Further, when the other repeating unit contains a polymerizable group, the amount thereof is, for example, preferably from 10 moles to 40 moles, more preferably from 15 moles to 35 moles, per 100 moles of the repeating unit.

Specific examples of the repeating unit having a polymerizable group are as follows. However, the invention is not limited to the specific examples.

[化36]

[化37]

<<<Acid base>>>

The acid group which may be contained in the dye polymer of the present invention may, for example, be a carboxylic acid group, a sulfonic acid group or a phosphoric acid group. In the present invention, it is preferred that the acid group be contained in the dye polymer in the form of a repeating unit having an acid group. The acid group may be contained alone or in combination of two or more.

When the acid group is contained, the acid value of the dye polymer used in the present invention is preferably from 0.3 mmol/g to 1.5 mmol/g, more preferably from 0.5 mmol/g to 1.2 mmol/g. Further preferably, it is 0.5 mmol/g to 1.0 mmol/g.

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

More specifically, it is preferred that in the above formula (P), P is a repeating unit of an acid group.

Further, when the dye polymer contains a repeating unit having an acid group, the proportion of the repeating unit having a repeating unit having an acid group is preferably 20 mol per gram of the repeating unit 100 containing the dye polymer. 80 moles, more preferably 20 moles to 65 moles.

<<<Other alkali soluble base>>>

The dye polymer of the present invention may contain an alkali-soluble group other than the above group. The alkali-soluble group which can be contained in the dye polymer used in the present invention is exemplified by a phenolic hydroxyl group.

In the present invention, it is preferred that the alkali-soluble group is contained in the dye polymer in the form of a repeating unit having an alkali-soluble group.

A method of introducing an alkali-soluble group into the dye polymer includes a method of introducing an alkali-soluble group into the dye monomer in advance. The method of introducing an alkali-soluble group into the dye polymer includes a monomer other than the dye monomer having an alkali-soluble group ((meth)acrylic acid, a caprolactone modification of acrylic acid, or a (meth)acrylic acid 2- Modification of succinic anhydride of hydroxyethyl ester, modification of phthalic anhydride of 2-hydroxyethyl (meth)acrylate, 1,2-cyclohexanedicarboxylic anhydride of 2-hydroxyethyl (meth)acrylate a carboxylic acid-containing monomer such as a carboxylic acid, a styrene carboxylic acid, an itaconic acid, a maleic acid or a norbornene carboxylic acid, and an acid a phosphoric acid-containing monomer such as a phosphonium oxyethyl methacrylate or a vinylphosphonic acid, or a sulfonic acid-containing monomer such as vinylsulfonic acid or 2-propenylamine-2-methylsulfonic acid; The method of polymerization.

More specifically, in the above formula (P), P is preferably a repeating unit of an alkali-soluble group.

When the alkali-soluble group is contained, the amount of the alkali-soluble group of the dye polymer is preferably from 0.3 mmol to 2.0 mmol, more preferably from 0.4 mmol to 1.5 mmol, based on 1 g of the dye polymer. 0.5mmol~1.0mmol.

Further, when the dye polymer 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 1 mol per 100 mol of the repeating unit containing the dye-polymer. Ears ~10 m.

<<<Other functional groups>>

In addition to the functional group, examples of the functional group which may be contained in the dye polymer used in the present invention include a lactone group, an acid anhydride group, a guanamine group, a -COCH ₂ CO- group, and a cyano group. A pro-hydrophobicity adjusting group such as a promoting group, a long-chain or a cyclic alkyl group, an aralkyl group, an aryl group, a polyalkylene oxide group, a hydroxyl group, a maleimine group or an amine group can be appropriately introduced. These may be contained alone or in combination of two or more.

Examples of the introduction method include a method of introducing into the dye structure in advance, and a method of copolymerizing a monomer having the functional group.

<<<Specific examples>>>

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

[39]

<<Characteristics of Pigment Polymers>>

The dye multimer of the present invention preferably has a maximum absorption wavelength of from 400 nm to 650 nm, more preferably from 450 nm to 600 nm.

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

In particular, in the case of a dye multimer containing an xanthene dye, it is preferably 8,000 to 20,000, more preferably 10,000 to 18,000.

In addition, in the case of a dye polymer containing a dipyrromethene dye, The best is 5,000 to 20,000, more preferably 9,000 to 15,000.

Further, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the dye polymer [(Mw) / (Mn)] is preferably from 1.0 to 3.0, more preferably from 1.0 to 2.5, particularly preferably from 1.0 to 4. 2.0.

The glass transition temperature (Tg) of the dye polymer of the present invention is preferably 50 ° C or higher, more preferably 100 ° C or higher. Further, the 5% weight loss temperature obtained by thermogravimetric analysis (TGA measurement) is preferably 120 ° C or higher, more preferably 150 ° C or higher, and still more preferably 200 ° C or higher. By being within this range, when the colored composition of the present invention is used for producing a color filter or the like, the concentration change caused by the heating process can be reduced.

Further, the light absorption coefficient per unit weight of the dye polymer of the present invention (hereinafter referred to as ε'. ε' = ε / average molecular weight, unit: L / g. cm) is preferably 30 or more, more preferably 60 or more. And then better than 100 or more. When a color filter is produced by applying the colored composition of the present invention within this range, a color filter excellent in color reproducibility can be produced.

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

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

The organic solvent may, for example, be an ester (for example, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, etc.), an ether. Classes (eg, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene) Alcohol monomethyl ether acetate, etc.), ketones (methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.), aromatic hydrocarbons (such as toluene, xylene, etc.), relative to 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% by mass or less, and further preferably 10% by mass or more and 30% by mass or less. By using the coloring composition of the present invention in the production of a color filter or the like by this range, a preferable coating surface state can be achieved, or a concentration reduction due to elution after coating other colors can be reduced. .

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

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

The mass ratio of the dye polymer to the pigment (pigment polymer/pigment) is preferably from 0.40 to 1.00, more preferably from 0.45 to 0.80, and still more preferably from 0.50 to 0.75.

The coloring agent component (the coloring matter polymer, the total of the pigments and other dyes described later) in the coloring composition of the present invention is preferably 50% by mass to 70% by mass, and more preferably 55 mass% of the total solid content of the coloring composition. %~65 mass%.

<Other components of the coloring composition>

The colored composition of the present invention may contain other components in addition to the dye polymer. For example, for the purpose of adjusting the color value, etc., the coloring composition used in the present invention preferably includes a pigment and a pigment dispersing agent in addition to the dye polymer.

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

For example, in the case where a coloring layer is formed by photoresist, the coloring composition of the present invention preferably contains the dye polymer of the present invention, an alkali-soluble resin as a curable compound, a pigment, a pigment dispersion, and photopolymerization. The composition of the starter. Further, it may contain a component such as a surfactant or a solvent.

In the case where the colored layer is formed by dry etching, it is preferably a composition containing the dye polymer of the present invention, a polymerizable compound as a curable compound, a pigment, a pigment dispersion, and a photopolymerization initiator. . Further, it may contain a component such as a surfactant or a solvent.

The details of these will be described below.

<<Pigment>>

The colored composition of the present invention preferably further contains a pigment.

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

Examples of the inorganic pigment include a metal compound represented by a metal oxide or a metal salt, and specific examples thereof include metal oxides and metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. Composite oxide.

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

The pigment which can be preferably used in the present invention is exemplified by the following pigments. however, The invention is not limited to these pigments.

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

These organic pigments may be used singly or in combination for adjusting the spectroscopic or improving the color purity. Specific examples of the combination are shown below. For example, the red pigment may be used alone as an anthraquinone pigment, an anthraquinone pigment, a diketopyrrolopyrrole pigment, or at least one of these pigments and a disazo yellow pigment, an isoporphyrin yellow pigment, a quinacridone. Mixing of a ketone-based yellow pigment or an anthraquinone-based red pigment. For example, CI pigment red 177 is exemplified, and CI pigment red 155 and CI pigment red 224 are exemplified as the ruthenium pigment, and CI pigment red 254 is exemplified as the diketopyrrolopyrrole pigment, and in terms of color decomposition property, Preferably, it is mixed with CI Pigment Yellow 139. another In addition, the quality of red pigment and yellow pigment is preferably 100:5~100:50. When it is 100:4 or less, it is difficult to suppress the light transmittance of 400 nm to 500 nm, and if it is 100:51 or more, the main wavelength may be shifted to a short wavelength, and the color separation ability may not be improved. In particular, the mass ratio is most suitably in the range of 100:10 to 100:30. Further, in the case where the red pigments are combined with each other, the adjustment can be performed in accordance with the required spectroscopic light.

Further, the green pigment may be a halogenated phthalocyanine-based pigment alone or a mixture thereof with a disazo-based yellow pigment, a quinophthalone-based yellow pigment, a carbamide-based yellow pigment or an iso-porphyrin-based yellow pigment. For example, such an example is preferably CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180 or CI Pigment. A mixture of yellow 185. The quality of green and yellow pigments is preferably 100:5~100:150. The quality bit is preferably in the range of 100:30 to 100:120.

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

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

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

Regarding the primary particle size of the pigment, it is used as a color filter. In view of color unevenness or contrast, it is preferably 100 nm or less, and from the viewpoint of dispersion stability, it is preferably 5 nm or more. The primary particle size of the pigment is preferably from 5 nm to 75 nm, more preferably from 5 nm to 55 nm, and particularly preferably from 5 nm 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 the group consisting of an anthraquinone pigment, a diketopyrrolopyrrole pigment, a phthalocyanine pigment, a quinophthalone pigment, an isoporphyrin pigment, a methylimine pigment, and a dioxazine pigment. Especially preferred is CI Pigment Red 177 (蒽醌 pigment), CI Pigment Red 254 (diketopyrrolopyrrole pigment), CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Blue 15:6 (酞Cyanine pigment), CI Pigment Yellow 138 (quinacridone pigment), CI Pigment Yellow 139, CI Pigment Yellow 185 (isoporphyrin pigment), CI Pigment Yellow 150 (methylimine pigment), CI Pigment Violet 23 (dioxin) Pyrazine pigment).

In the case where the pigment is formulated in the composition of the present invention, the content of the pigment is preferably 20% by mass to 50% by mass, and more preferably 25% by mass based on the total amount of the components of the coloring composition excluding the solvent. 50% by mass, and more preferably 30% by mass to 45% by mass.

The composition of the present invention may contain only one kind of pigment, or may contain two or more types. When two or more cases are contained, it is preferable that the total amount is the said range.

<<Pigment Dispersant>>

In the case where the colored composition of the present invention contains a pigment, a pigment dispersant may be used in combination as needed.

The pigment dispersing agent which can be used in the present invention may, for example, be a polymer dispersing agent [for example, polyamine-amine and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, Modified polyester, modified poly(meth)acrylate, (meth)acrylic copolymer, formalin condensate naphthalenesulfonate, and polyoxyalkylene phosphate, polyoxyalkylene oxide Surfactants such as base amines and alkanolamines, and pigment derivatives.

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

For example, the terminal-modified polymer having an anchor portion on the surface of the pigment has a phosphate group at the terminal, as described in JP-A-3-112992, JP-A-2003-533455, and the like. The polymer having a sulfonic acid group at the terminal described in JP-A-2002-273191, and the like, and the high molecular weight of the partial skeleton or heterocyclic ring having an organic dye described in Japanese Laid-Open Patent Publication No. Hei 9-77994 Molecules, etc. In addition, a polymer which introduces two or more fixed sites (acid groups, basic groups, partial skeletons of organic dyes, heterocyclic rings, etc.) to the surface of the pigment at the end of the polymer described in JP-A-2007-277514 It is also excellent in dispersion stability and is preferred.

The graft-type polymer having a fixed portion on the surface of the pigment is, for example, a polyester-based dispersant, and the like, and a Japanese Patent Laid-Open Publication No. Hei 54-37082, Japanese Patent Publication No. Hei 8-507960, and Japan The reaction product of the polyallylamine and the polyester described in JP-A-H09-169821, and the like, and the reaction product of the poly(lower alkylene imine) and the polyester described in JP-A-H09-169821, and the like. Japanese Patent Laid-Open No. Hei 10-339949, Japanese Patent Laid-Open No. 2004-37986 A copolymer of a macromonomer and a nitrogen atom monomer described in the International Publication No. WO2010/110491, etc., Japanese Patent Laid-Open No. 2003-238837, Japanese Patent Laid-Open No. 2008-9426, and Japanese Patent Laid-Open Publication No. 2008 a graft-type polymer having a partial skeleton or a heterocyclic ring of an organic dye, which is described in Japanese Laid-Open Patent Publication No. 2010-106268, and a copolymer of a macromonomer and an acid group-containing monomer described in JP-A-2010-106268 Wait. In particular, in view of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the coloring composition using the pigment dispersion, it is preferable to be alkaline as described in JP-A-2009-203462. Amphoteric dispersion resin with a base and an acidic group.

A known macromonomer can be used as the macromonomer used for the production of the graft-type polymer having a fixed portion on the surface of the pigment by radical polymerization, and examples thereof include a macromonomer AA-6 manufactured by East Asia Synthetic Co., Ltd. (polymethyl methacrylate with terminal group being methacryl fluorenyl), AS-6 (polystyrene with terminal group of methacryl fluorenyl), AN-6S (benzene with terminal group of methacryl fluorenyl) Copolymer of ethylene and acrylonitrile), AB-6 (polybutyl acrylate of methacryl fluorenyl group), Placcel FM5 manufactured by Daicel Chemical Industry Co., Ltd. 2-hydroxyethyl acrylate ε-caprolactone 5 molar equivalent plus finished product), FA10L (2-hydroxyethyl acrylate ε-caprolactone 10 molar equivalent plus finished product), and Japanese Patent Laid-Open 2- The polyester-based macromonomer described in the publication No. 272009. Among these macromonomers, in particular, from the viewpoint of dispersibility of the pigment dispersion, dispersion stability, and developability exhibited by the coloring composition using the pigment dispersion, it is particularly preferable that it is excellent in flexibility and solvophilicity. Polyester-based giant monomer, and further preferably Japanese Patent Laid-Open No. 2-272009 The polyester-based macromonomer represented by the polyester-based macromonomer described in the above.

The block type polymer which has a fixed part to the surface of the pigment is preferably a block type polymer described in JP-A-2003-49110, JP-A-2009-52010, and the like.

The pigment dispersing agent which can be used in the present invention can also be obtained as a commercially available product, and specific examples thereof include "DA-7301" manufactured by Nanben Chemical Co., Ltd., and "DiK Chemie" manufactured by BYK Chemie Co., Ltd. Disperbyk-101 (polyamine-amine phosphate), Disperbyk-107 (carboxylate), Disperbyk-110, Despap Disperbyk-111 (acid-based copolymer), Disperbyk-130 (polyamide), Disperbyk-161, Disperbyk -162, Disperbyk-163, Disperbyk-164, Disperbyk-165, Disperbyk-166, Dispa Disperbyk-170 (polymer copolymer), "BYK-P104, BYK-P105 (high molecular weight unsaturated polycarboxylic acid)", manufactured by EFKA "EFKA 4047, EFKA 4050, EFKA 4010, EFKA 4165 (polyurethane), EFKA 4330 ~Efka (EFKA) 4340 (block copolymer), Efka (EFKA) 4400 ~ Efka (EFKA) 44 02 (modified polyacrylate), Efka (EFKA) 5010 (polyester decylamine), Efka (EFKA) 5765 (high molecular weight polycarboxylate), Efka (EFKA) 6220 (fatty acid polyester ), Efka (EFKA) 6745 (phthalocyanine derivative), Efka (EFKA) 6750 (Azo pigment derivative), Ajisper PB821, Ajisper PB822, Ajisper, manufactured by Ajinomoto Fine-Techno PB880, Ajisper PB881, "Flowlen TG-710 (urethane oligomer)" and "Polyflow No" manufactured by Kyoeisha Chemical Co., Ltd. .50E, Polyflow No. 300 (Acrylic Copolymer), "Disperlon KS-860, Disperlon 873SN, Dispa, manufactured by Nanben Chemical Co., Ltd." Disperlon 874, Disperlon #2150 (aliphatic polycarboxylic acid), Disperlon #7004 (polyether ester), Disperlon DA-703-50 , Disperlon DA-705, Disperlon DA-725, Demol RN, Demol N, Naphthalene Sulfate Polycondensate), Demol MS, Demol C, Demol SN-B (aromatic sulfonate fumarate polycondensate), and "Homogenol L" -18 (polymer polycarboxylic acid), "Emulgen 920, admiration (Emulgen) 930, Emulgen 935, Emulgen 985 (polyoxyethylidene phenyl ether), and "Acetamin" 86 (stearylamine acetate) "Solsperse 5000 (phthalocyanine derivative), Solsperse 22000 (azo pigment derivative), Sonupa, manufactured by Lubrizol Japan Co., Ltd. Solsperse 13240 (polyesteramine), Solsperse 3000, Solsperse 17000, Solsperse 27000 (polymer with functional part at the end), Solsperse 24000, Sonupas (Solsperse) 28000, Solsperse 32000, Solsperse 38500 (grafted polymer), Nikkol T106 (Polyoxygen Ethyl Yam) manufactured by Nikko Chemical Co., Ltd. Hinoact T-8000E, manufactured by Kawasaki Seiki Co., Ltd., Nikkol MYS-IEX (polyoxyethylidene monostearate) Etc., the organic siloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd., "W001: Cationic surfactant" manufactured by Yushang Co., Ltd., polyoxyethylene ethyl lauryl ether, polyoxyethyl ether Aliphatic ether, polyoxyethylene ethyl oleyl ether, polyoxyethyl octyl phenyl ether, polyoxyethyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol Non-ionic surfactants such as stearate and sorbitan fatty acid ester, and anionic surfactants such as "W004, W005, and W017", "EFKA-46" manufactured by Morishita Industries Co., Ltd. EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, Eve Card (EFKA) Polymer 450", Disperse-aid 6, Disperse-aid 8, Disperse-aid, manufactured by Sannopco A polymer dispersant such as Disperse-aid 9100, Adeka Pluronic L31 and Adeka made by Adeko (ADEKA) Pluronic) F38, Adeka Pluronic L42, Adeka Pluronic L44, Adeka Pluronic L61, Adeka Pluronic L64, Eddie Adeka Pluronic F68, Adeka Proknik (Adeka) Pluronic) L72, Adeka Pluronic P95, Adeka Pluronic F77, Adeka Pluronic P84, Adeka Pluronic F87, Eddie Adeka Pluronic P94, Adeka Pluronic L101, Adeka Pluronic P103, Adeka Pluronic F108, Adeka Pluronic ) L121, Adeka Pluronic P-123, and Eonet (trade name) S-20 manufactured by Sanyo Chemicals Co., Ltd.

Further, a block copolymer or a copolymer having a narrow molecular weight distribution may be used in combination as a pigment dispersant, and the block copolymer or a copolymer having a narrow molecular weight distribution is transferred by a reversible addition fragmentation chain such as a dithiocarbonyl compound. The polymerizable unsaturated compound is obtained by radical polymerization in the presence of a reversible addition-fragmentation chain transfer (RAFT agent) and a radical initiator. Specific examples of such a resin include those described in paragraph number 0053 to paragraph number 0129 of JP-A-2008-242081, and paragraph number 0049 to paragraph number 0117 of JP-A-2008-176218. This is incorporated into the specification of the present application. Further, such a block copolymer or a copolymer having a narrow molecular weight distribution can also be used as the alkali-soluble resin.

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

When the coloring composition contains a pigment dispersant, the total content of the pigment dispersant is preferably from 1 part by mass to 80 parts by mass, more preferably from 5 parts by mass to 70 parts by mass, based on 100 parts by mass of the pigment. It is 10 parts by mass to 60 parts by mass. The composition of the present invention may contain only one kind of pigment dispersant, and may contain two or more types. When two or more cases are contained, it is preferable that the total amount is the said range.

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

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

In the coloring composition, the total content of the coloring matter and the content of the dispersing agent component is preferably 50% by mass or more and 90% by mass or less based on the total solid content of the coloring composition. More preferably 55 mass% The upper portion is 85 mass% or less, and more preferably 60 mass% or more and 80 mass% or less.

<<Dye>>

The colored composition of the present invention may contain a known dye other than the dye polymer. For example, Japanese Patent Laid-Open Publication No. SHO-64-90403, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2, 592, 207, U.S. Patent No. 4,808, 051, U.S. Patent No. 5, 568, 850, U.S. Patent No. 5, 567, 950, U.S. Patent No. 5, 505, 950, U.S. Patent No. 5, 567, 920, U.S. Patent No. 5, 317, 207, Japanese Patent Laid-Open No. Hei No. Hei. The dye disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. The chemical structure can be used: pyrazole azo, pyrromethylene, aniline azo, triphenylmethane, lanthanide, benzylidene, oxonium, pyrazolotriazole azo A dye such as a pyridone azo system, a cyanine system, a phenothiazine system, or a pyrrolopyrazole azomethine group.

The dye may be contained alone or in combination of two or more.

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

<<Photopolymerization initiator>>

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

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, preferably It is sensitive to the ultraviolet range to visible light. Further, it may be an active agent which generates a living radical by some action with a photo-excited sensitizer, or may be an initiator which initiates cationic polymerization depending on the kind of the monomer.

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

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

Further, from the viewpoint of exposure sensitivity, it is preferably selected from the group consisting of a trihalomethyltriazine compound, a benzoin dimethyl ketal compound, an α-hydroxyketone compound, an α-amino ketone compound, and a mercaptophosphine. a compound, a phosphine oxide compound, a metallocene compound, a hydrazine compound, a trially imidazol dimer, a hydrazine compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, and a derivative thereof, A compound of the group consisting of a cyclopentadiene-benzene-iron complex and a salt thereof, a halogenated methyl oxadiazole compound, and a 3-aryl-substituted coumarin compound.

Further preferred are trihalomethyltriazine compounds, α-amino ketone compounds, mercaptophosphine compounds, phosphorus oxide compounds, antimony compounds, triallyl imidazole dimers, triarylimidazole compounds, benzimidazole compounds , a hydrazine compound, a benzophenone compound, an acetophenone compound, particularly preferably selected from the group consisting of a trihalomethyltriazine compound, an α-amine At least one compound of the group consisting of a ketone compound, an anthracene compound, a triallyl imidazole compound, a benzophenone compound, a triarylimidazole compound, and a benzimidazole compound. Further, the triarylimidazole compound may also be a mixture with benzimidazole.

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

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

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

In particular, the colored composition of the present invention is used for producing a solid-state imaging device. In the case of a color filter, it is necessary to form a fine pattern in a sharp shape, and therefore it is important to develop the curable property without residue in the unexposed portion. From this point of view, the polymerization initiator is particularly preferably a ruthenium compound. In particular, when a fine pattern is formed in a solid-state image sensor, a stepper is used for exposure for curing, but the exposure machine may be damaged by halogen, and it is necessary to suppress the addition amount of the polymerization initiator to be low. Therefore, in consideration of these aspects, it is particularly preferable to use a ruthenium compound as the (D) photopolymerization initiator when forming a fine pattern such as a solid-state image sensor.

Examples of the halogenated hydrocarbon compound having a triazine skeleton include a compound described in "Bull. Chem. Soc. Japan" (42, 2924 (1969)), and a specification of British Patent No. 1388492. The compound described in Japanese Laid-Open Patent Publication No. SHO 53-133428, the compound described in the specification of German Patent No. 3337024, and the "J. Org. Chem." by FC Schaefer et al. The compound described in Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 5-. The compound described in the specification of U.S. Patent No. 4,212,976, in particular, the compound described in Paragraph No. 0075 of JP-A-2013-077009.

Further, the photopolymerization initiator other than the above may be an acridine derivative. Specific examples thereof include the compounds described in Paragraph No. 0076 of JP-A-2013-077009, the contents of which are incorporated herein by reference.

The ketone compound is, for example, a compound described in Paragraph No. 0077 of JP-A-2013-077009, which is incorporated herein by reference.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can also be preferably used. More specifically, for example, an amino acetophenone-based initiator as described in JP-A-10-291969, and a mercaptophosphine oxide-based initiator described in Japanese Patent No. 4,258,899 can be used.

The hydroxyacetophenone-based initiator can be used: IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, Yanjiagu (IRGACURE)-127 (trade name: all manufactured by BASF). Amino acetophenone-based initiators can be used as: commercially available products such as IRGACURE-907, IRGACURE-369 and IRGACURE-379 (trade names: all BASF) (Manufactured by BASF). The amine acetophenone-based initiator may also be a compound described in JP-A-2009-191179, which has an absorption wavelength matched to a long-wavelength light source such as 365 nm or 405 nm. Further, the mercaptophosphine-based initiator may also be used as a commercially available product, IRGACURE-819 or DAROCUR-TPO (trade name: all manufactured by BASF), Bichemistry TAZ series manufactured by (shares) (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123).

More preferably, the photopolymerization initiator is a ruthenium compound. As a specific example of the ruthenium compound, a compound described in Japanese Patent Laid-Open Publication No. 2001-233842 can be used. The compound described in JP-A-2000-80068, and the compound described in JP-A-2006-342166.

As the ruthenium compound such as an anthracene derivative which can be preferably used as the photopolymerization initiator of the present invention, for example, 3-benzylideneoxyiminobutan-2-one and 3-ethyloxyimide can be cited. Butyral-2-one, 3-propoxy methoxyiminobutan-2-one, 2-ethoxymethoxyiminopentan-3-one, 2-ethyloxyimino group- 1-phenylpropan-1-one, 2-benzylideneoxyimido-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2- Ketone and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

肟 compounds can be listed as: "Journal of the Chemical Society (JCS) Perkin II (1979) pp. 1653-1660, "Journal of the Chemical Society" , JCS) Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, Japan The compound described in each of the publications of Japanese Laid-Open Patent Publication No. 2000-86385, the Japanese Patent Laid-Open No. Hei.

Commercially available products such as IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), and TR-PBG-304 are also preferably used. Changzhou Power Electronic New Material Co., Ltd.).

In addition, the following compounds may also be used as the oxime compound other than the above description. The compound described in Japanese Patent Publication No. 2009-519904, which is attached to the N-position of the carbazole, and the compound described in U.S. Patent No. 7,626,957, which has a hetero substituent introduced into the benzophenone moiety, The ketone oxime compound described in Japanese Laid-Open Patent Publication No. 2010-15025, and the ketone oxime compound described in International Patent Publication No. 2009-131189, which contains a nitro group, has a nitro group, and contains a nitro group in the same molecule. A compound described in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

The cyclic ruthenium compound described in JP-A-2007-2318 and JP-A-2007-322744 is preferably used. In the case of the cyclic ruthenium compound, the condensed ring described in Japanese Patent Laid-Open Publication No. 2010-185072, and the Japanese Patent Publication No. 2010-185072, and the like. a cyclic guanidine compound on a carbazole dye.

In addition, the compound described in JP-A-2009-242469, which has an unsaturated bond at a specific site of a ruthenium compound, also regenerates an active radical by polymerizing an inactive radical, thereby achieving high sensitivity and being comparable. Good to use.

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

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

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

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

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

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

The alkyl group is preferably an alkyl group having 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, and an isopropyl group. Base, isobutyl, second butyl, tert-butyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, trifluoromethyl, 2-ethylhexyl, benzamidine methyl, 1-naphthalene Methyl mercaptomethyl, 2- Naphthylmethylmethyl, 4-methylamine benzenesulfonylbenzhydrylmethyl, 4-phenylamine benzenesulfonylbenzhydrylmethyl, 4-dimethylaminobenzimidylmethyl, 4- Cyanobenzylidene methyl, 4-methylbenzhydrylmethyl, 2-methylbenzimidylmethyl, 3-fluorobenzhydrylmethyl, 3-trifluoromethylbenzimidylmethyl and 3 - Nitrobenzidine methyl.

The aryl group is preferably an aryl group having 6 to 30 carbon atoms, and specific examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-fluorenyl group, a 9-phenanthryl group, and a 1-fluorenyl group. 5-thick tetraphenyl, 1-indenyl, 2-indenyl, 9-fluorenyl, terphenyl, tetraphenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, o-cumene Base, m-alkenyl and p-cumenyl, 2,4,6-trimethylphenyl, pentalenyl, binaphthalenyl, trinaphthyl, tetranaphthyl, hydrazine Heptenalenyl, biphenylenyl, indacenyl, fluoranthenyl, acenaphthylenyl, vinyl fluorenyl (aceanthrylenyl), propylene phenalenyl, fluorenyl, fluorenyl, hydrazino, triple fluorenyl, tetradecyl, anthraquinolyl, phenanthryl, benzo[9,10]phenanthrene Triphenylenyl, sulfhydryl, Chrysenyl, condensed tetraphenyl, pleiadenyl, picenyl, perylenyl, pentaphenyl, pentacenyl, tetraphenylenyl , hexaphenyl, hexaphenyl, rubicenyl, coronenyl, trinaphthylenyl, heptaphenyl, hexaphenyl, pyranthrenyl and ovalenyl ).

The fluorenyl group is preferably a fluorenyl group having 2 to 20 carbon atoms, and specific examples thereof include an ethyl group, a propyl group, a butyl group, a trifluoroethyl group, a pentamidine group, a benzamidine group, a 1-naphthylmethyl group, 2-naphthylmethyl, 4-methylamine phenylsulfonylbenzyl, 4-phenylamine phenylsulfonylbenzyl, 4-dimethylaminobenzimidyl, 4-diethyl Aminobenzylidene, 2-chlorobenzhydryl, 2-methylbenzhydryl, 2-methoxybenzimidyl, 2-butoxybenzhydryl, 3-chlorobenzhydrazide , 3-trifluoromethylbenzhydryl, 3-cyanobenzylidene, 3-nitrobenzhydryl, 4-fluorobenzhydryl, 4-cyanobenzylidene and 4- Methoxybenzhydryl.

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

Specific examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylamine benzenesulfonylphenoxycarbonyl group, and a 4-phenylamine benzenesulfonylphenoxy group. Carbocarbonyl, 4-dimethylaminophenoxycarbonyl, 4-diethylaminophenoxycarbonyl, 2-chlorophenoxycarbonyl, 2-methylphenoxycarbonyl, 2-methoxybenzene Oxycarbonyl, 2-butoxyphenoxycarbonyl, 3-chlorophenoxycarbonyl, 3-trifluoromethylphenoxycarbonyl, 3-cyanophenoxycarbonyl, 3-nitrophenoxy Carbonyl, 4-fluorophenoxycarbonyl, 4-cyanophenoxycarbonyl and 4-methoxyphenoxycarbonyl.

The heterocyclic group is preferably an aromatic or aliphatic heterocyclic group containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.

Specific examples thereof include: thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, furyl, pyranyl, isobenzofuranyl, benzopyrazine Chromenyl, Xanthenyl, phenoxathiinyl, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyridazinyl, isoindole , 3H-indenyl, fluorenyl, 1H-carbazolyl, fluorenyl, 4H-quinolizinyl, isoquinolinyl, quinolyl, phthalazinyl, naphthyridinyl, Quinoxalinyl, quinazolinyl, Cinnolinyl, pteridinyl, 4aH-carbazolyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, Perimidinyl, phenolinyl, phenazinyl, phenarsazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl ), phenoxazine, different Isochromanyl, benzochromanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolinyl, piperidinyl, piperazinyl, porphyrin A base, an isoindolyl group, a quinuclidinyl group, a morpholinyl group, and a thioxantrill.

Specific examples of the alkylthiocarbonyl group include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, a octylthiocarbonyl group, a decylthiocarbonyl group, an octadecylthiocarbonyl group, and a trifluoromethylthio group. Carbonyl.

Specific examples of the arylthiocarbonyl group include 1-naphthylthiocarbonyl, 2-naphthylthiocarbonyl, 4-methylaminobenzenesulfonylphenylthiocarbonyl, 4-phenylaminebenzenesulfophenylthiocarbonyl, 4- Dimethylaminophenylthiocarbonyl, 4-diethylaminophenylthiocarbonyl, 2-chlorophenylthiocarbonyl, 2-methylphenylthiocarbonyl, 2-methoxyphenylthiocarbonyl, 2 -butoxyphenylthiocarbonyl, 3-chlorophenylthiocarbonyl, 3-trifluoromethylphenylthiocarbonyl, 3-cyanophenylthiocarbonyl, 3-nitrophenylthiocarbonyl, 4-fluorobenzene Thiocarbonyl, 4-cyanophenylthiocarbonyl and 4-methoxyphenylthiocarbonyl.

In the formula (OX-1), the monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. In addition, the groups may have more than one substituent. The substituents described above can be exemplified as the substituents described above. Further, the substituents described above may be further substituted with other substituents.

Among them, the structure shown below is particularly preferable.

In the following structures, Y, X and n are the same as Y, X and n in the following general formula (OX-2), and preferred examples are also the same.

In the formula (OX-1), the divalent organic group represented by A may, for example, be an alkylene group having a carbon number of 1 to 12, a cycloalkyl group or an alkynylene group. In addition, the groups may have more than one substituent. The substituents described above can be exemplified as the substituents described above. Further, the substituents described above may be further substituted with other substituents.

Among them, in terms of improving sensitivity and suppressing coloring caused by heating over time, A in the formula (OX-1) is preferably an unsubstituted alkylene group or an alkyl group (e.g., methyl group, ethyl group). , a tert-butyl, dodecyl) substituted alkylene group, an alkyl group substituted by an alkenyl group (e.g., a vinyl group, an allyl group), an aryl group (e.g., phenyl, p-tolyl, xylyl) , cumenyl, naphthyl, anthracenyl, phenanthryl, styryl) substituted alkylene.

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. The substituent may be exemplified by the same group as the substituent introduced into the substituted aryl group as exemplified above as a specific example of the aryl group which may have a substituent.

Among them, a substituted or unsubstituted phenyl group is preferred in terms of improving sensitivity and suppressing coloration caused by heating over time.

In the formula (OX-1), in terms of sensitivity, the structure of "SAr" formed by Ar in the formula (OX-1) and S adjacent thereto is preferably the structure shown below. Further, Me represents a methyl group, and Et represents an ethyl group.

[化44]

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

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

In the general formula (OX-2), the monovalent substituent represented by X may, for example, be an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a decyloxy group, a decyl group, an alkoxycarbonyl group, an amine group or a hetero group. Ring group, halogen atom. In addition, the groups may have more than one substituent. The substituents described above can be exemplified as the substituents described above. Further, the substituents described above may be further substituted with other substituents.

Among these, X in the formula (OX-2) is preferably an alkyl group in terms of improving solvent solubility and absorption efficiency in a long wavelength range.

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

In the general formula (OX-2), the divalent organic group represented by Y may be exemplified by the structures shown below. Further, in the group shown below, "*" indicates a bonding position of a carbon atom adjacent to Y in the formula (OX-2).

[Chem. 46]

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

Further, the ruthenium compound is preferably a compound represented by the following formula (OX-3) or (OX-4).

[48]

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

R, X, A, Ar and n in the formula (OX-3) or (OX-4) have the same meanings as R, X, A, Ar and n in the formula (OX-2), respectively. The preferred examples are also the same.

Hereinafter, specific examples (C-4) to specific examples (C-13) of the ruthenium compound which can be preferably used are shown below, but the present invention is not limited to these specific examples.

[化49]

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

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

A known method can be used for the molar absorption coefficient of the compound. Specifically, for example, an ultraviolet-visible spectrophotometer (Cary-5) spectrophotometer manufactured by Varian Co., Ltd. is preferably used. )), using an ethyl acetate solvent to measure at a concentration of 0.01 g/L.

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 the total solid content of the coloring composition. It is 0.5% by mass or more and 30% by mass or less, and more preferably 1% by mass or more and 20% by mass or less. Better sensitivity and pattern formation can be obtained within this range.

The composition of the present invention may contain only one photopolymerization initiator, and may contain two or more kinds. When two or more cases are contained, it is preferable that the total amount is the said range.

<<Cure compound>>

<<<Polymerized compound>>>

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

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

Such a compound group is widely known in the industrial field, and these compounds can be used without particular limitation in the present invention. The compounds may be, for example, the following chemical forms Any of the monomers: prepolymers, ie, dimers, trimers, and oligomers or mixtures thereof, and such polymers. The polymerizable compounds of 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 (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, maleic acid, etc.) or esters thereof. The guanamines and the polymers thereof are preferably esters of an unsaturated carboxylic acid and an aliphatic polyol compound, and guanamines of an unsaturated carboxylic acid and an aliphatic polyamine compound, and the like. Things. Further, it is also preferred to use the following reactants: an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group, or an addition of a monofunctional or polyfunctional isocyanate or epoxy group. a reactant, or a dehydration condensation reaction with a monofunctional or polyfunctional carboxylic acid, or the like. Further, the following reactants are also preferred: an unsaturated carboxylic acid ester or a guanamine having an electrophilic substituent such as an isocyanate group or an epoxy group, and a monofunctional or polyfunctional alcohol, an amine or a thiol. The reactants further include a substituted carboxylic acid ester of a detachable substituent such as a halogen group or a tosyloxy group, or a substituted reactant of a monofunctional or polyfunctional alcohol, an amine or a thiol. Further, as another example, a compound group of a vinylbenzene derivative such as an unsaturated phosphonic acid or styrene, a vinyl ether or an allyl ether may be used instead of the unsaturated carboxylic acid.

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

In addition, the polymerizable compound preferably also has at least one additive additive A compound having an ethylenically unsaturated group having a polymerized vinyl group and having a boiling point of 100 ° C or higher under normal pressure. Examples thereof include monofunctional acrylates or methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate; Ethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(a) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, hexane diol (meth) acrylate, trimethylolpropane tris(propylene oxypropyl) ether (Isopropyl methacrylate), (meth) acrylated by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylolethane (Meth)acrylic acid urethanes, such as those described in Japanese Patent Laid-Open Publication No. SHO-48-41708 Japanese Patent Publication No. Sho 48-64183, Japanese Patent Publication No. Sho 49-43191, Japanese Patent Publication No. Sho 52-30490 Acrylate and methacrylate mixture of such multifunctional acrylates or polyester message described as a reaction product of an epoxy resin and (meth) acrylic acid epoxy acrylates.

Further, a polyfunctional (meth) acrylate or the like which is a compound having a cyclic ether group and an ethylenically unsaturated group such as glycidyl (meth)acrylate, and a polyfunctional (meth) acrylate may be mentioned. The carboxylic acid is obtained by a reaction.

In addition, other preferred polymerizable compounds may be used, such as those described in JP-A-2010-160418, JP-A-2010-129825, and JP-A No. 4,364,216. Above A compound having an ethylenically unsaturated group, Cardo resin.

Further, a compound having a boiling point of 100 ° C or higher and having at least one ethylenically unsaturated group capable of undergoing addition polymerization under normal pressure is also preferably a paragraph number [0254] of JP-A-2008-292970. The compound described in paragraph No. [0257].

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

[化50]

[化51]

In the formula, n is 0 to 14, and m is 1 to 8. A plurality of R and T in one molecule may be the same or different.

In each of the polymerizable compounds represented by the general formulae (MO-1) to (MO-5), at least one of a plurality of Rs represents -OC(=O)CH=CH ₂ or -OC(=O). C(CH ₃ )= group represented by CH ₂ .

Specific examples of the polymerizable compound represented by the formula (MO-1) to the formula (MO-5) may be those described in Paragraph No. 0248 to Paragraph No. 0251 of JP-A-2007-269779. It is preferably used in the present invention.

In addition, the following compound can also be used as a polymerizable compound: it is added to the polyfunctional alcohol as the general formula (1) and the general formula (2) as described in Japanese Patent Laid-Open No. Hei 10-62986 A compound obtained by esterifying (meth) acrylate with ethylene oxide or propylene oxide.

Among them, the polymerizable compound is preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available as Kaya) KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol (meth) acrylate (commercial product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and these The structure of (meth)acrylonyl group interspersed with ethylene glycol residues and propylene glycol residues (for example, SR454, SR494, SR499, etc., commercially available from Sartomer Co., Ltd.). These types of oligomers can also be used. Further, tris(2-hydroxyethyl)triacrylate isomeric cyanurate (commercial product: SR368; manufactured by Sartomer Co., Ltd.) can also be used.

The polymerizable compound may be a polyfunctional monomer, and may have an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. When 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, and if necessary, a non-aromatic carboxylic anhydride can be reacted with a hydroxyl group of the ethylenic compound to introduce an acid group. In this case, specific examples of the non-aromatic carboxylic anhydride to be used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and alkylated six. Hydrogen phthalic anhydride, succinic anhydride, maleic anhydride.

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and preferably has a non-aromatic carboxylic anhydride reacting with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acid group. The polyfunctional monomer is particularly preferably one in which the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. Commercially available products include M-510 and M-520 which are polybasic acid-modified acrylic oligomers manufactured by East Asia Synthetic Co., Ltd., for example.

These monomers may be used singly, but it is difficult to use a single compound in terms of production, and it is also possible to use two or more kinds in combination. Further, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as a monomer, as needed.

The preferred acid value of the polyfunctional monomer having an acid group is from 0.1 mgKOH/g to 40 mgKOH/g, particularly preferably from 5 mgKOH/g to 30 mgKOH/g. When the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are lowered. When the acid value of the polyfunctional monomer is too high, production or handling becomes difficult, photopolymerization performance is lowered, and curability such as surface smoothness of pixels is deteriorated. Therefore, when a polyfunctional monomer having two or more acid groups is used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is preferred to use an acid group of the entire polyfunctional monomer. Adjustments within the scope of the description.

Further, a polyfunctional monomer having a caprolactone structure is also preferable as a polymerizable compound.

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 ε-caprolactone-modified polyfunctional (meth) acrylate, and ε- Caprolactone modified polyfunctional (meth) acrylate by trimethylolethane, di-trimethylolethane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, two Polyols such as pentaerythritol, tripentaerythritol, glycerin, diglycerin, and trimethylol melamine are obtained by esterification with (meth)acrylic acid and ε-caprolactone. Among them, a polyfunctional monomer having a caprolactone structure represented by the following formula (Z-1) is preferred.

[化52]

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

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

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

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

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

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

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

In the general formula (Z-4), the total of the acryloyl group and the methacryl fluorenyl group is 3 or 4, and m each independently represents an integer of 0 to 10, and the total value of each m is an integer of 0 to 40. . In the case where the total value of each of m is 0, any one of X is a carboxyl group.

In the general formula (Z-5), the total of the acryloyl group and the methacryl fluorenyl group is 5 or 6, and n each independently represents an integer of 0 to 10, and the total value of each n is an integer of 0 to 60. . However, when the total value 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. Further, the total value of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.

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

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

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

The compound represented by the formula (Z-4) or the formula (Z-5) may be used alone or in combination of two or more. Particularly preferred is a form in which all six of X in the formula (Z-5) are an acrylonitrile group.

Further, the compound represented by the formula (Z-4) or the formula (Z-5) is polymerized. The total content in the conjugated compound is preferably 20% by mass or more, and more preferably 50% by mass or more.

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

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

Specific examples thereof include the compounds represented by the following formulas (a) to (f) (hereinafter also referred to as "exemplary compounds (a) to exemplified compounds (f)"). Among them, preferred examples are compounds (a) and exemplified. Compound (b), exemplified compound (e), and exemplified compound (f).

[化56]

[化57]

Commercial products of the polymerizable compound represented by the formula (Z-4) and the formula (Z-5) include, for example, a tetrafunctional acrylic acid having four ethylene oxide chains manufactured by Sartomer Co., Ltd. Ester SR-494, a hexafunctional acrylate DPCA-60 having six pentyloxy chains, three trifunctional acrylates TPA-330 having an extended isobutoxy chain, and the like, manufactured by Nippon Kayaku Co., Ltd.

In addition, the polymerizable compound is also preferably disclosed in Japanese Patent Publication No. Sho 48-41708, Japanese Patent Application Laid-Open No. SHO-51-37193, Japanese Patent Publication No. Hei 2-32293, and Japanese Patent Publication No. Hei 2-16765. Documented propylene The acid urethanes are described in Japanese Patent Publication No. Sho 58-49860, Japanese Patent Publication No. SHO 56-17654, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. SHO 62-39418. A urethane compound of an ethylene oxide skeleton. Further, an amine group structure or a thioether structure is contained in the molecule as described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. As the polymerizable compound, an addition polymerizable compound can obtain a curable composition having a very excellent photospeed.

Commercial products of the polymerizable compound include urethane oligomer UAS-10, urethane oligomer UAB-140 (manufactured by Shanyang Guoce Pulp Co., Ltd.), "UA-7200" (Xinzhongcun Chemical Co., Ltd.) Manufactured by the company, DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Co., Ltd.).

Regarding a cyclic ether (epoxy or oxetane), for example, as a compound having an epoxy group, the bisphenol A type epoxy resin is JER-827, JER-828, JER-834, JER-1001, JER- 1002, JER-1003, JER-1055, JER-1007, JER-1009, JER-1010 (above is manufactured by Japan Epoxy Resin Co., Ltd.), Epiclon 840, EPICLON 860, Epiclon 1050, Epiclon 1051, Epiclon 1055 (above is manufactured by Di Aisheng (DIC) Co., Ltd.), bisphenol F epoxy resin is JER-806, JER-807, JER-4004, JER-4005, JER-4007, JER-4010 (above made by Japan Epoxy Resin Co., Ltd.), Abby Clones (EPICLON) 830, Abby Cloone (EPICLON) 835 (the above is manufactured by Di Ai Sheng (DIC) Co., Ltd.), LCE-21, RE-602S (the above is manufactured by Nippon Chemical Co., Ltd.), etc., and the phenol novolak type epoxy resin is JER-152. JER-154, JER-157S70, JER-157S65 (above made by Japan Epoxy Resin Co., Ltd.), Epiclon N-740, EPICLON N-740, Epiclon N-770, EPICLON N-775 (the above is manufactured by Di Aisheng (DIC) Co., Ltd.), etc., cresol novolak type epoxy resin can be listed as Epiclon (EPICLON) N-660, Abby Cloning (EPICLON) N-665, Epiclon N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, Abby Cloning (EPICLON) N-695 (above is manufactured by Di Ai Sheng (DIC) Co., Ltd.), EOCN-1020 (above is manufactured by Nippon Kayaku Co., Ltd.), and aliphatic epoxy resin can be listed as Adeco resin (ADEKA RESIN) ) EP-4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (above ADEKA), Celloxide 2021P, Celloxide 2081, Celloxide 2083, Cyrusid ( Celloxide) 2085, EHPE-3150 (1,2-epoxy-4-(2-oxopropyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol), EPOLEAD PB 3600, EPOLEAD PB 4700 (above produced by Daicel Chemical Industry Co., Ltd.), Denacol EX-211L, Denacol (Denacol) EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L, Denacol EX-850L (above) for Nagase Chemtex (manufactured by Nagase Chemtex), ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, Ai ADEKA RESIN EP-4011S (above ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above) It is manufactured by ADEKA Co., Ltd., JER-1031S (made by Nippon Epoxy Co., Ltd.), Epiclon (HPC200) HP7200 (manufactured by Dickson (DIC) Co., Ltd.), and the like. The epoxy compound is suitable for the case of forming a pattern by dry etching.

Regarding the polymerizable compounds, the details of the method of use, the use alone or in combination, the amount of addition, and the like can be arbitrarily set depending on the final performance design of the coloring composition. For example, from the viewpoint of sensitivity, it is preferred that the structure has a large content of unsaturated groups per molecule, and in many cases, it is preferably a difunctional or higher. In addition, from the viewpoint of improving the strength of the cured film formed by the colored composition, it is preferably a trifunctional or higher functional group, and further, a combination of different functional groups and different polymerizable groups (for example, acrylate or methacrylic acid) A method of adjusting both sensitivity and strength by an ester, a styrene compound, or a vinyl ether compound is also effective. Further, a polymerizable compound having a trifunctional or higher functional group and a different ethylene oxide chain length is preferably used in that the developability of the colored composition can be adjusted, and excellent pattern forming ability can be obtained.

In addition, the compatibility and dispersibility of other components (for example, a photopolymerization initiator, a dispersion, an alkali-soluble resin, and the like) contained in the coloring composition are also important for the selection and use of the polymerizable compound. The factors can be improved, for example, by using a low-purity compound or a combination of two or more. In addition, it will improve From the viewpoint of the adhesion of the hard surface of the support or the like, a specific structure may be selected.

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

The composition of the present invention may contain only one kind of polymerizable compound, and may contain two or more types. When two or more cases are contained, it is preferable that the total amount is the said range.

<<<Alkali Soluble Resin>>

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

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

The alkali-soluble resin can be appropriately selected from the following alkali-soluble resins, which are linear organic high molecular polymers, and are molecules (preferably molecules having an acrylic copolymer or a styrene copolymer as a main chain). There is at least one group that promotes alkali solubility. From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, or an acrylic acid/acrylamide copolymer resin is preferred in terms of controlling developability. In particular, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin is preferable.

Examples of the group which promotes 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, and are preferably soluble in an organic solvent and can be developed by a weakly basic aqueous solution. As the group, a (meth)acrylic group can be cited as Very good. These acid groups may be used alone or in combination of two or more.

Examples of the monomer which can give an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate or a monomer having an epoxy group such as glycidyl (meth)acrylate, ( A monomer having an isocyanate group such as 2-ethyl isocyanatoethyl methacrylate. These monomers for introducing an acid group may be used alone or in combination of two or more. In order to introduce an acid group into the alkali-soluble resin, for example, a monomer having an acid group and/or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as "a monomer for introducing an acid group") may be used. The polymerization may be carried out as a monomer component.

In the case where a monomer capable of imparting an acid group after polymerization is introduced as a monomer component, it is necessary to carry out a treatment for imparting an acid group as described later after the polymerization.

When the alkali-soluble resin is produced, for example, a known method using a radical polymerization method can be applied. The polymerization conditions such as the temperature, the pressure, the type and amount of the radical initiator, and the kind of the solvent when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art, and can also be determined experimentally. condition.

The linear organic high molecular polymer used as the alkali-soluble resin is preferably a polymer having a carboxylic acid in a side chain, and examples thereof include a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, and a butenoic acid copolymer. , an alkali-soluble phenol resin such as a maleic acid copolymer, a partially esterified maleic acid copolymer, or a novolac type resin, and an acidic cellulose derivative having a carboxylic acid in a side chain, and a polymer addition to a hydroxyl group Anhydride is the only one. In particular, copolymers of (meth)acrylic acid with other monomers copolymerizable therewith are suitable as alkali-soluble resins. Other monomers copolymerizable with (meth)acrylic acid Examples thereof include alkyl (meth)acrylate, aryl (meth)acrylate, and a vinyl compound. Examples of the alkyl (meth)acrylate and the aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Ester, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate , (methyl) methacrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc., and examples of the vinyl compound include styrene, α-methyl styrene, vinyl toluene, and methacrylic acid. Glycidyl ester, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, etc., Japanese Patent Laid-Open 10 N-phenylmaleimide, N-cyclohexylmaleimide, which is a N-substituted maleimide monomer described in the publication No. -300922. Further, these other monomers copolymerizable with (meth)acrylic acid may be used alone or in combination of two or more.

The alkali-soluble resin preferably contains a polymer (a) which is a single compound (hereinafter sometimes referred to as "ether dimer") which is represented by the following formula (ED). The body components are polymerized.

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.

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

Specific examples of the ether dimer include dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate (dimethyl-2,2'-[oxybis(methylene)]. Bis-2-propenoate), diethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, di(n-propyl)-2,2'-[oxybis( Methylene)]bis-2-acrylate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(n-butyl)-2, 2'-[oxybis(methylene)]bis-2-acrylate, di(isobutyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, two (t-butyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(third amyl)-2,2'-[oxybis(methylene) )] bis-2-acrylate, bis(stearyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, Bis(lauryl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(2-ethylhexyl)-2,2'-[oxybis(methylene) )] bis-2-acrylate, bis(1-methoxyethyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(1-ethoxyB) -2,2'-[oxybis(methylene)]bis-2-acrylate, dibenzyl-2,2'-[oxybis(methylene)]bis-2-acrylate , diphenyl-2,2'-[oxybis(methylene)]bis-2-acrylate, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2- Acrylate, bis(t-butylcyclohexyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(dicyclopentadienyl)-2,2'- [oxybis(methylene)]bis-2-acrylate, bis(tricyclodecyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, two ( Isobornyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, diamantyl-2,2'-[oxybis(methylene)]bis-2 - acrylate, bis(2-methyl-2-adamantyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, and the like. In these specific examples, particularly preferred is dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, diethyl-2,2'-[oxybis(Asia Methyl)]bis-2-acrylate, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-acrylate, dibenzyl-2,2'-[oxy double (Methylene)] bis-2-acrylate. These ether dimers may be used alone or in combination of two or more. The structure derived from the compound represented by the general formula (ED) may also copolymerize other monomers.

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

[化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 an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. Indicates an integer from 1 to 15)

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

Further, in order to improve the crosslinking efficiency of the colored composition of the present invention, an alkali-soluble resin having a polymerizable group may also be used. The alkali-soluble resin having a polymerizable group is preferably an alkali-soluble resin containing an allyl group, a (meth)acrylic group, an allyloxyalkyl group or the like in a side chain. Examples of the polymerizable group-containing polymer include Dianan NR series (manufactured by Mitsubishi Rayon Co., Ltd.) and Photomer 6173 (COOH-containing acrylic urethane oligomer (polyurethane). Acrylic oligomer), manufactured by Diamond Shamrock Co., Ltd., Biscoat R-264, KS Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.) ), Cyclomer P series, Placcel CF200 series (all manufactured by Daicel Chemical Industry Co., Ltd.), Ebecryl 3800 (Daicel UCB) Limited stock Company manufacturing) and so on. The alkali-soluble resin containing a polymerizable group is preferably a resin containing a polymerizable double bond modified by a urethane, which is left by reacting an isocyanate group with an OH group in advance. An unreacted isocyanate group containing a (meth) acrylonitrile group-containing compound and a reaction with a carboxyl group-containing acrylic resin; and an unsaturated group-containing acrylic resin which is a carboxyl group-containing acrylic resin and a molecule The reaction is carried out by a reaction of a compound having an epoxy group and a polymerizable double bond; an acid side-position epoxy acrylate resin; and an OH group-containing acrylic resin and a dibasic acid anhydride having a polymerizable double bond; An acrylic resin containing a polymerizable double bond; a resin obtained by reacting an OH group-containing acrylic resin, an isocyanate, and a compound having a polymerizable group; Japanese Patent Laid-Open No. 2002-229207 and Japanese Patent Laid-Open No. 2003- A resin obtained by subjecting the following resin to alkaline treatment as described in Japanese Patent Publication No. 335814, wherein the resin has a halogen atom or a sulfonate at the α-position or the β-position on the side chain. An ester group such as an acid ester group or the like. Further, Acrycure RD-F8 (manufactured by Nippon Shokubai Co., Ltd.) is also preferable.

The alkali-soluble resin is particularly preferably a benzyl (meth)acrylate/(meth)acrylic copolymer or a multicomponent copolymer comprising benzyl (meth)acrylate/(meth)acrylic acid/other monomer. In addition, benzyl (meth)acrylate/(meth)acrylic acid/(meth)acrylic acid-2-hydroxyethyl ester copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate may be mentioned. Japanese Patent Publication No. 7-140654, 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-2-acrylate- 3-phenoxypropyl ester/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene giant Methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, etc. a copolymer of benzyl acrylate/methacrylic acid, and the like.

The alkali-soluble resin can be referred to the following paragraphs 0558 to 5571 of the Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to U.S. Patent Application Publication No. 2012/0235099, the specification of [0685] to [0700]). The content is incorporated into the specification of the present application.

Further, it is preferable to use the following resin: the copolymer (B) described in Paragraph No. 0029 to Paragraph No. 0063 described in JP-A-2012-32767, and the alkali-soluble resin used in the examples, Japanese Patent Laid-Open No. 2012 The adhesive resin described in Paragraph No. 0088 to Paragraph No. 0098 of the Japanese Patent Publication No. 208474, and the adhesive resin used in the examples, and the adhesive described in Paragraph No. 0022 to Paragraph No. 0032 of JP-A-2012-137531 The binder resin used in the resin and the examples, the binder resin described in paragraph No. 0132 to paragraph number 0143 of JP-A-2013-024934, and the binder resin used in the examples, Japanese Patent Laid-Open No. 2011- The adhesive resin described in Paragraph No. 0092 to Paragraph No. 0098 of the Japanese Patent Publication No. 242752, and the adhesive resin used in the examples, and the paragraph number 0030 to paragraph 0072 of JP-A-2012-032770. This is incorporated into the specification of the present application. More specifically, the following resins are preferred.

[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, particularly preferably from 70 mgKOH/g to 120 mgKOH/g.

Further, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably from 2,000 to 50,000, more preferably from 5,000 to 30,000, particularly preferably from 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 from 1% by mass to 15% by mass, more preferably from 2% by mass to 12% by mass, based on the total solid content of the coloring composition. It is particularly preferably from 3 mass% to 10 mass%.

The composition of the present invention may contain only one alkali-soluble resin, or may contain two or more kinds. When two or more cases are contained, it is preferable that the total amount is the said range.

<Other ingredients>

The coloring composition of the present invention may contain an organic solvent, a crosslinking agent, a polymerization inhibitor, a surfactant, an organic carboxylic acid, or an organic substance in addition to the above-described respective components, without departing from the effects of the present invention. Other components such as carboxylic anhydride.

<<Organic solvent>>

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

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

The organic solvent may preferably be exemplified by 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, alkyl oxyacetate (eg methyl oxyacetate, oxy) Ethyl acetate, butyl oxyacetate (such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3 - alkyl oxypropionates (for example, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate) , 3-ethoxypropionate methyl ester, 3-ethoxypropionate ethyl ester, etc.), 2-oxypropionic acid alkyl esters (such as methyl 2-oxypropionate, 2-oxypropane) Ethyl acetate, propyl 2-oxypropionate, etc. (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxyl) Methyl propionate, ethyl 2-ethoxypropionate), methyl 2-oxy-2-methylpropanoate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy) Methyl 2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, B Acetic acid B , methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.; and as an ether such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, A Cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether An acid ester, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.; and as a ketone such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc.; And as aromatic hydrocarbons, for example, toluene, xylene, and the like.

The organic solvent is preferably mixed in two or more kinds from the viewpoints of improving the solubility of the ultraviolet absorber and the alkali-soluble resin, the surface condition of the coating, and the like. In this case, it is particularly preferable to be a mixture of two or more selected from the following organic solvents. Solution: the methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3 Methyl methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate.

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

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

The composition of the present invention may contain only one kind of organic solvent, and may contain two or more types. When two or more cases are contained, it is preferable that the total amount is the said range.

<<Crosslinker>>

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

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

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

In the case where the coloring composition of the present invention contains a crosslinking agent, the amount of the crosslinking agent to be added is not particularly limited, but is preferably 2% by mass to 30% by mass, more preferably 3% by mass based on the total solid content of the composition. %~20% by mass.

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

<<Polymerization inhibitor>>

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

The polymerization inhibitor which can be used in the present invention may, for example, be hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-Asia Nitrophenylhydroxylamine sulfonium salt and the like.

When the coloring composition of the present invention contains a polymerization inhibitor, the amount of the polymerization inhibitor added is preferably from about 0.01% by mass to about 5% by mass based on the mass of all the components.

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

<<Interfacial active agent>>

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

In particular, since the coloring composition of the present invention contains a fluorine-based surfactant, the solution characteristics (especially fluidity) at the time of preparation of the coating liquid are further improved, so that the uniformity of the coating thickness or the liquid-saving property can be further improved.

In other words, when the film formation is carried out using a coating liquid using a coloring composition containing a fluorine-based surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the surface to be coated is applied. The wettability is improved, and the coatability to the coated surface is improved. Therefore, even when a film having a thickness of a few micrometers (μm) is formed with a small amount of liquid, it is possible to more preferably form a film having a uniform thickness having a small thickness unevenness, which is effective in this respect.

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

Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, and Megafac F141. , Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781 (above produced by Di Aisheng (DIC)), Vlad (Fluorad) FC430, Fluorad FC431, Fluorad FC171 (above Sumitomo 3M (share)), Surflon S-382, Surflon SC-101 , Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, sand Surflon SC-383, Surflon S393, Surflon KH-40 (above manufactured by Asahi Glass), PF636, PF656, PF6320, PF6520, PF7002 (Ounofa ( OMNOVA) manufactured by the company).

A block polymer can be used as the fluorine-based surfactant. Specific examples thereof include a compound described in JP-A-2011-89090.

Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates (for example, propoxylated glycerin, ethoxylated glycerin). Etc.), polyoxyethylene ethyl lauryl ether, polyoxyethylene ethyl stearyl ether, polyoxyethylene ethyl olefin ether, polyoxyethyl octyl phenyl ether, polyoxyethyl thiol Phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, manufactured by BASF), Pluronic L31 , Pluronic L61, Pluronic L62, Pluronic 10R5, Pluronic 17R2, Pluronic 25R2, Tetronic 304, Tetronic 701, Tetronic 704, Tetronic 901, Tetronic 904, Tetronic 150R1), Solsperse 20000 (Japan Road) Lubrizol (shares) and so on.

Specific examples of the cationic surfactant include a phthalocyanine derivative (trade name: Efka (EFKA)-745, manufactured by Morishita Industries Co., Ltd.), and an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). , (meth)acrylic (co)polymer Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (Kyoeisha Chemicals ( () manufacturing), W001 (Yu Shang (share) manufacturing) and so on.

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

Examples of the fluorenone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, and East, manufactured by Toray-Dow Corning Co., Ltd. Toray Silicone DC11PA", "Toray Silicone SH21PA", "Toray Silicone SH28PA", "Toray Silicone SH29PA", "Dong Lizhen" Toray Silicone SH30PA", "Toray Silicone SH8400", "TSF-4440", "TSF-4300", "TSF-4445" manufactured by Momentive Performance Materials "TSF-4460" and "TSF-4452", "KP341", "KF6001" and "KF6002" manufactured by Shin-Etsu Chemical Co., Ltd., "BYK 307" manufactured by BYK Chemie , "BYK 323", "BYK" 330, etc.

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

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

<<Organic carboxylic acid, organic carboxylic anhydride>>

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

Specific examples of the organic carboxylic acid compound include an aliphatic carboxylic acid or an aromatic carboxylic acid. Examples of the aliphatic carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, glycolic acid, acrylic acid, and methacrylic acid, and oxalic acid, malonic acid, and amber. Dicarboxylic acids such as acid, glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, etc. Tricarboxylic acid such as 2,3-propanetricarboxylic acid or aconitic acid. Further, examples of the aromatic carboxylic acid include a carboxylic acid in which a carboxyl group such as benzoic acid or phthalic acid is directly bonded to a phenyl group, and a carboxylic acid in which a carboxyl group is bonded from a phenyl group via a carbon bond. Among these, a molecular weight of 600 or less, particularly a molecular weight of 50 to 500 is particularly preferable, and specific examples thereof include 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, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, and Malay. An aliphatic carboxylic acid such as an acid anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride Anhydride. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. The In particular, it is particularly preferably a molecular weight of 600 or less, particularly a molecular weight of 50 to 500. Specifically, for example, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferable.

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

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

By adding these organic carboxylic acids and/or organic carboxylic anhydrides having a molecular weight of 1,000 or less, high pattern adhesion can be maintained, and the remaining of the colored composition can be further reduced.

In addition to the additives, various additives such as a filler, a adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomerating agent, and the like may be blended as needed in the coloring composition. The additives are described in paragraphs 0155 to 0156 of JP-A-2004-295116, the contents of which are incorporated herein by reference.

The coloring composition of the present invention may contain the sensitizer or light stabilizer described in paragraph 0078 of JP-A-2004-295116, and the heat-resistant polymerization agent described in paragraph 0081 of the publication.

The composition of the present invention may contain only one kind of the above components, and may contain two or more kinds. When two or more cases are contained, it is preferable that the total amount is the said range.

<Method for Preparing Colored Composition>

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

Further, when preparing a colored composition, each component constituting the colored composition may be formulated at once, or each component may be dissolved and dispersed in a solvent, and then successively formulated. In addition, the order of input or the working conditions at the time of preparation are not particularly limited. For example, all the components may be simultaneously dissolved and dispersed in a solvent to prepare a composition, and if necessary, each component may be appropriately prepared into two or more kinds of solutions and dispersions, and mixed at the time of use (at the time of coating). It was prepared into a composition.

In order to remove foreign matter, reduce defects, and the like, the colored composition of the present invention is preferably filtered by a filter. It is not particularly limited as long as it has been used for filtration purposes and the like. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon-6 or nylon-6, 6 or a polyolefin resin such as polyethylene or polypropylene (including polypropylene) may be mentioned. Filters such as density, ultra high molecular weight). Among these raw materials, polypropylene (including high density polypropylene) is preferred.

The pore diameter of the filter is preferably from about 0.01 μm to about 7.0 μm, more preferably from about 0.01 μm to about 3.0 μm, and still more preferably from about 0.05 μm to about 0.5 μm. By setting this range, it is possible to reliably remove fine foreign matter which prevents the preparation of the uniform and smooth coloring composition in the subsequent steps.

Different filters can also be combined when using filters. At this time, the filtration by the first filter may be performed only once or twice or more.

Further, the first filters having different pore diameters may be combined in the above range. this The aperture of the filter can be referred to the nominal value of the filter maker. Commercially available filters are available, for example, from Pall Co., Ltd., Advantec Toyo Co., Ltd., and Japan's Entegris Co., Ltd. (formerly Japan's Microris) Ltd.) or a variety of filters available from KITZ Micro Filter Co., Ltd., etc.

The second filter can be formed of the same material or the like as the first filter.

For example, the filtration by the first filter may be performed using only the dispersion, and the second filtration may be performed after mixing the other components.

The colored composition of the present invention can be preferably used for the formation of a coloring layer of a color filter. More specifically, since the colored composition of the present invention can form a cured film excellent in heat resistance and color characteristics, it can be preferably used for forming a colored pattern (colored layer) of a color filter. In addition, the coloring composition of the present invention can be preferably used for a solid-state imaging device (for example, a CCD, a complementary metal oxide semiconductor (CMOS), or the like) or a liquid crystal display (LCD). A coloring pattern such as a color filter used in a display device is formed. Further, it can also be preferably used for production of printing inks, inkjet inks, paints, and the like. Among them, it can be preferably used as a color filter for producing a solid-state imaging device such as a CCD or a CMOS.

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

Next, the cured film, the pattern forming method, and the color filter of the present invention will be described in detail by a method for producing the same. Further, 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 hardening the colored composition of the present invention. The cured film can be preferably used for a color filter.

The pattern forming method of the present invention applies the coloring composition of the present invention to a support to form a colored composition layer, and removes an unnecessary portion to form a colored pattern.

The pattern forming method of the present invention can be preferably used to form a color pattern (pixel) which the color filter has.

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

That is, the first embodiment of the pattern forming method of the present invention can be exemplified by a pattern forming method including the steps of applying a colored composition to a support to form a colored composition layer, and patterning the colored composition layer in a pattern. a step of exposing; and a step of developing the unexposed portion to form a colored pattern.

Further, a second embodiment of the pattern forming method of the present invention can be exemplified by a pattern forming method comprising the steps of applying a colored composition to a support to form a colored composition layer, and hardening it 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 etch mask .

This patterning method is used to fabricate a colored layer of a color filter. That is, in the present invention, a method of manufacturing a color filter including the pattern forming method of the present invention is also disclosed.

The methods are described in detail below.

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

<<Steps of forming a colored composition layer>>

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

For the support which can be used in this step, for example, a substrate (for example, a germanium substrate) may be provided with a charge coupled device (CCD) or a complementary metal-oxide semiconductor (CMOS). A substrate for a solid-state image sensor of an element (light receiving element).

The colored pattern of the present invention can be formed on the imaging element forming surface side (surface) of the solid-state imaging device substrate, or can be formed on the surface side (back surface) where the imaging element is not formed.

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

Further, on the support, an undercoat layer may be provided as needed to improve adhesion to the upper layer, to prevent diffusion of substances, or to planarize the surface of the substrate. In the undercoat layer, The solvent, the alkali-soluble resin, the polymerizable compound, the polymerization inhibitor, the surfactant, the photopolymerization initiator, and the like may be appropriately selected, and the components are preferably appropriately selected from the components formulated into the composition of the present invention. .

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

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

<Case where pattern formation is performed by photolithography>

<<Steps for exposure>>

In the exposure step, an exposure device such as a stepper is used for the colored composition layer formed in the colored composition layer forming step, and a mask having a predetermined mask pattern is interposed to perform pattern exposure. Thereby, a cured film can be obtained.

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

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

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

Further, in this step, a cured film having a thin film thickness of 0.7 μm or less can be preferably formed, and the obtained cured film can be developed by a pattern forming step described later, whereby a film can be obtained, and developability can be obtained. A coloring pattern excellent in surface roughness suppression and pattern shape.

<<Development step>>

Then, an alkali development treatment is performed, whereby the colored composition layer of the portion which is not irradiated with light in the exposure step is eluted into the alkaline aqueous solution, and only the photohardened portion remains.

The developer is desirably an organic alkali developer which does not cause damage to the underlying imaging element or circuit. The development temperature is usually 20 ° C to 30 ° C, and the development time is 20 seconds to 90 seconds. In order to further remove the residue, in recent years, it has been carried out for 120 seconds to 180 seconds. Further, in order to further improve the residue removal property, the following steps may be repeated several times: the developer is removed every 60 seconds, and the developer is further supplied again.

Examples of the alkaline agent used in the developing solution include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. Preferably, an organic basic compound such as a solution of a solution such as ammonium amide, trimethylbenzylammonium hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo-[5.4.0]-7-undecene is preferred. An alkaline aqueous solution obtained by diluting the alkali agent so as to have a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass, is used as a developing solution.

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

Further, in the case of using a developing solution containing such an alkaline aqueous solution, it is usually washed (rinsed) with pure water after development.

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

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

The heating film or a convection oven (hot air circulation dryer), a high-frequency heating machine or the like may be used to perform the post-drying of the developed coating film in a continuous or batch manner in such a manner as to be the condition. Baked.

For the formation of a pattern by dry etching, the contents of the Japanese Patent Application Laid-Open No. 2013-64993 are incorporated herein by reference.

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

Further, in the case of using the colored composition of the present invention, for example, clogging of the nozzle or the piping portion of the coating device discharge portion or adhesion, sedimentation, and drying of the colored composition or pigment in the coater may occur. Pollution and so on. Therefore, in order to efficiently clean the contamination caused by the coloring composition of the present invention, it is preferred to use a solvent related to the present composition described above as a cleaning liquid. In addition, the Japanese patent special Kaiping Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A cleaning liquid described in, for example, Japanese Patent Application Laid-Open No. Hei. No. 2007-2102, Japanese Patent Laid-Open Publication No. Hei No. 2007-281523, and the like can be preferably used in the present invention. The cleaning of the colored composition is removed.

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

These solvents may be used singly or in combination of two or more. In the case of mixing two or more kinds, it is preferred to mix a solvent having a hydroxyl group with a solvent having no hydroxyl group. The mass ratio of the solvent having a hydroxyl group to the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. Particularly preferred is a mixed solvent of Propyleneglycol monomethylether acetate (PGMEA) and Propyleneglycol monomethylether (PGME) in a ratio of 60/40. Further, in order to increase the permeability of the cleaning liquid to the contaminants, a surfactant related to the above-described composition 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 pattern shape of the formed color pattern (colored pixel) is excellent, and the surface of the pattern is rough or The residue of the developing unit is suppressed, so that the color characteristics are excellent.

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

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

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

<Solid image sensor>

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

The solid-state imaging device has a configuration in which a plurality of photodiodes (photodiodes) constituting a light receiving region of a solid-state imaging device (a CCD image sensor, a CMOS image sensor, or the like) and a polycrystalline germanium or the like are provided on a support. The transmission electrode has a light-shielding film containing tungsten or the like which is opened only by the light-receiving portion of the photodiode, and has a light-shielding film covering the entire surface of the light-shielding film and the photodiode light-receiving portion. The element protective film containing tantalum nitride or the like is formed, and the color filter for solid-state imaging device of the present invention is provided on the element protective film.

Further, it may be configured to have a light collecting means (for example, a microlens or the like, the same applies hereinafter) on the element protective layer and under the color filter (on the side close to the support), or The color filter has a configuration of a light collecting mechanism and the like.

<Image display device>

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

The definition of the display device or the details of each display device is described in, for example, "Electronic display device (Sasaki Sasaki, Industrial Research Association, stocks, issued in 1990)", "Display elements (Ibuki Shun, industrial books) (shares), issued in 1989) and so on. In addition, the liquid crystal display device is described, for example, in "Next-Generation Liquid Crystal Display Technology (Editor Uchida Ronjin, Industrial Research Association, issued in 1994)". The liquid crystal display device to which the present invention is applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the "next-generation liquid crystal display technology".

The color filter of the present invention can also be used in a liquid crystal display device of a Thin Film Transistor (TFT) type. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., issued in 1996)". Furthermore, the present invention can also be applied to an enlarged liquid crystal display such as a transverse electric field driving method such as In-Plane Switching (IPS) or a pixel division method such as multi-domain vertical alignment (MVA). Device or Super Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (Vertical Alignment, VA), Optically Compensated Splay (OCS), Fringe Field Switching (FFS), and Reflective-Optically Compensated Bend (R-OCB).

In addition, the color filter of the present invention can also be used in a bright and high-definition Color-filter On Array (COA) mode. In the COA liquid crystal display device, in addition to the usual required characteristics as described above, the required characteristics of the color filter layer may require the required characteristics of the interlayer insulating film, that is, low dielectric constant and resistance. Stripping liquidity. In the color filter of the present invention, since the coloring matter is excellent in color purity and light transmittance, and the color tone of the colored pattern (pixel) is excellent, it is possible to provide a high resolution and excellent long-term durability. COA liquid crystal display device. Further, in order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.

These image display methods are described, for example, in "Electroluminescence (EL), Plasma Display Panel (PDP), Liquid Crystal Display (LCD) displays - technology and market. Trends - (Toray Research Center, Research and Research Department, issued in 2001), 43 pages, etc.

The liquid crystal display device including the color filter of the present invention comprises, in addition to the color filter of the present invention, an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle securing film. . The color filter of the present invention can be applied to a liquid crystal display device composed of such known members. These components are described, for example, in the "94 LCD Peripheral Materials - Chemicals City" Field (Kentaro Kentaro, CMC (shares), issued in 1994)", "The status and future prospects of the liquid crystal-related market in 2003 (volume) (Former Liangji, Fuji Kamelai Institute (share), issued in 2003)" .

The backlight is recorded on the 18th page of the December 2005 issue of the "SID meeting Digest" (1380 (2005)) (A. Konno et al.) or the monthly display. 24 pages (Island Kang Yu) and the document 25 to 30 pages (Yamu Longming) and so on.

When the color filter of the present invention is used in a liquid crystal display device, high contrast can be achieved when combined with a three-wavelength tube of a conventionally known cold cathode tube, and the red, green, and blue LED light source can be realized by RGB-LED is set as a backlight, and can provide a liquid crystal display device with high brightness and high color reproducibility.

[Examples]

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

<Synthesis Example 1: Synthesis of Pigment Multimer Used in Example 1>

31.2 g of cyclohexanone was added to a three-necked flask, and the mixture was heated to 90 ° C under a nitrogen atmosphere. Monomer 1 (35.0 g, 32.3 mmol), methacrylic acid (9.64 g, 112 mmol), dodecanethiol (2.75 g, 13.6 mmol), polyethylene glycol monomethyl group were added dropwise to the solution for 1 hour. Acrylate [trade name: Blemmer PE-90, manufactured by Nippon Oil Co., Ltd.)] (3.52g), 2,2'-azobis(isobutyric acid) dimethyl ester [trade name: V601 , a mixed solution of Wako Pure Chemical Industries Co., Ltd. (6.25 g, 27.1 mmol) and cyclohexanone (81.2 g). Thereafter, the mixture was stirred at 90 ° C for 3 hours, cooled to room temperature, and added dropwise to a mixed solvent of ethyl acetate / acetonitrile = 1530 mL / 170 mL to carry out reprecipitation. After drying at 40 ° C for one day, 25.3 g of Pigment Polymer 2 was obtained. The acid value of the dye polymer 2 was 2.23 mmol/g, and the composition ratio (mole ratio) was confirmed by ¹ H-NMR. As a result, the dye portion: methacrylic acid portion: PE-90 portion = 20:68:12.

The obtained Pigment Polymer 2 (12.5 g), glycidyl methacrylate (2.19 g), tetraethylammonium bromide (0.40 g), and p-methoxyphenol (0.015 g) were added to a three-necked flask. Cyclohexanone (83.3 g) was stirred at 105 ° C for 4 hours under air. Thereafter, the mixture was cooled to room temperature, and added dropwise to a mixed solvent of ethyl acetate / acetonitrile = 748 mL / 39 mL to carry out reprecipitation. After drying at 40 ° C for one day, a pigment polymer 3 of 6.52 g was obtained. The acid value of the dye polymer 3 was 1.01 mmol/g, and the composition ratio (mol ratio) was confirmed by ¹ H-NMR. As a result, the dye portion: methacrylic acid portion: polymerizable base: PE-90 portion = 20: 36:32:12.

<Synthesis of Pigment Polymers Used in Other Examples and Comparative Examples>

<Synthesis of Pigment Polymers (Examples 2 to 42 and Comparative Examples 1 to 11)

The monomers 1 and methacrylic acid and polyethylene glycol monomethacrylate in Synthesis Example 1 were changed to form a repeating unit described in the following Table 1, and the same operation was carried out to synthesize the same. .

<Synthesis Example 2: Synthesis of Pigment Polymer Used in Example 43>

39.2 g of N-ethylpyrrolidone was added to a three-necked flask, and the mixture was heated to 90 ° C under a nitrogen atmosphere. In this solution, monomer 4 (40.0 g, 35.4 mmol), methacrylic acid (MAA, 4.62 g, 53.7 mmol), dodecanethiol (2.79 g, 13.8 mmol), polyethylene glycol were added dropwise over 1 hour. Monomethacrylate [trade name: Blemmer PE-90, manufactured by Nippon Oil Co., Ltd.] (3.38 g), ethylene glycol mono-2-bromoisobutyrate monomethacrylate (BBEM, 12.5 g, 44.8 mmol), 2,2'-azobis(isobutyric acid) dimethyl ester [trade name: V601, manufactured by Wako Pure Chemical Industries, Ltd.] (6.25 g, 27.1 mmol), N-ethyl A mixed solution of pyrrolidone (91.4 g). Thereafter, 10.54 g of N-ethylpyrrolidone was added, and the mixture was stirred at 90 ° C 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 radical were added to the reaction mixture, and the mixture was slowly added. 47.6 g of azabicycloundecene (DBU) was stirred at room temperature for 14 hours. Then, it 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 slowly added. After the reaction, the reaction solution was added dropwise to 4800 mL of 1 mol/l hydrochloric acid water, followed by precipitation, and the solid obtained by filtration was added to 250 parts of acetonitrile for suspension washing, and the filtrate was again filtered to obtain the present invention shown below. Pigment polymer 6 50.0 g. The weight average molecular weight (polystyrene equivalent value) of the dye polymer 6 was 8,000, and the acid value was 0.74 mmol/g by titration with a 0.1 mol/l sodium hydroxide aqueous solution. When the composition ratio (Morby ratio) was confirmed by ¹ H-NMR, the dye portion: methacrylic portion: polymerizable base: PE-90 portion = 28:31:27:14.

<Synthesis of Pigment Polymer (Examples 44 to 75)>

The monomer 4, the methacrylic acid, and the polyethylene glycol monomethacrylate in the synthesis example 2 were changed in the same manner as the repeating unit described in the following Table 3, and the same operation was carried out to synthesize the same. .

1. Preparation of resist liquid

A component liquid of the following composition was mixed and dissolved to prepare a resist liquid for an undercoat layer.

Composition of resist liquid for undercoat layer

. Solvent: propylene glycol monomethyl ether acetate 19.20 parts

. Solvent: ethyl lactate 36.67 parts

. Alkali-soluble resin: benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer (mol ratio = 60 / 22 / 18, weight average molecular weight of 15,000, number average molecular weight of 9,000) 40 30.51 parts of %PGMEA solution

. Compound containing ethylenically unsaturated double bond: dipentaerythritol hexaacrylate 12.20 parts

. Polymerization inhibitor: p-methoxyphenol 0.0061 parts

. Fluorine-based surfactant: F-475, Dickson (DIC) (share) manufacturing 0.83

. Photopolymerization initiator: 0.586 parts of photo-polymerization initiator of trihalomethyltriazine

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

2. Fabrication of tantalum wafer substrate with undercoat

The undercoated silicon wafer used in the evaluation was fabricated in the following manner.

Apply CT-4000L evenly on a 200mm (8吋) tantalum wafer by spin coating (Fujifilm Electro-Materials) was used to form a coating film, and the formed coating film was treated in an oven at 220 ° C for 1 hour to cure the coating film to form a primer. Floor. Further, the application rotation speed of the spin coating was adjusted so that the film thickness of the coating film after the heat treatment became about 0.1 μm.

3. Preparation of coloring composition

3-1. Preparation of Blue Pigment Dispersion

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

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

That is, 19.4 parts by mass of CI Pigment Blue 15:6 (blue pigment; hereinafter also referred to as "PB15:6") was contained by a beads mill (zirconia beads, diameter: 0.3 mm) (on average A mixed liquid of a particle dispersing agent of 55 nm), a pigment dispersing agent BY-161 (manufactured by BYK Co., Ltd.) of 2.95 parts by mass, 2.95 parts by mass of an alkali-soluble resin 1 and 172.3 parts by mass of PGMEA was mixed and dispersed for 3 hours. Then, using a high-pressure disperser NANO-3000-10 (manufactured by BEE Co., Ltd.) equipped with a pressure reducing mechanism, a dispersion treatment was carried out at a flow rate of 500 g/min under a pressure of 2000 kg/cm ³ . The dispersion treatment was repeated 10 times to obtain a CI Pigment Blue 15:6 dispersion as a pigment dispersion. The obtained CI Pigment Blue 15:6 dispersion was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)), The result was 24 nm.

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

In the preparation of the P1, the following dispersant D1 is used as a pigment dispersant, Otherwise, the pigment dispersion liquid P2 was prepared by the same operation.

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

In the preparation of the P1, the following dispersant D2 was used as the pigment dispersant, and the pigment dispersion liquid P3 was prepared by the same operation.

3-2. Preparation of coloring composition

(Preparation of Colored Composition 1) (Examples 1 to 40, Comparative Example 1 to Comparative Example 11)

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

. Organic solvent (cyclohexanone): 17.12 parts

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

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

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

. A cyclohexanone solution of a pigment polymer (solid content concentration of 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 (ethylene ethoxylate modified dipentaerythritol hexaacrylate, NK ester (NK Ester) A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)): 1.96 parts

. Polymerization inhibitor (p-methoxyphenol): 0.0007 parts

. Fluorine-based surfactant (F475, 1% PGMEA solution manufactured by Di's Health (DIC)): 2.50 parts

(Preparation of Coloring Composition 2) (Example 41, Example 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 Corporation, epoxy equivalent: 180-220 (g/eq.)): 4.395 parts

. A cyclohexanone solution of a pigment polymer (solid content concentration of 12.3%): 24.57 parts

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

. Polymerization inhibitor (p-methoxyphenol): 0.0007 parts

. Fluorine-based surfactant (F475, 1% PGMEA solution manufactured by Di's Health (DIC)): 2.50 parts

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

The following components were mixed to obtain a colored composition 3.

. Organic solvent (cyclohexanone): 14.69 parts

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

. Alkali-soluble resin 2 (Acrycure RD-F8 (manufactured by Nippon Shokubai Co., Ltd.)): 0.05 parts

. Photopolymerization initiator: 0.78 parts

. A cyclohexanone solution of a pigment polymer (solid content concentration of 12.3%): 28.45 parts

. Pigment Dispersion (C.I. Pigment Blue 15:6 Dispersion, PGMEA Solution, Solid Concentration 12.8%): 51.23

. Polymeric compound: 1.61 parts

. Epoxy compound: 0.39 parts

. Polymerization inhibitor (p-methoxyphenol): 0.0007 parts

. Fluorine-based surfactant (F475, 1% PGMEA solution manufactured by Di's Health (DIC)): 2.50 parts

(Preparation of Coloring Composition 4) (Example 47, Example 48)

The following components were mixed, dispersed, and dissolved to obtain a colored composition 4.

. Organic solvent (cyclohexanone): 17.12 parts

. Epoxy compound (E1): 4.395 parts

. A cyclohexanone solution of a pigment polymer (solid content concentration of 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 parts

. Fluorine-based surfactant (F475, 1% PGMEA solution manufactured by Di's Health (DIC)): 2.50 parts

4. Production of color filter (coloring pattern)

4-1: Production of color filters using photolithography

The colored composition 1 and the colored composition 3 prepared above were applied onto the undercoat layer of the undercoated germanium wafer prepared above to form a colored layer (coating film). Then, heat treatment (prebaking) was performed for 120 seconds using a hot plate of 100 ° C so that the dried film thickness of the coating film was 1 μm.

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

Thereafter, the germanium wafer substrate on which the irradiated coating film is formed is placed on the rotary jet On a horizontal rotating table of a shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), CD-2000 (manufactured by Fujifilm Electronics Materials Co., Ltd.) was used at 23 ° C. After 60 seconds of immersion development, a colored pattern was formed on the undercoat layer of the undercoated germanium wafer.

The germanium wafer on which the colored pattern is formed is fixed on the horizontal rotating table by vacuum chucking, and the crucible wafer is rotated at 50 rpm by the rotating device, and the nozzle is sprayed from above the center of rotation to spray (shower) The pure water was supplied to the rinsing treatment, and then spray-dried, and post-baking was performed at 200 ° C for 300 seconds using a hot plate to obtain a transparent pattern (cured film) having a film thickness of 1 μm on the ruthenium wafer.

As described above, a tantalum wafer with a colored pattern formed of a colored pattern (color filter) is provided on the undercoat layer of the underlying germanium wafer.

Thereafter, the size of the colored pattern was measured using a length-measuring scanning electron microscope (SEM) "S-9260A" (manufactured by Hitachi High-technologies Co., Ltd.).

Patterning property, development residue, and color unevenness (color unevenness) were evaluated using a coloring pattern having a pattern size of 1.0 μm.

4-2: Production of color filters using dry etching

The coloring composition 2 and the coloring composition 4 obtained in the above were applied onto a 7.5 cm × 7.5 cm glass substrate with a film thickness of 0.5 μm using a spin coater, and were carried out at 200 ° C using a hot plate. The coating film was cured by heating in a minute to prepare a colored layer. The film thickness of the colored layer was 0.5 μm.

Next, apply positive-type photoresist "FHi622BC" (Fuji film electronic material (Fujifilm) A fabric baking process was performed at 90 ° C for 1 minute to form a photoresist layer having a film thickness of 0.8 μm.

Then, the photoresist layer was subjected to pattern exposure using an i-ray stepper (manufactured by Canon) at an exposure amount of 350 mJ/cm ² , and the temperature of the photoresist layer or the ambient temperature was 90 ° C. Heat treatment for 1 minute. Thereafter, development treatment was carried out for 1 minute using a developing solution "FHD-5" (manufactured by Fujifilm Electronics Materials Co., Ltd.), and further subjected to post-baking treatment at 110 ° C for 1 minute to form a resist pattern. . The size of the resist pattern was formed in consideration of an etching transition difference (reduction in pattern width due to etching) of 1.0 μm on one side.

Next, the obtained glass substrate was attached to a 200 mm (8 Å) ruthenium wafer, and a dry etching apparatus (U-621, manufactured by Hitachi High-technologies Co., Ltd.) was used, with an RF power of 800 W. Antenna bias: 400W, wafer bias: 200W, internal pressure of the chamber: 4.0Pa, substrate temperature: 50 °C, gas type and flow rate of mixed gas are CF ₄ : 80mL / min, O ₂ : 40mL / min, An etching process of the first stage of 80 seconds was performed in the manner of Ar: 800 mL/min.

Secondly, the same etching chamber is used as follows: RF power: 600 W, antenna bias: 100 W, wafer bias: 250 W, internal pressure of the chamber: 2.0 Pa, substrate temperature: 50 ° C, mixed gas The second stage etching treatment was carried out for 28 seconds in the type and flow rate of N ₂ : 500 mL/min, O ₂ : 50 mL/min, Ar: 500 mL/min (N ₂ /O ₂ /Ar = 10/1/10) , over-etching treatment.

After dry etching under the conditions described above, the photoresist stripping solution "MS230C" was used. (Fujifilm Electronics Materials Co., Ltd.) The peeling treatment was performed at 50 ° C for 120 seconds to remove the resist to form a green colored pattern. Further, washing with pure water and spin drying were carried out, followed by dehydration baking treatment at 100 ° C for 2 minutes. A color filter is obtained in the manner described.

5. Evaluation

5-1. Pattern formation

The obtained color filter was cut with a glass cutter, and the 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 having a line width of 1.0 μm was formed with good linearity.

B: A slight unevenness was observed on the pattern having a line width of 1.0 μm, but it was practically problem-free.

C: The linearity of the pattern having a line width of 1.0 μm was remarkably deteriorated.

5-2. Development residue

Using a scanning electron microscope, a region other than the colored pattern formation region in the ruthenium wafer (unexposed portion) was observed at a magnification of 30,000 times, and evaluated according to the following evaluation criteria.

A: No residue was observed in the region other than the colored pattern formation region (unexposed portion).

B: A slight residue was observed in a region other than the colored pattern formation region (unexposed portion), but it was practically free from problems.

C: A region other than the colored pattern forming region (unexposed portion) is clearly confirmed Residue.

5-3. Spot

The obtained monochromatic color filter (colored pattern) is placed between the observation lens of the optical microscope and the light source, and the light is irradiated toward the observation lens, and the transmission is observed by an optical microscope provided with a digital camera having a magnification of 1000 times. Light state. A 1200-pixel CCD was mounted on a digital camera provided in an optical microscope to capture the surface of the film in a transmitted light state. The captured image is stored as a digital image (digital image) which is digitally converted in the form of a bit map of 8 bits.

Further, the filming of the surface of the film of the colored pattern was performed on 20 regions selected arbitrarily. Further, regarding the digitally converted data, the luminance of the B color is quantized and stored for the captured image with a density distribution of 256 levels of 0 to 255.

Then, the stored digital image is divided into a lattice shape so that one grid size corresponds to 2 μm square on the actual substrate, and the luminance in one block is averaged. In the present embodiment, a digital camera of 1.28 million pixels is used to capture an image 1000 times optically, so 2 μm on the actual substrate becomes 2 mm on the captured image, and the image size on the display is 452 mm × 352 mm, so one The total number of blocks in the area is 39,776.

For all blocks of each region, the average brightness of any one block and all adjacent blocks adjacent thereto is measured. A block having a difference of 5 or more from the average brightness of adjacent blocks is identified as a significant difference block, and the average total number of significant difference blocks in the entire area is calculated as the total difference between the blocks in the entire area and the average total number of blocks in the entire area. Block The ratio of the number (39,776) (hereinafter also referred to as "proportion"). The smaller the value, the less the color unevenness (stain) is judged. It is judged that the number of significant difference blocks is 800 or less and the ratio is 3% or less, which is a practically problem-free level.

Evaluation basis for uneven color (stain)

A: The number of significant differences is less than 500 and the ratio is less than 2%, which is an excellent level.

B: The number of significant difference blocks is 800 or less and the ratio is 3% or less (excluding the case of the A), which is a practically problem-free level.

C: At least one of the number of significant difference blocks exceeding 800 and the ratio exceeding 3% is a practical problem.

5-4. Fading resistance

The coloring composition was applied to the glass substrate so that the film thickness became 0.6 μm by a spin coater, and heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 °C. Then, heat treatment (post-baking) was performed for 300 seconds using a hot plate of 220 ° C to prepare a cured film.

The color filter thus obtained was measured for transmittance in a wavelength range of 300 nm to 800 nm by a spectrophotometer (see: glass substrate) of an ultraviolet-visible near-infrared spectrophotometer UV3600 (manufactured by Shimadzu Corporation). Further, a differential interference image was observed by a reflection observation (magnification of 50 times) using an optical microscope BX60 manufactured by OLYMPUS.

Then, it was immersed in an alkali developing solution FHD-5 (manufactured by Fujifilm Electronics Materials Co., Ltd.) for 5 minutes, dried, and subjected to spectroscopic measurement again to evaluate the change in transmittance before and after solvent impregnation (during solvent immersion) The transmittance before the staining is set to T0, the transmittance after the solvent immersion is set to T1, and the value represented by the formula |T0-T1|) is abnormal with the film surface, and is evaluated by the following criteria. .

AA: Good Transmittance before and after solvent impregnation is less than 2% over the entire range of 300 nm to 800 nm

A: slightly better. The transmittance change before and after solvent immersion is 2% or more and less than 5% in the entire range of 300 nm to 800 nm.

B: sufficient to change the transmittance before and after solvent immersion to more than 5% and less than 10% in the entire range of 300 nm to 800 nm.

C: Insufficient The transmittance change before and after solvent immersion is 10% or more over the entire range of 300 nm to 800 nm.

The repeating unit of the dye polymer used in the examples of the present application is shown below.

<Repeating unit 1>

[化65]

The intermediate X ^- is the anion shown in Table 1, Table 2.

[化66]

The middle X is shown in the state before the anion shown in Table 1 and Table 2 is dissociated.

[67]

The intermediate X ^- is the anion shown in Table 1, Table 2.

[化68]

The intermediate X ^- is the anion shown in Table 1, Table 2.

[化69]

The intermediate X ^- is the anion shown in Table 1, Table 2.

<Repeating unit 2 to repeating unit 4>

[化70]

Anion X

Photopolymerization initiator: the following structure

[化72]

Alkali-soluble resin 1: the following structure

[化73]

Polymeric compound

Z1: ethoxylate-modified dipentaerythritol hexaacrylate, NK ester (NK Ester) A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)

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

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

Z4: ethoxylated (3) trimethylolpropane triacrylate, SR454 (manufactured by Sartomer)

Z5: ethoxylated (6) trimethylolpropane triacrylate, SR499 (manufactured by Sartomer)

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

Z7: Tris(2-hydroxyethyl)triacrylate, SR368 (manufactured by Sartomer)

Epoxy compound

E1: EHPE 3150, manufactured by Daicel (share)

E2: Epiclon 840 (made by Di Love (DIC))

E3: Epiclon (EPICLON) N660 (made by Di Love (DIC))

As can be seen from the results, the coloring composition of the present invention is excellent in fading resistance different. Further, it was found that the pattern formation property, the development residue, and the color spot were also excellent. In particular, it is known that in the formulation containing the pigment and the dispersant, the fading resistance is remarkably improved.

Claims (16)

A colored composition comprising a pigment multimer comprising: (a) a repeating unit having a pigment structure, and (b) having 2 to 20 unsubstituted alkoxy groups in the side chain A repeating unit of a chained group. The colored composition according to claim 1, wherein the pigment structure is derived from a selected from the group consisting of a dipyrromethene dye, a triarylmethane dye, a xanthene pigment, a cyanine pigment, and a squaraine pigment. Pigment. The colored composition according to claim 1 or 2, wherein the dye polymer further has an acid group. The colored composition according to claim 1 or 2, wherein the colored composition further comprises a pigment and a pigment dispersant. The coloring composition according to Item 1 or 2, wherein the coloring composition further comprises a polymerizable compound and a photopolymerization initiator. The colored composition according to claim 1 or 2, wherein the dye polymer is a (meth)acrylic resin. The colored composition according to claim 1 or 2, wherein (a) the ratio of the repeating unit having a dye structure is 10 mol% to 35 mol of all repeating units constituting the dye polymer. ear%. The colored composition according to claim 1 or 2, wherein (b) a repeating unit having a group in which a side chain has 2 to 20 unsubstituted alkylene oxide chains is repeated. The ratio is from 2 mol% to 20 mol% of all repeating units constituting the dye polymer. The colored composition according to claim 1 or 2, wherein the dye multimer comprises a polymerizable group. The colored composition according to claim 1 or 2, which is used for forming a coloring layer of a color filter. A cured film obtained by hardening the coloring composition according to any one of claims 1 to 10. A color filter having a cured film as described in claim 11 of the patent application. A pattern forming method comprising the steps of applying a colored composition according to any one of claims 1 to 10 to a support to form a colored composition layer; and exposing the colored composition layer a step of patterning; developing a non-exposed portion to form a colored pattern. A method of producing a color filter comprising the pattern forming method according to claim 13 of the patent application. A solid-state image pickup device comprising the color filter according to claim 12 or the color filter obtained by the method for producing a color filter according to claim 14. An image display device comprising the color filter according to claim 12 or the color filter obtained by the method for producing a color filter according to claim 14.