KR20180133568A - Coloring composition, cured film using same, color filter, pattern forming method, method for producing color filter, solid-state imaging element and image display device - Google Patents

Abstract

A color filter, a color filter manufacturing method, a solid-state image pickup device, and an image display device using the coloring composition, which are excellent in color irregularity and spectroscopic characteristics.
A colorant composition comprising a repeating unit a1 having a dye structure and a repeating unit a2 having a dye structure having a skeleton different from the dye structure of the repeating unit a1; and a curable compound.

Description

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

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

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

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

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

Specifically, Patent Document 1 discloses a coloring composition containing a pigment multimer having a pigment skeleton derived from a dipyrammethene metal complex compound.

Patent Document 2 discloses a coloring composition containing a colorant multimer having an alkali-soluble group having a weight average molecular weight (Mw) of 5,000 to 20,000 and a dispersion degree of 1.00 to 2.50 as a colorant.

Patent Document 1: JP-A-2012-46708 Patent Document 2: JP-A No. 2011-213925

There is an increasing demand for coloring compositions containing such a colorant multimer as described above and a coloring composition capable of forming a pattern having excellent color heterogeneity and spectroscopic characteristics by recent technological innovations is required.

As a method of adjusting the spectroscopic characteristics, there is a method of using a plurality of dye multimer in combination, and as a result of the investigation by the present inventors, it has been found that color unevenness tends to occur depending on the combination of dye multimers.

In view of the above circumstances, it is an object of the present invention to provide a colored composition excellent in color irregularity and spectroscopic characteristics.

As a result of a study by the inventors of the present invention, it was found that a colored composition excellent in color irregularity and spectroscopic characteristics can be obtained by introducing a pigment structure of another skeleton into a pigment multimer, and to complete the present invention It came.

Specifically, the above-mentioned problem is solved by the following means <1>, preferably by <2> to <17>.

&Lt; 1 > A coloring composition comprising a repeating unit a1 having a dye structure and a repeating unit a2 having a dye structure having a skeleton different from the dye structure of the repeating unit a1, and a curable compound.

At least one of the dye structure of the repeating unit a1 and the dye structure of the repeating unit a2 is at least one selected from the group consisting of a di-pyromethene dye, a triaryl methane dye, a zane dye, an azo dye, a diketopyrrolopyrrol dye, The coloring composition according to < 1 >, which is derived from a coloring matter selected from a cyanine dye, a cyanine dye and a squarylium dye.

&Lt; 3 > The dye according to any one of < 3 >, wherein at least one of the dye structure of the repeating unit a1 and the dye structure of the repeating unit a2 is at least one selected from the group consisting of a dipyramethine dye, a triarylmethane dye, a xanthene dye, an azo dye, a diketopyrrolopyrrol dye, The coloring composition according to < 1 > or &lt; 2 &gt;, wherein the coloring composition is derived from a coloring matter selected from cyanine dyes.

&Lt; 4 > The liquid crystal composition according to < 4 >, wherein the dye structure of the repeating unit a1 and the dye structure of the repeating unit a2 are selected from the group consisting of a dipyramethine dye, a triarylmethane dye, a xanthate dye, an azo dye, a diketopyrrolopyrrol dye, &Lt; 3 >, wherein the coloring composition according to any one of &lt; 1 &gt; to &lt; 3 &gt;

<5> The pigment multimer according to any one of <1> to <4>, which has a repeating unit represented by the following formula (a1-1) and a repeating unit represented by the following formula (a2-1) Composition;

[Chemical Formula 1]

In the general formulas (a1-1) and (a2-1), Q ¹ and Q ² each independently represent a trivalent linking group, L ¹ and L ² each independently represent a single bond or a divalent linking group, D ¹ represents a dye structure, D ² represents a dye structure having a skeleton different from D ^1, and * represents a bonding hand.

&Lt; 6 > The coloring composition according to any one of < 1 > to < 5 >, further comprising a repeating unit having an acid group.

<7> The coloring composition according to any one of <1> to <6>, wherein the dye multimer further comprises a repeating unit having a polymerizable group.

<8> The coloring composition according to any one of <1> to <7>, wherein the curable compound is a polymerizable compound and further contains a photopolymerization initiator.

<9> The coloring composition according to any one of <1> to <8>, wherein the colorant multimer is one kind selected from a (meth) acrylic resin, a styrene resin, and a (meth) acrylic / styrene resin.

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

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

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

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

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

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

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

According to the present invention, it becomes possible to provide a colored composition excellent in color irregularity and spectroscopic characteristics. Further, it becomes possible to provide a cured film, a color filter, a pattern forming method, a color filter manufacturing method, a solid-state image pickup device and an image display device using the above colored composition.

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

In the present specification, the total solid content refers to the total mass of the components excluding the solvent from the total composition of the coloring composition. The solid content refers to the solid content at 25 占 폚.

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

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

In the present specification, " (meth) acrylate " represents both or either of acrylate and methacrylate, and " (meth) acrylic " represents both acrylate and methacrylate, &Quot; (Meth) acryloyl " represents both acryloyl and methacryloyl.

In the present specification, the terms " monomer " and " monomer " are synonyms. Monomers in the present specification are distinguished from oligomers and polymers and refer to compounds having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group involved in the polymerization reaction.

In the present specification, Me in the formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, iPr represents an isopropyl group, Bu represents a butyl group, t-Bu represents a tert-butyl group and Ph represents a phenyl group.

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

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

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

The coloring composition of the present invention contains a repeating unit a1 having a pigment structure and a dye multimer having at least repeating unit a2 having a pigment structure having a skeleton different from that of the repeating unit a1 and a curing compound

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

&Lt;

The dye multimer used in the present invention has at least a repeating unit a1 having a pigment structure and a repeating unit a2 having a pigment structure having a skeleton different from that of the repeating unit a1. Hereinafter, the repeating unit a1 having a dye structure is referred to as a repeating unit (a1), and the repeating unit a2 having a dyeing structure is also referred to as a repeating unit (a2).

When the spectral characteristics are adjusted by mixing a plurality of colorant oligomers, color unevenness may occur depending on the combination of the colorant oligomers due to compatibility or the like. Particularly, when the content of the pigment multimer is increased in order to increase the dye concentration, the influence due to compatibility tends to increase and color heterogeneity tends to occur. However, in the dye multimer used in the present invention, ) And the repeating unit (a2), there is no problem caused by the compatibility, and the color heterogeneity and spectral characteristics are excellent. In addition, even when a colorant composition contains a large amount of a pigment multimer used in the present invention, color irregularity can be less likely to occur, and the coloring matter concentration can be increased.

In the present invention, " pigment structure having another skeleton " means a pigment structure derived from a pigment compound having a different parent structure. For example, when the dye structure of the repeating unit (a1) is a dye structure derived from a dipyramethine dye, the dye structure of the repeating unit (a2) is a dye structure derived from a dye other than a dipyramethine dye .

In the present invention, the dye structure of the repeating unit (a1) and the dye structure of the repeating unit (a2) may contain only one kind of dye structure having the same skeleton, Or the like may contain two or more different pigment structures. The dye may further contain a repeating unit (hereinafter referred to as repeating unit (a3)) having a dye structure having a skeleton, which is different from the dye structure of the repeating unit (a1) and the dye structure of the repeating unit (a2).

The dye multimer is not particularly limited as long as it contains a dye structure, but it is preferably one selected from a (meth) acrylic resin, a styrene resin, and a (meth) acrylic / styrene resin.

The (meth) acrylic resin means a resin containing a (meth) acrylic resin as a main component. (Meth) acrylic resin as a main component means that the (meth) acrylic resin preferably contains 50 mass% or more of the (meth) acrylic resin, more preferably 60 mass% or more, more preferably 70 mass% or more Is particularly preferable.

The styrene-based resin means a resin containing a styrene resin as a main component. The content of the styrene resin as the main component is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more of styrene resin in the styrene resin .

The (meth) acrylic / styrene resin means a resin containing a (meth) acrylic resin and a styrene resin as main components. (Meth) acrylic / styrene resin as a main component is preferably a (meth) acrylic / styrene resin containing a total of 50 mass% or more of a (meth) acrylic resin and a styrene resin in a total amount of 60 mass% Or more, more preferably 70 mass% or more.

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

<< Structure of the repeating unit (a1) and the repeating unit (a2) >>

The skeleton structure of the repeating unit (a1) and the repeating unit (a2) is not particularly limited, but may be a skeleton structure represented by general formulas (A), (B) and It is preferable that at least one of the constitutional units represented by the formula (C) is a skeleton, or a large amount of a dye represented by the formula (D) is preferable. The description of paragraphs 0276 to 0304 of Japanese Laid-Open Patent Publication No. 2013-28764 is incorporated herein by reference.

In the present invention, it is preferable to have a repeating unit represented by the following general formula (a1-1) and a repeating unit represented by the following general formula (a2-1).

The proportion of the repeating unit (a1) and the proportion of the repeating unit (a2) in the total repeating units constituting the pigment multimer vary depending on the required spectroscopy, so that the ratio is not particularly limited. For example, the proportion of the repeating unit (a1) is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and still more preferably 25 to 75 mol% of the total repeating units constituting the dye multimer desirable. The proportion of the repeating unit (a2) is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and still more preferably 25 to 75 mol% of the total repeating units constituting the dye multimer.

The total amount of repeating units having a dye structure in all the repeating units constituting the dye multimer is preferably from 30 to 100 mol%, more preferably from 40 to 100 mol%.

(2)

In the general formulas (a1-1) and (a2-1), Q ¹ and Q ² each independently represent a trivalent linking group, L ¹ and L ² each independently represent a single bond or a divalent linking group, D ¹ represents a dye structure, D ² represents a dye structure having a skeleton different from D ^1, and "*" represents a binding site.

In the general formulas (a1-1) and (a2-1), Q ¹ and Q ² each independently represent a trivalent linking group. Q ¹ and Q ² represent a linking group formed by polymerization, which forms a repeating unit corresponding to a main chain formed by a polymerization reaction. In addition, the parts indicated by two " * " are repeat units.

Q ¹ and Q ² are not particularly limited as long as they are a linking group formed by a known polymerizable monomer, and in particular, linking groups represented by the following formulas (XX-1) to (XX-24) (XX), (XX-18) and (XX-19) represented by the formula (XX-10) Vinyl-based linking chain, and more preferably a (meth) acrylic linkage chain represented by (XX-1) and (XX-2), and a styrene-based linkage chain represented by (XX- (Meth) acrylic linkage chain represented by (XX-1) and (XX-2) and a styrene-based linkage chain represented by (XX-11) Is more preferable.

(XX-1) to (XX-24), it is connected to L ¹ or L ² at the position indicated by *. Me represents a methyl group. In the formulas (XX-18) and (XX-19), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

(3)

[Chemical Formula 4]

In the general formulas (a1-1) and (a2-1), L ¹ and L ² each independently represent a single bond or a divalent linking group.

Examples of the divalent linking group include a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (e.g., a methylene group, an ethylene group, a trimethylene group, a propylene group, and a butylene group), a substituted or unsubstituted A substituted or unsubstituted heterocyclic linking group, -CH = CH-, -O-, -S-, -C (= O) -, -CO ₂ - _{, -NR-, -CONR-, -O 2 C-} , -SO-, -SO 2 - , and these represent a bonding group formed by linking two or more. It is also preferable that L ¹ and L ² contain an anion. L ¹ and L ² are more preferably a single bond or an alkylene group, and are more preferably a single bond or - (CH ₂ ) n- (n is an integer of 1 to 5). Here, R represents, independently of each other, a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

D ¹ and D ² represent a dye structure derived from a dye compound to be described later. D ² is a dye structure having a skeleton different from D ¹ .

The dye multimer having the repeating unit (a1) and the repeating unit (a2) is obtained by (1) a method of synthesizing a monomer having a pigment residue by addition polymerization, (2) a method of synthesizing a monomer having a pigment residue by an isocyanate group, an acid anhydride group or an epoxy group , And a dye having a functional group capable of reacting with a highly reactive group (such as a hydroxyl group, a primary or secondary amino group, or a carboxyl group).

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

Among them, the dye polymer multimer of the present invention is preferably a radical polymer obtained by radical polymerization using a dye monomer having an ethylenically unsaturated bond from the viewpoint of heat resistance.

<< Color Structure >>

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

Specific examples of the dye include pigments such as a dipyramethine dye, a carbonium dye (diphenylmethane dye, triarylmethane dye, xanthine dye, and acridine dye), a polymethine dye (oxolin dye, (A benzoquinone dye, a naphthoquinone dye, an anthraquinone dye, an anthrapyridone dye, etc.), an azo dye, etc. The present inventors have found that the coloring matter of the present invention can be obtained from at least one selected from the group consisting of at least one selected from the group consisting of at least one selected from the group consisting of at least one selected from the group consisting of at least one selected from the group consisting of at least one selected from the group consisting of at least one selected from the group consisting of at least one selected from the group consisting of at least one selected from the group consisting of: A pigment structure derived from a selected coloring matter, and the like.

At least one of D ¹ and D ² is selected from a dipyramethine dye, a triarylmethane dye, a xanthine dye, an azo dye, a diketopyrrolopyrrol dye, a phthalocyanine dye, a cyanine dye and a squarylium dye And a dye structure derived from a dye selected from a dypyrromethene dye, a triarylmethane dye, a xanthine dye, an azo dye, a diketopyrrolopyrrol dye, a phthalocyanine dye, Is more preferable. More preferably, D ¹ and D ² are a dye structure derived from a dye selected from a dypyrromethene dye, a triarylmethane dye, a xanthine dye, an azo dye, a diketopyrrolopyrrol dye, a phthalocyanine dye, to be.

Among them, from the viewpoint of spectroscopic characteristics, either one of D ¹ and D ² is a dye structure derived from a pigment selected from a phthalocyanine dye, an azo dye, and a diketopyrrolopyrrol dye, It is preferably a dye structure derived from a yellow colorant. Examples of the yellow colorant include a xanthine dye, a triarylmethane dye, an azo dye, a quinoxaline dye, a quinophthalone dye, an isoindolin dye, and the like.

From the viewpoint of spectroscopic characteristics, it is preferable that either of D ¹ and D ² has a dye structure derived from a dipyramethine dye and the other dye has a dye structure derived from a xanthine dye or a triarylmethane dye desirable.

Specific dye compounds capable of forming a dye structure are described in detail in "New Edition Dye Handbook" (edited by Organic Synthetic Chemistry Association, Maruzen, 1970), "Society of Dyers and colourists", " Kodansha, 1986).

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

<<< Dipyromethane coloring >>>

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

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

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

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

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

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

[Chemical Formula 5]

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

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

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

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

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

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

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

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

~ Metal or metal compound ~

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

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

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

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

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

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

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

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

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

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

[Chemical Formula 6]

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

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

A die pyrromethene metal complex compound represented by the general formula (7), the introduction portion of the case of introducing a structural unit represented by the general formula (A) ~ (D) is not particularly limited, but from the viewpoint of synthesis suitability, R ⁴ ~ R preferably introduced in any of the parts of ^{9 and, R 4, R 6, R} 7 and R ^9, and in more preferred to be introduced in any one, R ⁴ and R ⁹ of which is introduced according to any one Is more preferable.

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

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

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

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

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

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

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

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

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

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

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

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

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

(7)

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

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

Region to introduce a die pyrromethene metal complex compound represented by the general formula (8) to the structural unit represented by the general formula (A) ~ (D) it is, without compromising the effect of the present invention is not particularly limited, R ¹¹ ~ R ¹⁷ , X ¹ , and Y ¹ to Y ² . Among them, it is preferably introduced in any one of R ¹¹ to R ¹⁶ and X ¹ in terms of the compatibility with the synthesis, and more preferably it is introduced in any one of R ¹¹ , R ¹³ , R ¹⁴ and R ¹⁶ , And more preferably, it is introduced in any one of R ¹¹ and R ¹⁶ .

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

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

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

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

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

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

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

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

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

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

In formula (8), R ¹¹ and Y ¹ are bonded to each other to form a 5-membered ring (for example, a cyclopentane ring, a pyrrolidine ring, a tetrahydrofuran ring, a dioxolane ring, a tetrahydrothiophene ring, A benzofuran ring, a benzothiophene ring), a 6-membered ring (for example, a cyclohexane ring, a piperidine ring, a piperazine ring, a morpholine ring, a tetrazole ring, (For example, a cycloheptane ring, a hexamethyleneimine ring), or a 7-membered ring (for example, a cyclohexane ring, a dioxane ring, a pentamethylene ring, a dicyanamine ring, a benzene ring, a pyridazin ring, a quinoline ring, .

In formula (8), R ¹⁶ and Y ² are bonded to each other to form a 5-membered ring (for example, a cyclopentane ring, a pyrrolidine ring, a tetrahydrofuran ring, a dioxolane ring, a tetrahydrothiophene ring, A benzofuran ring, a benzothiophene ring), a 6-membered ring (for example, a cyclohexane ring, a piperidine ring, a piperazine ring, a morpholine ring, a tetrazole ring, (For example, a cycloheptane ring, a hexamethyleneimine ring), or a 7-membered ring (for example, a cyclohexane ring, a dioxane ring, a pentamethylene ring, a dicyanamine ring, a benzene ring, a pyridazin ring, a quinoline ring, .

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

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

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

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

a represents 0, 1 or 2;

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

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

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

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

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

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

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

[Chemical Formula 8]

[Chemical Formula 9]

Of the above specific examples, (PM-8) and (PM-10) are particularly preferable from the viewpoints of color characteristics and heat resistance.

<<< Carbonium coloring >>>

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

Triarylmethane dye

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

The general formula (TP)

[Chemical formula 10]

(Formula (TP) of, Rtp ¹ ~ Rtp ⁴ are, each independently, represent a hydrogen atom, alkyl group or aryl group. Rtp ⁵ is a hydrogen atom, an alkyl group, an aryl group or NRtp ⁹ Rtp ¹⁰ (Rtp ⁹ and Rtp ¹⁰ represents a represents a hydrogen atom, an alkyl group or an aryl group). Rtp ^6, Rtp ⁷ and Rtp ⁸ shows a substituent. a, b and c represents an integer of 0 ~ 4. a, b and c is 2 or more Rtp ⁶ , Rtp ⁷ and Rtp ⁸ may be connected to form a ring, and X ^- represents an anion structure.

For a preferable range and specific examples of the compound represented by the formula (TP), reference can be made to the description of paragraphs 0170 to 0178 of Japanese Laid-Open Patent Publication No. 2013-28764, the contents of which are incorporated herein by reference.

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

Specific examples of the compound represented by formula (TP) are shown below, but the present invention is not limited thereto. X represents an anion (hereinafter, they are the same unless otherwise specified). In the present invention, any one hydrogen atom of the following dye structures is bonded to the polymer skeleton.

Xanthan

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

(11)

(In the formula (J), R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represents a hydrogen atom or a monovalent substituent, R ⁸⁵ independently represents a monovalent substituent, X ^- represents an anion, X ^- does not exist, and at least one of R ⁸¹ to R ⁸⁵ includes an anion.

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

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

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

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

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

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

When X ^- represents an anion, reference may be made to the case where the counter anion described later is a separate molecule. When X ^- does not exist and at least one of R ⁸¹ to R ⁸⁵ contains an anion, Can be referred to in the case where the same repeating unit exists.

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

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

<< Azo dye >>

One of the dye structures according to the present invention has a partial structure derived from an azo dye (azo compound). In the present invention, an azo compound generally refers to a compound having a dye moiety containing N = N groups in a molecule. The azo dye can be appropriately selected from known azo dyes (for example, substituted azo benzene). For example, as the azo dye, reference can be made to the description of paragraphs 0084 to 0134 of Japanese Laid-Open Patent Publication No. 2013-41097 and the description of paragraphs 0029 to 0136 of Japanese Laid-Open Patent Publication No. 2011-162760, Is used.

<< Dykeetopyrrolopyrrol dye >>

One of the dye structures according to the present invention has a partial structure derived from a diketopyrrolopyrrole dye (diketopyrrolopyrrole compound). The diketopyrrolopyrrole dye includes a dye multimer having a partial structure derived from a compound represented by the following general formula (DK) (diketopyrrolopyrrole compound) as a partial structure of a dye moiety. In the present invention, the diketopyrrolopyrrole compound generally refers to a compound having a dye moiety containing a diketopyrrolopyrrole skeleton in a molecule.

[Chemical Formula 16]

In the general formula (DK), R ¹¹⁰ and R ¹¹¹ each independently represent a hydrogen atom, an alkyl group or an aryl group, R ¹¹² and R ¹¹³ each independently represent a hydrogen atom, an alkyl group or an aryl group, Lt; / RTI &gt;

<< Phthalocyanine color >>

One of the dye structures according to the present invention has a partial structure derived from a phthalocyanine dye (phthalocyanine compound). The phthalocyanine dye includes a dye oligomer having a partial structure derived from a compound represented by the following formula (F) (phthalocyanine compound) as a partial structure of a dye moiety. The phthalocyanine compound in the present invention refers to a compound having a pigment moiety including a phthalocyanine skeleton in a molecule.

[Chemical Formula 17]

In Formula (F), M ¹ represents a metal, and Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a hydrogen atom, an atom selected from a hydrogen atom, a carbon atom, Represents the group of atoms necessary to form a ring.

The general formula (F) will be described in detail.

Examples of the metal represented by M ¹ in the general formula (F) include metal atoms such as Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Metal chlorides such as AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ and GeCl ₂ , metal oxides such as TiO ₂ and VO ₂ and metal hydroxides such as Si (OH) Do.

In the general formula (F), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represents an atom necessary for forming a 6-membered ring comprising an atom selected from a hydrogen atom, a carbon atom and a nitrogen atom Respectively. The 6-membered ring may be a saturated ring, an unsaturated ring, or may be unsubstituted or may have a substituent. As the substituent, there can be mentioned the substituents in the group of Substituent Group A below. When the 6-membered ring has 2 or more substituents, the substituents may be the same or different. The 6-membered ring may be condensed with another 5-membered or 6-membered ring. The 6-membered rings include benzene rings, cyclohexane rings and the like.

Among the phthalocyanine dyes represented by the general formula (F), phthalocyanine dyes represented by the following general formula (F-1) are preferable.

[Chemical Formula 18]

In the general formula (F-1), M ² is the same as M ¹ in the general formula (F), and preferred embodiments thereof are also the same.

In the general formula (F-1), each of R ¹⁰¹ to R ¹¹⁶ independently represents a hydrogen atom or a substituent, and when the substituent represented by R ¹⁰¹ to R ¹¹⁶ is a further substitutable group, , And when they are substituted with two or more substituents, the substituents may be the same or different.

The substituent represented by R ¹⁰¹ to R ¹¹⁶ is preferably a hydrogen atom, a halogen atom, SO ₂ NR ¹¹⁷ R ¹¹⁸ (wherein R ¹¹⁷ and R ¹¹⁸ are each a hydrogen atom, a straight chain or branched alkyl group having 3 to 20 carbon atoms, Alkyl group), SR ¹¹⁹ (R ¹¹⁹ is a straight chain or branched alkyl group having 3 to 20 carbon atoms which may have a substituent).

<<< Cyanine color >>>

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

<<< Subphthalocyanine pigment >>>

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

<< Squarylium pigment >>

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

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

Substituent group A:

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

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

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

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

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

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

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

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

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

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

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

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

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

<<< counter negative ion >>>

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

If the counter anion is in the same repeat unit

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

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

In formula (A1)

[Chemical Formula 19]

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

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

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

In general formula (A1-1)

[Chemical Formula 20]

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

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

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

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

In general formula (A2)

[Chemical Formula 21]

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

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

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

In the present embodiment, the skeleton of the dye multimer used in the present invention includes a structural unit represented by the general formula (B). (B-dp-1), (B-mp-1), (B-xt-1) and (B-xt-2) in the examples of the repeating units having a dye structure .

If the counter anion is a separate molecule

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

Examples of the anion in this case include a fluorine anion, a chlorine anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, and a non-nucleophilic anion, and the non-nucleophilic anion is preferable.

The counter anion of the non-nucleophilic nature may be an organic anion, an inorganic anion, or an organic anion. Examples of the counter anion used in the present invention include known non-nucleophilic anions described in Japanese Patent Application Laid-Open No. 2007-310315, paragraph No. 0075, the contents of which are incorporated herein by reference.

Preferably, the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion, tetra aryl borate anions, B ^- (CN) _n1 (OR ^a) _4-n1 (R ^a represents an alkyl group having 1 to 10 carbon atoms or aryl group having a carbon number of 6 ~ 10, n1 represents 1 to 4) and _{^{PF n2 R P (6-n2}} ) - (R P represents a fluorinated alkyl group having a carbon number of 1 ~ 10, n2 is an integer of 1-6 , And more preferably selected from a bis (sulfonyl) imide anion, a tris (sulfonyl) methyl anion and a tetraaryl borate anion, and more preferably a bis (sulfonyl) imide anion. By using such an anion having an acetonuclear nature, the effect of the present invention tends to be more effectively exerted.

As the bis (sulfonyl) imide anion which is an anion of a non-nucleophilic group, a structure represented by the following general formula (AN-1) is preferable.

[Chemical Formula 22]

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

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

As the tris (sulfonyl) methyl anion which is an opposite anion of an acetyl nucleus, a structure represented by the following general formula (AN-2) is preferable.

(23)

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

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

The tetraarylborate anion, which is an anion of an acetonuclear nature, is preferably a compound represented by the following formula (AN-5).

&Lt; EMI ID =

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

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

The aryl group represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may have a substituent. A halogen atom, an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbonyloxy group, a carbamoyl group, a sulfo group, a sulfonamido group and a nitro group, More preferably a fluorine atom or an alkyl group, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently preferably a phenyl group having an alkyl group having a halogen atom and / or a halogen atom, and a phenyl group having an alkyl group having a fluorine atom and / More preferable.

The counter anion of the non-nucleophilic group may also be -B (CN) _n1 (OR ^a ) _4-n1 (wherein R ^a represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms and n1 represents an integer of 1 to 4) ). R ^a as an alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. R ^a as an aryl group having 6 to 10 carbon atoms is preferably a phenyl group or a naphthyl group.

n1 is preferably 1 to 3, more preferably 1 to 2.

The counter anion of the non-nucleophilic group is further preferably -PF ₆ R ^P _{(6-n 2)} ^- (wherein R ^P is a fluorinated alkyl group having 1 to 10 carbon atoms and n 2 is an integer of 1 to 6) . R ^P is preferably an alkyl group having 1 to 6 carbon atoms and more preferably a fluorine atom having 1 to 4 carbon atoms, more preferably a perfluoroalkyl group having 1 to 3 carbon atoms.

n2 is preferably an integer of 1 to 4, more preferably 1 or 2.

The mass per molecule of the non-nucleophilic counter anion used in the present invention is preferably 100 to 1,000, more preferably 200 to 500.

The dye multimer of the present invention may contain only one kind of non-nucleophilic counter anion or two or more kinds of non-nucleophilic counter anions.

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

(25)

(26)

(27)

(28)

[Chemical Formula 29]

In the second embodiment, the anion may be a mass of anion. As the multimer in this case, there is exemplified a multimer containing a constituent unit containing an anion and not containing a constituent unit derived from a pigment structure containing a cation. Here, as the constitutional unit containing an anion, a constitutional unit containing an anion described in the third embodiment to be described later can be mentioned as a preferable example. Further, the multimer containing an anion may have a constitutional unit other than the constitutional unit containing an anion. As such a constitutional unit, other repeating units which may be contained in the dye multimer used in the present invention to be described later are exemplified as preferable examples.

When the cation and the anion are included in each other repeating unit of the dye multimer

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

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

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

In the general formula (C)

(30)

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

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

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

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

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

In general formula (D)

(31)

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

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

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

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

As the counter anion, the anion moiety described in the case where the opposite anion is present in the same constituent unit is exemplified as a preferable anion.

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

(32)

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

(33)

(34)

(35)

(36)

(37)

Examples of the repeating unit (a1) and the repeating unit (a2), which are preferably used in the present invention, are shown below. It is needless to say that the present invention is not limited to these. X ^- represents a counter anion. It is to be noted that some Xs are shown in a state in which the anion structure is not dissociated, but it is needless to say that the dissociation state is also included in the present invention.

(38)

[Chemical Formula 39]

(40)

(41)

(42)

(43)

(44)

[Chemical Formula 45]

(46)

<< Other functional groups and repeating units >>

The dye multimer of the present invention may have another functional group in the dye structure portion of the above-mentioned colorant multimer. Examples of the other functional groups include a polymerizable group and an alkali-soluble group (preferably, an acid group).

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

The dye multimer of the present invention may contain other repeating units in addition to the repeating unit (a1) and the repeating unit (a2) described above. The other repeating unit may have a functional group. As other repeating units, repeating units containing at least one of a polymerizable group and an alkali-soluble group (preferably, an acid group) are exemplified.

That is, the dye multimer of the present invention may have other repeating units other than the repeating unit (a1) and the repeating unit (a2) described above. The other repeating units may be contained in only one kind or two or more kinds in one coloring matter multimer.

The dye multimer of the present invention may contain another functional group in the dye multimer. The details of these will be described below.

<<< Polymeric group >>>>>

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

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

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

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

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

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

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

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

isocyanatoethyl methacrylate, 2-isocyanatoethyl methacrylate, and 2-isocyanatoethyl methacrylate in the method (b) of reacting the hydroxyl group or the amino group of the dye oligomer with the unsaturated bond-containing isocyanate compound -Isocyanatoethyl acrylate, and 1,1-bis (acryloyloxymethyl) ethyl isocyanate. Of these, 2-isocyanatoethyl methacrylate has a crosslinking property and storage stability Which is preferable. As the reaction conditions, known conditions can be used.

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

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

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

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

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

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

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

The proportion of the repeating unit containing a repeating unit having a polymerizable group as a polymeric monomer is preferably 5 to 50 moles, more preferably 10 to 20 moles, per 100 moles of the total repeating units.

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

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

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

<<< Alkali-soluble group >>>

As an example of the alkali-soluble group which may be contained in the dye multimer in the present invention, an acid group can be mentioned. Examples of the acid group include a carboxylic acid group, a sulfonic acid group and a phosphoric acid group. In the present invention, it is preferable that the acid group is a repeating unit having an acid group and is contained in the dye multimer. The acid group may be contained only in one kind or in two or more kinds.

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

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

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

When the dye multimer contains a repeating unit containing a dye monomer and a repeating unit having an acid group, the proportion of the repeating unit containing an acid group-containing repeating unit is preferably in the range of, for example, 100 moles per 100 moles of the repeating unit containing the dye monomer Preferably 5 to 70 moles, and more preferably 10 to 50 moles.

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

The number of repeating alkyleneoxy chains of the repeating unit (b) is preferably 2 to 15, more preferably 2 to 10.

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

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

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

In general formula (P)

(49)

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

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

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

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

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

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

(50)

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

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

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

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

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

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

(56)

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

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

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

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

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

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

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

Specific examples of the structure represented by the formula (1) are shown below, but the present invention is not limited thereto. In the structure shown below, " * " represents the bonding of the structure represented by formula (2) and the polymer backbone.

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(58)

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

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

[Chemical Formula 59]

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

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

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

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

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

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

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

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

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(63)

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

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

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

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

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

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

&Lt; EMI ID =

(65)

In the formula (5), R ¹⁰ to R ¹² each independently represent an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. n4 to n6 each independently represent an integer of 0 to 5; n7 to n9 each independently represent 0 or 1, and at least one of n7 to n9 represents 1. &Quot; * " represents the combined hand of the structure represented by formula (5) and the polymer skeleton.

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

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

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

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

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

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

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

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

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

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

(66)

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

(E)

(67)

In the general formula (E), X ³ is the same as Q ¹ in the general formula (a1-1). L ⁴ is synonymous with L ¹ in the general formula (a1-1). Z ¹ represents a structure represented by the above-mentioned formulas (1) to (5).

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

(68)

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

<<< Specific end >>>

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

The compound of formula (I)

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

In the general formula (I), Z represents a monovalent substituent. Z represents a hydrogen atom, a halogen atom, a carboxyl group, a cyano group, an alkyl group having 1 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having a total of 3 to 30 carbon atoms valent heterocyclic ^{group, -OR 1, -SR 1, -OC} (= O) R 1, -N (R 1) (R 2), -C (= O) OR 1, -C (= O) N (R ^A monovalent group having ¹ ) (R ² ), -P (═O) (OR ¹ ) ₂ , -P (═O) (R ¹ ) ² or a polymer chain is preferable, and -SR ¹ , an aryl group, Is preferably selected from an amino group, an alkoxy group, and an aryloxy group substituted with an alkyl group and / or an aryl group, and is preferably selected from -SR ¹ (preferably an alkylthio group, an arylthio group) More preferably an alkyl thio group or an aryl group, particularly preferably an alkyl thio group.

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

R ¹ and R ² each independently represent an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, or a monovalent aromatic hydrocarbon group having 3 to 30 A monovalent heterocyclic group having 3 to 30 total atoms of carbon atoms and a bivalent atom, and R &lt; ¹ &gt; and R &lt; ² may be all substituted or not substituted. Examples of the substituent when it is substituted include an alkyl group and an aryl group.

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

In general formula (II)

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

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

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

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

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

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

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

(Ia)

&Lt; EMI ID =

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

The compound of formula (IIa)

(75)

In the general formula (IIa), A and B are synonymous with the general formula (II). D represents a monovalent organic group.

(IIb)

[Formula 76]

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

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

&Lt;

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

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

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

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

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

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

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

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

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

In the coloring composition of the present invention, it is preferable to use the above-mentioned colorant multimer in the present invention singly, but two or more of them may be used in combination.

In addition, a dye multimer (hereinafter, referred to as another dye multimer) other than the dye multimer in the present invention may be used in combination. Examples of the other colorant multimer include dye multimer having only one of the repeating unit (a1) and the repeating unit (a2) described above. The content of the other pigment multimer is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less, based on the total mass of the pigment.

The content of the pigment multimer in the coloring composition of the present invention is not particularly limited. For example, when a pigment multimer is used together with a pigment to be described later, it is set after taking into account the content ratio of the pigment multimer and the pigment.

In the case of using the pigment in combination with the pigment, the mass ratio (pigment multimer / pigment) of the pigment multimer to the pigment is preferably 0.40 to 1.00, more preferably 0.45 to 0.80, further preferably 0.50 to 0.75 Do.

The colorant component (the total amount of the pigment multimer, pigments and other dyes described later) in the coloring composition of the present invention is preferably from 50 to 70 mass%, more preferably from 55 to 65 mass%, of the total solid content of the coloring composition desirable.

<Curable compound>

The coloring composition of the present invention contains a curable compound. As the curable compound, a polymerizable compound or an alkali-soluble resin (including an alkali-soluble resin containing a polymerizable group) is exemplified and appropriately selected according to the application and the production method.

<< Polymerizable compound >>

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

Such a group of compounds is well known in the industrial field of the present invention and can be used in the present invention without particular limitation. These may be, for example, monomers, prepolymers, that is, any of a dimer, a trimer and an oligomer or a mixture thereof and a chemical form thereof such as a multimer thereof. The polymerizable compounds in the present invention may be used alone or in combination of two or more.

More specifically, examples of the monomer and the prepolymer thereof include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and the like), esters thereof, amides, And amides of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound and an oligomer of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or multifunctional isocyanate or an epoxide, a monofunctional or polyfunctional A dehydration condensation reaction product with a carboxylic acid, and the like are suitably used. In addition, it is also possible to use an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group, an addition reaction product of monofunctional or polyfunctional alcohols, amines, thiols, Unsaturated carboxylic acid esters or amides having a desilyl substituent group and mono- or polyfunctional alcohols, amines, and thioes are also suitable. As another example, in place of the above unsaturated carboxylic acid, it is also possible to use a compound group substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an ally ether or the like.

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

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

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

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

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

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

[Formula 77]

(78)

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

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

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

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

Among them, dipentaerythritol triacrylate (KAYARAD D-330, manufactured by Nippon Kayaku Kabushiki Kaisha) and dipentaerythritol tetraacrylate (commercially available products such as KAYARAD D-320; Nippon Kayaku Co., (KAYARAD D-310 manufactured by Nippon Kayaku K.K.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) (Manufactured by Kayaku K.K.), and a structure in which the (meth) acryloyl group intervenes between ethylene glycol and propylene glycol moieties. These oligomer types can also be used.

The polymerizable compound is a polyfunctional monomer and may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. If the ethylenic compound has an unreacted carboxyl group as described above, the ethylenic compound can be used as it is. However, if necessary, the acid group may be introduced by reacting the hydroxyl group of the above-mentioned ethylenic compound with a nonaromatic carboxylic acid anhydride. In this case, specific examples of the non-aromatic carboxylic acid anhydrides to be used include anhydrous tetrahydrophthalic acid, alkylated anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, alkylated anhydrous hexahydrophthalic acid, succinic anhydride, and maleic anhydride.

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

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

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

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

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

(79)

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

(80)

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

[Formula 81]

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

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

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

Also, the polymerizable compound is preferably at least one selected from the group of compounds represented by the following general formula (Z-4) or (Z-5).

(82)

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

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

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

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

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

The sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

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

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

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

The compound represented by the general formula (Z-4) or the general formula (Z-5) can be produced by subjecting pentaerythritol or dipentaerythritol, which is a conventionally known process, to a ring opening skeleton And a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride on the terminal hydroxyl group of the ring-opening skeleton. Each process is a well-known process, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).

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

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

(83)

(84)

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

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

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

JER-827, JER-834, JER-1001, JER-1002, JER-1003, and JER-823 as the bisphenol A type epoxy resin having an epoxy group, as the cyclic ether (epoxy, oxetane) EPICLON1051, EPICLON1051, and EPICLON1055 (manufactured by DIC Corporation), and the like, and bisphenol F type epoxy resin (trade name: JER-1055, JER- (Manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 (manufactured by DIC Corporation), and JER-806, JER-807, JER-4004, JER-4005, JER- JER-152, JER-157S70, and JER-157S65 (above, Japan Epoxy Resin Co., Ltd.) as phenol novolak type epoxy resin, (EPICLON N-660, EPICLON N-665, EPICLON N-770, and EPICLON N-775 manufactured by DIC Corporation) EPICLON N-690, EPICLON N-690, EPICLON N-670, EPICLON N-680, (Manufactured by Nippon Kayaku Co., Ltd.), and aliphatic epoxy resins such as ADEKA RESIN EP-4080S, EP-4085S and EP-4088S (manufactured by ADEKA), Celloxide 2021P, Celloxide 2081, Side 2083, Celloxide 2085, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of EHPE-3150 (2,2-bis (hydroxymethyl) PB 3600 and PB 4700 (manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-211L, EX-212L, EX-214L, EX-216L, EX-321L and EX- NC-2000, NC-3000, NC-7300, XD (manufactured by Nippon Shokubai Co., Ltd.), ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP- -1000, EPPN-501, EPPN-502 (manufactured by ADEKA) and JER-1031S (manufactured by Japan Epoxy Resin Co., Ltd.). Such a polymerizable compound is suitable for forming a pattern by a dry etching method.

Details of the structure, the use of the polymerizable compound, whether it is used singly or in combination, and the amount of the polymerizable compound can be arbitrarily set in accordance with the final performance design of the coloring composition. For example, from the viewpoint of sensitivity, a structure having a large amount of unsaturated groups per molecule is preferable, and in many cases, a bifunctionality or more is preferable. Further, from the viewpoint of enhancing the strength of the cured film formed by the coloring composition, it is preferable to use trifunctional or more functional groups and the number of functional groups different from each other (e.g., acrylic acid ester, methacrylic acid ester, styrene series compound, vinyl ether group compound) A method of controlling both sensitivity and strength is also effective. In addition, it is preferable to use a polymerizable compound having three or more functional groups and having different ethylene oxide chain lengths from the viewpoint that the developability of the coloring composition can be controlled and excellent pattern forming ability can be obtained.

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

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

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

<Polyfunctional thiol compound>

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

The compound of formula (I)

(85)

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

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

&Lt; EMI ID =

The blending amount of the polyfunctional thiol compound in the coloring composition of the present invention is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass, based on the total solid content excluding the solvent.

The polyfunctional thiol compound may contain only one kind or two or more kinds thereof. When two or more kinds are included, the total amount is preferably in the above range.

The polyfunctional thiol may be added for the purpose of improving stability, odor, resolution, developability and adhesion.

<Alkali-soluble resin>

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

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

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

Examples of the group capable of promoting alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, and the like, preferably soluble in an organic solvent and capable of being developed by a weakly alkaline aqueous solution , And (meth) acrylic acid are particularly preferable. These acid groups may be only one kind, or two or more kinds.

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

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

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

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

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

[Chemical Formula 87]

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

(ED2)

[Formula 88]

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

As a result, the colored composition of the present invention can form a cured film having excellent heat resistance as well as transparency. In the general formula (ED) representing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited and includes, for example, methyl, ethyl, A linear or branched alkyl group such as methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl or 2-ethylhexyl; An aryl group such as phenyl; Alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl and the like; An alkyl group substituted by alkoxy such as 1-methoxyethyl or 1-ethoxyethyl; An alkyl group substituted with an aryl group such as benzyl; And the like. Of these, an acid such as methyl, ethyl, cyclohexyl, benzyl and the like and a substituent of a primary or secondary carbon which is difficult to desorb by heat are preferable from the viewpoint of heat resistance.

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

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

(89)

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

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

In order to improve the crosslinking efficiency of the coloring composition of the present invention, an alkali-soluble resin having a polymerizable group may be used. When such an alkali-soluble resin is used, the effect of the present invention tends to be further improved. In addition, light resistance and heat resistance tend to be improved. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. Examples of the above-mentioned alkali-soluble resin containing a polymerizable group include a dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (a polyurethane acrylic oligomer containing COOH, manufactured by Diamond Shamrock Co., Ltd.), Viscot R- KS resist 106 (all manufactured by Osaka Yuki Kagaku Kogyo K.K.), Cyclomer P series, Flaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel Chemical Industries, Ltd.) . As the alkali-soluble resin containing these polymerizable groups, it is preferable that an isocyanate group and an OH group are previously reacted to leave an unreacted isocyanate group, and a compound containing a (meth) acryloyl group and a An unsaturated group-containing acrylic resin obtained by reaction of an urethane-modified polymerizable double bond-containing acrylic resin obtained by the reaction of an acrylic resin, an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule, Acid pendant epoxy acrylate resin, a polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond, an acrylic resin containing an OH group, an isocyanate and a polymerizable group , A resin obtained by reacting a compound having an epoxy group-containing compound 207 and JP-A No. 2003-335814, a resin obtained by basic treatment of a resin having on its side chain an ester group having a leaving group such as a halogen atom or a sulfonate group on? In addition, ARC Liqueur RD-F8 (manufactured by Nippon Shokubai Co., Ltd.) is also preferable.

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

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

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

(90)

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

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

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

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

&Lt; Other components of coloring composition >

The coloring composition of the present invention may contain other components in addition to the colorant multimer. For example, for the purpose of controlling the color value, the coloring composition used in the present invention may contain a pigment and a pigment dispersant in addition to the pigment multimer and the curable compound. When a polymerizable compound is used as the curable compound, it may further contain a photopolymerization initiator.

For example, in the case of forming a colored layer by a photoresist, the coloring composition of the present invention is preferably a composition comprising a pigment multimer, an alkali-soluble resin as a curable compound, and a photopolymerization initiator in the present invention. It may also contain components such as a pigment, a pigment dispersant, a surfactant, and a solvent.

In the case of forming a colored layer by dry etching, a composition containing a pigment multimer, a polymerizable compound as a curable compound, and a photopolymerization initiator in the present invention is preferable. It may also contain components such as pigments, pigment dispersions, surfactants, and solvents.

The details of these will be described below.

<< Pigment >>

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

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

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

As the organic pigment, for example,

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

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

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

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

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

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

C. I. Pigment Brown 25, 28;

C. I. Pigment Black 1, 7;

And the like.

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

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

C. I. Pigment Orange 36, 71,

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

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

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

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

C. I. Pigment Black 1, 7

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

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

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

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

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

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

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

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

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

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

<< Pigment dispersant >>

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

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

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

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

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

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

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

Specific examples of such a pigment dispersant usable in the present invention are commercially available products such as "DA-7301" manufactured by Goosumoto Kasei Co., Ltd., "Disperbyk-101" (polyamide amine phosphate) manufactured by BYK Chemie, 107 (Copolymers containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166 and 170 (polymeric copolymers) "," BYK-P104, P105 Unsaturated polycarboxylic acid "), EFKA 4047, 4050 to 4010 to 4165 (polyurethane resin), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (High molecular weight polycarboxylic acid salt), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ", Ajisper PB821, PB822, PB880, PB881" manufactured by Ajinomoto Fine Techno Co., Fluorene TG-710 (uretene oligomer) ", " Polyflow No. 50E, No. 300 (Arc 873, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725 ", " Demol RN, N (naphthalene sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) ", " Homogenol L- , "Acetamine 86 (Stearylamine Acetate)", "Nippon Lubrizol Co., Ltd.", "Solpres 5000" (manufactured by Nippon Polyurethane Industry Co., Ltd.), "Emulsion 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) (Graft polymer) ", 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 17000, 27000 (polymer having functional group at the terminal), 24000, 28000, 32000, 38500 (Polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Kawaken Fine Chemicals Co., Ltd.," Hinoact T-8000E "manufactured by Kawaken Fine Chemicals Co., Quot; "W001: cationic surfactant", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl (trade name) Nonionic surfactants such as phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic surfactants such as " W004, W005, W017 & Based surfactant, EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450, manufactured by Morishita Sangyo Co., F38, L42, L44, L61, L64, F68, L72, L64, L64, L64, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 "manufactured by Sanyo Chemical Industries, &Quot; and the like.

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

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

In the case of containing the pigment dispersant in the coloring composition, the total content of the pigment dispersant is preferably 1 part by mass to 80 parts by mass, more preferably 5 parts by mass to 70 parts by mass, and more preferably 10 parts by mass per 100 parts by mass of the pigment To 60 parts by mass is more preferable. The coloring composition of the present invention may contain only one pigment dispersant, or may contain two or more pigment dispersants. When two or more kinds are included, the total amount is preferably in the above 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 in the range of 10 parts by mass to 80 parts by mass, based on 100 parts by mass of the pigment .

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

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

<< Dye >>

The coloring composition of the present invention may contain a known dye other than a colorant multimer. For example, Japanese Patent Application Laid-Open Nos. 64-90403, 64-91102, 1-94301, 6-11614, 2592207, Japanese Patent Publication No. 4808501, US Pat. No. 5,667,920, US Pat. No. 5,05950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, A pigment disclosed in JP-A-6-194828 can be used. Examples of the chemical structure include a pyrazole group, a pyromethene group, an anilino group, a triphenylmethane group, an anthraquinone group, a benzylidene group, an oxolane group, a pyrazolotriazole group, a pyridazo group, And pyrrolopyrazole azo methane phosphoric acid, can be used.

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

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

<< Photopolymerization initiator >>

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

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

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

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

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

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

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

[Formula 91]

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

&Lt; EMI ID =

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

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

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

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

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

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

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 (all trade names, manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all trade names, manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which the absorption wavelength is matched to a long-wavelength light source such as 365 nm or 405 nm may be used. As the acylphosphine type initiator, commercial products IRGACURE-819 and DAROCUR-TPO (trade names, all of which are manufactured by BASF) and Midori Kagaku TAZ series (such as TAZ-107, TAZ-110 and TAZ- , TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123).

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

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

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

IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF) and TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.) .

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

Preferably, the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744 can be suitably used. Of the cyclic oxime compounds, cyclic oxime compounds which are covalently bound to the carbazole dyes described in JP-A-2010-32985 and JP-A-2010-185072 are preferred from the viewpoint of high sensitivity due to their high light absorption.

Also, the compounds described in JP-A-2009-242469 having an unsaturated bond in a specific part of an oxime compound can attain high sensitivity and can be suitably used by regenerating active radicals from polymerization inert radicals.

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

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

&Lt; EMI ID =

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

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

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

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

Specific examples (C-4) to (C-13) of the compound represented by formula (OX-1) are shown below, but the present invention is not limited thereto.

(94)

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

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

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

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

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

<Other Ingredients>

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

<< Organic solvents >>

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

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

Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, , Methyl lactate, ethyl lactate, alkyloxyacetate (such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, Ethoxyacetic acid ethyl, etc.), 3-oxypropionic acid alkyl esters (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Ethoxypropionate, ethyl 3-ethoxypropionate), 2-oxypropionic acid alkyl esters (e.g., methyl 2-oxypropionate, 2-oxypropionate Ethyl propionate, ethyl 2-ethoxypropionate), propyl 2-hydroxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, , Methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy- Examples of the ethers include diethyleneglycol dimethylether, tetraethyleneglycol dimethylether, tetraethyleneglycol dimethylether, tetraethyleneglycol dimethylether, and tetraethyleneglycol dimethacrylate, as methyl, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Ether, diethylene glycol Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Examples of the aromatic hydrocarbon include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like, and toluene, xylene and the like are suitably used.

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

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

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

<< Cross-linking agent >>

The coloring composition of the present invention may contain a crosslinking agent. By containing the crosslinking agent, the hardness of the cured film obtained by curing the coloring composition can be further increased.

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

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

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

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

<< Polymerization inhibitor >>

The coloring composition of the present invention preferably contains a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during or during the production of the coloring composition.

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

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

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

<< Surfactant >>

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

&Lt; Preparation method of colored composition >

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

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

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

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

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

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

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

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

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

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

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

As a second embodiment of the pattern forming method of the present invention, a step of applying a coloring composition onto a support to form a coloring composition layer and curing to form a colored layer, a step of forming a photoresist layer on the colored layer , A step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry-etching the colored layer using the resist pattern as an etching mask.

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

The details of these will be described below.

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

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

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

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

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

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

If necessary, an undercoat layer may be provided on the support in order to improve adhesion with the upper layer, prevent diffusion of the substance, or planarize the surface of the substrate. The undercoat layer may contain a solvent, an alkali-soluble resin, a polymerizable compound, a polymerization inhibitor, a surfactant, a photopolymerization initiator, and the like. These components may be appropriately selected from the components incorporated in the above- .

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

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

<Step of forming a pattern by photolithography method>

<< Process of Exposure >>

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

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

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

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

In the present step, a cured film having a thin film thickness of 0.7 m or less can be suitably formed, and the obtained cured film is subjected to development processing in a pattern forming step described later to improve the developability, surface roughness , And a colored pattern excellent in the pattern shape can be obtained.

<< Development Process >>

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

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

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

As the developing solution, an inorganic alkali may be used. As the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate and the like are preferable.

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

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

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

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

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

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

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

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

These solvents may be used alone or in combination of two or more. When mixing two or more species, it is preferable to mix a solvent having a hydroxyl group with a solvent having no hydroxyl group. The mass ratio of the solvent having a hydroxyl group to the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. It is particularly preferable that the mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) has a ratio of 60/40. Further, in order to improve the permeability of the cleaning liquid to the contaminants, the surfactant relating to the present composition described above may be added to the cleaning liquid.

Since the color filter of the present invention uses the coloring composition of the present invention, it is possible to perform exposure with excellent exposure margin, and the formed color pattern (colored pixel) has excellent pattern shape, and the roughness of the pattern surface And the residue in the developing portion is suppressed, so that the color characteristic is excellent.

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

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

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

<Solid-state image sensor>

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

A plurality of photodiodes constituting a light receiving area of a solid-state image sensor (a CCD image sensor, a CMOS image sensor, or the like) and a transfer electrode made of polysilicon or the like are formed on a support, and only a photodiode light- A device shielding film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion, and having a color filter for a solid-state imaging device of the present invention .

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

<Image Display Device>

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

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

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

Further, the color filter in the present invention can be used for a bright, high definition COA (Color-filter On Array) method. In the COA type liquid crystal display device, the required characteristics for the color filter layer may require the characteristics required for the interlayer insulating film, that is, the low dielectric constant and the peel liquid resistance, in addition to the above-mentioned usual required characteristics. In the color filter of the present invention, since a color pigment having excellent color is good, color purity, light transmittance and the like are good and coloring pattern (pixel) is excellent in color tone, a COA type liquid crystal display device having high resolution and long- . Further, in order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.

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

The liquid crystal display device provided with the color filter in the present invention is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film in addition to the color filter in the present invention. The color filter of the present invention can be applied to a liquid crystal display device constituted by these known members. These members are described in, for example, "Market of Liquid Crystal Display Materials and Chemicals (1994) issued by Shimadaira Co., Ltd. (CMC)", "2003 Liquid crystal display market trends and future prospects (Issued by Fuji Chimera Soken Co., Ltd., 2003).

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

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

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it departs from the spirit thereof. In addition, "% " and " part " are on a mass basis unless otherwise specified.

&Lt; Synthesis Example 1: Synthesis of pigment oligomer P-1 >

&Lt; EMI ID =

(1.41 g), monomer 2 (1.10 g), methacrylic acid (0.52 g), dodecyl mercaptan (0.07 g) and cyclohexanone (7.05 g) were added to a three-necked flask. Lt; 0 &gt; C. To this solution was added a monomer 1 (1.41 g), monomer 2 (1.10 g), methacrylic acid (0.52 g), dodecylmercaptan (0.07 g), dimethyl 2,2'-azobis (isobutyrate) : V601, manufactured by Wako Pure Chemical Industries, Ltd.) (0.30 g) and cyclohexanone (7.05 g) was added dropwise over 1 hour. Thereafter, the mixture was stirred for 4 hours and then cooled to obtain a cyclohexanone solution of (PM-1). Next, glycidyl methacrylate (0.90 g), tetrabutylammonium bromide (0.16 g) and p-methoxyphenol (70 mg) were added and heated at 100 ° C. for 6 hours in an air atmosphere to obtain methacrylic acid It was confirmed that glycidyl was lost. After cooling, the solution was added dropwise to an acetonitrile / ion-exchange water mixed solvent and re-applied to obtain 6.15 g of a colorant oligomer (P-1).

The composition ratio (molar ratio) of the resulting dye multimer was confirmed by ¹ H-NMR, and it was confirmed that repeating units having a dye structure derived from a dypyrromethene dye-derived (monomer 1 derived) dye structure: Unit: repeating unit having an acid group: repeating unit having a polymerizable group = 13: 14: 37: 36. The weight average molecular weight (Mw) was 12,000 (GPC).

&Lt; Synthesis Example 2: Synthesis of pigment multimer P-2 >

&Lt; EMI ID =

N-methyl-2-pyrrolidone (hereinafter referred to as " NMP ") (2.00 g) was added to a three-necked flask and heated to 90 占 폚 under a nitrogen atmosphere. To this solution was added a monomer 3 (2.27 g), monomer 4 (2.73 g), methacrylic acid (1.04 g), dodecyl mercaptan (0.15 g), 2,2'-azobis (isobutyric acid) : V601, manufactured by Wako Pure Chemical Industries, Ltd.) (0.34 g) and NMP (12.10 g) was added dropwise over 1 hour. Thereafter, the mixture was stirred for 4 hours and then cooled to obtain an NMP solution of (PM-2). Next, glycidyl methacrylate (0.90 g), tetrabutylammonium bromide (0.16 g) and p-methoxyphenol (70 mg) were added and heated at 100 ° C. for 15 hours in an air atmosphere to obtain methacrylic acid It was confirmed that glycidyl was lost. After cooling, the solution was added dropwise to an acetonitrile / ion-exchange water mixed solvent and re-applied to obtain 5.11 g of a colorant oligomer (P-2).

The composition ratio (molar ratio) of the resulting dye multimer was confirmed by ¹ H-NMR, and it was confirmed that the dye unit derived from the triarylmethane dye (monomer 3 derived from repeating unit: xanthine dye-derived monomer 4) Repeating unit: repeating unit having an acid group: repeating unit having a polymerizable group = 19: 19: 32: 30. The weight average molecular weight (Mw) was 11,500 (GPC).

&Lt; Synthesis Example 3: Synthesis of pigment multimer P-3 >

[Formula 97]

To the three-necked flask, NMP (2.00 g) was added, and the mixture was heated to 90 占 폚 under a nitrogen atmosphere. To this solution was added a monomer 5 (2.92 g), monomer 6 (2.08 g), methacrylic acid (0.80 g), dodecylmercaptan (0.12 g), dimethyl 2,2'-azobis (isobutyrate) : V601, manufactured by Wako Pure Chemical Industries, Ltd.) (0.26 g) and NMP (15.40 g) was added dropwise over 1 hour. Thereafter, the mixture was stirred for 4 hours and then cooled to obtain an NMP solution of (PM-3). Next, glycidyl methacrylate (0.49 g), tetrabutylammonium bromide (0.09 g) and p-methoxyphenol (63 mg) were added and heated at 100 ° C. for 15 hours in an air atmosphere to obtain methacrylic acid It was confirmed that glycidyl was lost. After cooling, the solution was added dropwise to an acetonitrile / ion-exchange water mixed solvent and re-dissolved to obtain 5.44 g of a colorant oligomer (P-3).

The composition ratio (molar ratio) of the obtained dye multimer was confirmed by ¹ H-NMR, and it was confirmed that the dye of the repeating unit derived from the triarylmethane dye (monomer 5): phthalocyanine dye (derived from monomer 6) : Repeating unit having an acid group: repeating unit having a polymerizable group = 24: 10: 44: 22. The weight average molecular weight (Mw) was 13,100 (GPC).

&Lt; Synthesis Example 4: Synthesis of pigment oligomer P-4 >

(98)

N-ethyl-2-pyrrolidone (hereinafter also referred to as " NEP ") (2.00 g) was added to a three-necked flask and heated to 90 캜 in a nitrogen atmosphere. To this solution was added a monomer (6) (4.20 g), monomer 7 (0.80 g), methacrylic acid (1.04 g), dodecyl mercaptan (0.13 g), 2,2'-azobis : V601, manufactured by Wako Pure Chemical Industries, Ltd.) (0.30 g) and NEP (16.12 g) was added dropwise over 1 hour. Thereafter, the mixture was stirred for 4 hours and then cooled to obtain (PM-4) NEP solution. Next, glycidyl methacrylate (0.72 g), tetrabutylammonium bromide (0.13 g) and p-methoxyphenol (70 mg) were added and heated at 100 ° C. for 15 hours in an air atmosphere to obtain methacrylic acid It was confirmed that glycidyl was lost. After cooling, the solution was added dropwise to an acetonitrile / ion-exchange water mixed solvent and re-applied to obtain 6.07 g of a colorant oligomer (P-4).

The composition ratio (molar ratio) of the resulting dye multimer was confirmed by ¹ H-NMR, and it was confirmed that the dye structure of the repeating unit having azo dye structure derived from phthalocyanine dye (monomer 6): azomethanone derived from monomer 7 : Repeating unit having an acid group: repeating unit having a polymerizable group = 18: 8: 44: 30. The weight average molecular weight (Mw) was 13,600 (GPC).

&Lt; Synthesis Example 5: Synthesis of pigment multimer P-5 >

[Formula 99]

To the three-necked flask, NMP (2.00 g) was added, and the mixture was heated to 80 占 폚 under a nitrogen atmosphere. To this solution were added 3.09g of monomer 8, 1.91g of monomer 7, 0.74g of methacrylic acid, 0.13g of dodecylmercaptan, dimethyl 2,2'-azobis (isobutyrate) : V601, manufactured by Wako Pure Chemical Industries, Ltd.) (0.31 g) and NMP (15.40 g) was added dropwise over 1 hour. Thereafter, the mixture was stirred for 4 hours and then cooled to obtain an NMP solution of (PM-5). Next, glycidyl methacrylate (0.43 g), tetrabutylammonium bromide (0.08 g) and p-methoxyphenol (62 mg) were added and heated at 100 ° C. for 15 hours in an air atmosphere to obtain methacrylic acid It was confirmed that glycidyl was lost. After cooling, the solution was added dropwise to a mixed solvent of methanol / ion-exchanged water and subjected to re-precipitation to obtain 4.73 g of a colorant oligomer (P-5).

The composition ratio (molar ratio) of the obtained dye multimer was confirmed by ¹ H-NMR, and it was confirmed that the repeating unit having a dye structure derived from an azo dye (monomer 8) Unit: repeating unit having an acid group: repeating unit having a polymerizable group = 20: 29: 34: 17. The weight average molecular weight (Mw) was 12,200 (GPC).

&Lt; Synthesis Example 6: Synthesis of pigment multimer P-6 >

(100)

Cyclohexanone (2.00 g) was added to the three-necked flask, and the mixture was heated to 90 占 폚 under a nitrogen atmosphere. To this solution were added 4.30 g of monomer 6 (4.35 g), monomer 7 (0.65 g), 2-methacryloyloxyethyl succinic acid (1.49 g), dodecylmercaptan (0.09 g), 2,2'-azobis (Trade name: V601, manufactured by Wako Pure Chemical Industries, Ltd.) (0.20 g) and cyclohexanone (44.30 g) was added dropwise over 1 hour. Thereafter, the mixture was stirred for 4 hours and then cooled to obtain a cyclohexanone solution of (PM-6).

The composition ratio (molar ratio) of the resulting dye multimer was confirmed by ¹ H-NMR, and it was confirmed that the dye structure of the repeating unit having azo dye structure derived from phthalocyanine dye (monomer 6): azomethanone derived from monomer 7 : Repeating unit having an acid group = 29: 10: 61. The weight average molecular weight (Mw) was 9,900 (GPC).

&Lt; Synthesis Example 7: Synthesis of pigment oligomer P-7 >

(101)

(1.41 g), monomer 2 (1.10 g), methacrylic acid (0.52 g), dodecyl mercaptan (0.07 g), polyethylene glycol monomethacrylate (trade name: BLEMMER PE- 90, manufactured by Nippon Oil Co., Ltd.) (0.12 g) and cyclohexanone (7.05 g) were added, and the mixture was heated to 90 占 폚 under a nitrogen atmosphere. To this solution were added monomer 1 (1.41 g), monomer 2 (1.10 g), methacrylic acid (0.52 g), dodecylmercaptan (0.07 g), blemmer PE-90 (0.12 g), 2,2'- A mixed solution of dimethyl (trade name: V601, manufactured by Wako Pure Chemical Industries, Ltd.) (0.30 g) and cyclohexanone (7.05 g) was added dropwise over 1 hour. Thereafter, the mixture was stirred for 4 hours and then cooled to obtain a cyclohexanone solution of (PM-7). Was carried out in the same manner as in Synthesis Example 1 to obtain 6.01 g of a colorant oligomer (P-7).

The composition ratio (molar ratio) of the resulting dye multimer was confirmed by ¹ H-NMR, and it was confirmed that repeating units having a dye structure derived from a dypyrromethene dye-derived (monomer 1 derived) dye structure: Unit: repeating unit having an acid group: repeating unit having a polymerizable group: repeating unit derived from a blemmer PE-90 = 11: 12: 35: 34: 8. The weight average molecular weight (Mw) was 10,400 (GPC).

&Lt; Synthesis Example 8: Synthesis of dye multimer P-8 >

&Lt; EMI ID =

To a three-necked flask was charged 2.81 g of monomer 1 (2.19 g), monomer 2 (1.04 g), 2-cyano-2-propyldodecyl trithiocarbonate (0.28 g), cyclohexanone 14.09 g), and the mixture was heated to 85 캜 under a nitrogen stream. To this solution, 2,2'-azobisisobutyronitrile (trade name: V60, manufactured by Wako Pure Chemical Industries, Ltd.) (0.13 g) was added and the mixture was stirred at 85 ° C for 6 hours and then cooled PM-8) was obtained. Next, glycidyl methacrylate (0.90 g), tetrabutylammonium bromide (0.16 g) and p-methoxyphenol (70 mg) were added and heated at 100 ° C. for 6 hours in an air atmosphere to obtain methacrylic acid It was confirmed that glycidyl was lost. After cooling, the solution was added dropwise to an acetonitrile / ion-exchange water mixed solvent and re-applied to obtain 6.35 g of a pigment-like polymer (P-8).

The composition ratio (molar ratio) of the resulting dye multimer was confirmed by ¹ H-NMR, and it was confirmed that repeating units having a dye structure derived from a dypyrromethene dye-derived (monomer 1 derived) dye structure: Unit: repeating unit having an acid group: repeating unit having a polymerizable group = 13: 13: 38: 36. The weight average molecular weight (Mw) was 9,300 (GPC).

&Lt; Synthesis Example 9: Synthesis of pigment oligomer P-9 >

&Lt; EMI ID =

(1.41 g), monomer 2 (1.10 g), methacrylic acid (0.52 g), dodecyl mercaptan (0.07 g), and pentamethylpiperidinyl methacrylate (trade name: 711MM, manufactured by Hitachi Chemical Co., Ltd.) (0.12 g) and cyclohexanone (7.05 g) were added, and the mixture was heated to 90 DEG C under a nitrogen atmosphere. To this solution was added monomer 1 (1.41 g), monomer 2 (1.10 g), methacrylic acid (0.52 g), dodecylmercaptan (0.07 g), pancuryl FA-711 MM (0.12 g), 2,2'- A mixed solution of dimethyl (trade name: V601, manufactured by Wako Pure Chemical Industries, Ltd.) (0.30 g) and cyclohexanone (7.05 g) was added dropwise over 1 hour. Thereafter, the mixture was stirred for 4 hours and then cooled to obtain a cyclohexanone solution of (PM-9). Was carried out in the same manner as in Synthesis Example 1 to obtain 5.40 g of a colorant oligomer (P-9).

The composition ratio (molar ratio) of the resulting dye multimer was confirmed by ¹ H-NMR, and it was confirmed that repeating units having a dye structure derived from a dypyrromethene dye-derived (monomer 1 derived) dye structure: Unit: repeating unit having an acid group: repeating unit having a polymerizable group: repeating unit derived from pancryl FA-711MM = 12: 12: 35: 34: 7. The weight average molecular weight (Mw) was 10,100 (GPC).

&Lt; Synthesis Example 1 &gt; Synthesis of dye oligomer P-20 >

&Lt; EMI ID =

(P-20) was prepared in the same manner as in Synthesis Example 1 except that the monomer 1 (1.41 g) and the monomer 2 (1.10 g) used in Synthesis Example 1 were changed to monomer 1 (2.50 g) g.

Recording unit having a dye structure derived from a dipyramethine dye (derived from monomer 1): repeating unit having an acid group: repeating unit having a polymerizable group = 30 (molar ratio) of the obtained dye multimer was confirmed by ¹ H- : 48: 22. The weight average molecular weight (Mw) was 11,500 (GPC).

&Lt; Synthesis Example 2 &gt; Synthesis of dye oligomer P-21 >

&Lt; EMI ID =

Cyclohexanone (2.00 g) was added to the three-necked flask, and the mixture was heated to 90 占 폚 under a nitrogen atmosphere. To this solution were added 5.00 g of monomer 2, 1.04 g of methacrylic acid, 0.15 g of dodecyl mercaptan, dimethyl 2,2'-azobis (isobutyrate) (trade name: V601, manufactured by Wako Pure Chemical Industries, (0.34 g) and cyclohexanone (12.10 g) was added dropwise over 1 hour. Thereafter, the mixture was stirred for 4 hours and then cooled to obtain a cyclohexanone solution of (PM-21). Next, glycidyl methacrylate (0.90 g), tetrabutylammonium bromide (0.16 g) and p-methoxyphenol (70 mg) were added and heated at 100 ° C. for 6 hours in an air atmosphere to obtain methacrylic acid It was confirmed that glycidyl was lost. After cooling, the solution was added dropwise to a mixed solvent of acetonitrile / ion-exchange water and re-applied to obtain 5.88 g of a colorant oligomer (P-21).

The composition ratio (molar ratio) of the obtained dye multimer was confirmed by ¹ H-NMR, and it was confirmed that the repeating unit having a dye structure derived from xanthine dye (derived from monomer 2): repeating unit having an acid group: repeating unit having a polymerizable group = : 35. The weight average molecular weight (Mw) was 10,800 (GPC).

&Lt; Synthesis Example 3 ': Synthesis of pigment multimer P-22 >

&Lt; EMI ID =

(P-22) was obtained in the same manner as in Synthesis Example 2 'except that monomer 2 used in Synthesis Example 2' was changed to monomer 3 and cyclohexanone was changed to NMP.

The composition ratio (molar ratio) of the resulting dye multimer was confirmed by ¹ H-NMR, and it was confirmed that the repeating unit having a dye structure derived from xanthine color (monomer 3): repeating unit having an acid group: repeating unit having a polymerizable group = 36: 33 : 31. The weight average molecular weight (Mw) was 13,900 (GPC).

&Lt; Synthesis Example 4 &gt; Synthesis of pigment multimer P-23 >

&Lt; EMI ID =

A colorant oligomer (P-23) was obtained in the same manner as in Synthesis Example 2 'except that the monomer 2 used in Synthesis Example 2' was changed to Monomer 4 and cyclohexanone was changed to NMP.

(Molar ratio) of the obtained dye multimer was confirmed by ¹ H-NMR, the following repeating unit having a dye structure derived from a triarylmethane dye (derived from monomer 4): repeating unit having an acid group: repeating unit having a polymerizable group = 31:34:34. The weight average molecular weight (Mw) was 10,100 (GPC).

&Lt; Synthesis Example 5 ': Synthesis of dye multimer P-25 >

(108)

(P-25) was obtained in the same manner as in Synthesis Example 3 except that the monomer 5 (2.92 g) and the monomer 6 (2.08 g) used in Synthesis Example 3 were changed to monomer 6 (5.00 g) .

( ¹ ): the repeating unit having a dye structure derived from phthalocyanine dye (derived from monomer 5): repeating unit having an acid group: repeating unit having a polymerizable group = 28:47:25. The weight average molecular weight (Mw) was 12,500 (GPC).

&Lt; Synthesis Example 6 ': Synthesis of dye oligomer P-26 >

(109)

(P-26) was obtained in the same manner as in Synthesis Example 5, except that the monomer 8 (3.09 g) and the monomer 7 (1.91 g) used in Synthesis Example 5 were changed to monomer 8 (5.00 g) .

The composition ratio (molar ratio) of the obtained dye multimer was confirmed by ¹ H-NMR, and it was confirmed that the repeating unit having a dye structure derived from an azo dye (derived from monomer 8): repeating unit having an acid group: repeating unit having a polymerizable group = 50: : 17. The weight average molecular weight (Mw) was 9,200 (GPC).

&Lt; Synthesis Example 7 &gt; Synthesis of dye oligomer P-28 >

(110)

(P-28) was obtained in the same manner as in Synthesis Example 5, except that the monomer 8 (3.09 g) and the monomer 7 (1.91 g) used in Synthesis Example 5 were changed to Monomer 7 (5.00 g) .

Repeating units having a dye structure derived from an azomethine dye (monomer 7): repeating units having an acid group: repeating units having a polymerizable group = 48 (molar ratio) of the obtained dye multimer was confirmed by ¹ H-NMR : 35: 17. The weight average molecular weight (Mw) was 9,900 (GPC).

1. Preparation of resist solution

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

Composition of resist solution for undercoat layer

Solvent: propylene glycol monomethyl ether acetate Section 19.20

Solvent: Ethyl lactate 36.67 parts

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

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

Polymerization inhibitor: p-methoxyphenol 0.0061 part

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

Photopolymerization initiator: A photopolymerization initiator of a trihalomethyltriazine type

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

2. Fabrication of silicon wafer substrate with undercoat layer

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

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

3. Preparation of coloring composition

(Coloring composition 1)

The following components were mixed, dispersed and dissolved to obtain Coloring Composition 1.

Organic solvent (cyclohexanone): 17.12 parts

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

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

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

· Cyclohexanone solution of the colorant multimer (solid content concentration: 12.3%): 73.96 parts

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

Polymerization inhibitor (p-methoxyphenol): 0.0007 part

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

(Preparation of colored composition 2)

The following components were mixed, dispersed and dissolved to obtain Coloring Composition 2.

Organic solvent (cyclohexanone): 17.12 parts

Epoxy resin JER1031S (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 180-220 (g / eq.)): 4.40 parts

· Cyclohexanone solution of the colorant multimer (solid content concentration: 12.3%): 73.96 parts

Polymerization inhibitor (p-methoxyphenol): 0.0007 part

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

4. Fabrication of color filter (coloring pattern)

4-1: Fabrication of color filter by photolithography

The colored composition 1 prepared above was coated on the undercoat layer of the silicon wafer with the undercoat layer prepared above to form a colored layer (coating film). Then, a heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 캜 so that the dried film thickness of the coated film became 1 탆.

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

Thereafter, the silicon wafer substrate on which the coated film was irradiated was placed on a horizontal rotation table of a spin shower developing machine (DW-30 type, manufactured by Chemtronics Co., Ltd.), and a CD-2000 (FUJIFILM ELECTRONIC MATERIALS Ltd.) for 60 seconds at 23 ° C to form a colored pattern on the undercoat layer of the silicon wafer with the undercoat layer.

A silicon wafer having a colored pattern formed thereon is fixed to the horizontal rotary table by a vacuum chucking method and the silicon wafer is rotated at a rotation speed of 50 rpm by a rotary device and purified water is supplied from a spray nozzle Followed by spray drying, and post-baking was performed on a hot plate at 200 占 폚 for 300 seconds to obtain a transparent pattern (cured film) having a film thickness of 1 占 퐉 on a silicon wafer.

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

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

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

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

The colored composition 2 obtained above was applied on a glass substrate of 7.5 cm x 7.5 cm using a spin coater so as to have a film thickness of 0.5 m and heated at 200 캜 for 5 minutes using a hot plate, The film was cured to prepare a colored layer. The film thickness of this colored layer was 0.5 mu m.

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

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

Next, the obtained glass substrate was attached to an 8-inch silicon wafer, and RF power: 800 W, antenna bias: 400 W, wafer bias: 200 W, internal pressure of chamber: A first stage etching treatment was performed for 80 seconds at a substrate temperature of 50 ° C and a gas species and flow rate of a mixed gas of CF ₄ : 80 mL / min, O ₂ : 40 mL / min, and Ar: 800 mL / did.

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

After the dry etching under the above conditions, the photoresist stripping liquid "MS230C" (manufactured by Fuji Film Electronics Materials Co., Ltd.) was subjected to a stripping treatment at 50 ° C for 120 seconds to remove the resist, thereby forming a green coloring pattern . Further, washing with pure water and spin drying were performed, and dehydration baking treatment was then performed at 100 ° C for 2 minutes. Thus, a color filter was obtained.

5. Evaluation

5-1. Spectral characteristics

A coloring pattern was produced in the same manner as in the color filter of the photolithography method except that an Island pattern mask having a size of 7.0 mu m was used and the absorbance in a wavelength range of 400 to 700 nm in the formed coloring pattern was measured with a brown spectrophotometer (LCF-1500M, manufactured by Otsuka Denshi Co., Ltd.), and evaluated according to the following evaluation criteria.

A: The absorbance at the maximum absorption wavelength (? Max) is 1.0 or more, and the absorbance at the maximum absorption wavelength (? Max) is at least 200 times the absorbance at the minimum absorption wavelength (? Min).

B: The absorbance of the maximum absorption wavelength? Max is 1.0 or more, and the absorbance of the maximum absorption wavelength? Max is less than 200 times the absorbance at the minimum absorption wavelength? Min.

5-2. Color heterogeneity

An evaluation substrate was prepared in the same manner as the method of forming a color filter coloring pattern by a photolithography method, except that a glass substrate was used instead of the wafer with an undercoat layer, and the wafer was directly exposed without using a mask. The luminance distribution was analyzed by the following method and based on the ratio of the pixels whose deviation from the average is within ± 5% to the total number of pixels.

A method of measuring the luminance distribution will be described. First, an image obtained by photographing the luminance distribution of the glass plate with the colored layer with a microscope MX-50 (manufactured by Olympus) was analyzed.

In the luminance distribution, the luminance with the largest number of pixels is defined as the average luminance.

-Evaluation standard-

A: More than 99% of the total number of pixels of a pixel whose deviation from the average is within ± 5%

B: 98% or more and less than 99% of the pixels in which the deviation from the average is within ± 5%

C: 97% or more and less than 98% of the pixels in which the deviation from the average is within ± 5%

D: 95% or more and less than 97% of the pixels in which the deviation from the average is within ± 5%

E: a pixel within ± 5% of the deviation from the average is less than 95% of the total number of pixels

5-3. Light transmittance

A coloring pattern was produced in the same manner as in the color filter by the photolithography method except that the island pattern mask of 7.0 탆 square was used. The absorbance in a wavelength range of 200 to 700 nm in the formed coloring pattern was measured with a brown spectrophotometer LCF-1500M manufactured by Otsuka Denshi Co., Ltd.), and the transmittance at the maximum transmittance was evaluated according to the following evaluation criteria.

A: transmittance of 80% or more

B: transmittance of 70% or more and less than 80%

C: transmittance less than 70%

5-4. Heat resistance

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

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

A: The value of? E * ab is less than 10

B:? E * ab value is 10 or more and less than 20

C:? E * ab value is 20 or more

5-5. Solvent resistance

The coloring composition was coated on a glass wafer using a spin coater so as to have a film thickness of 0.6 mu m after drying, and then heated with a hot plate at 200 DEG C for 300 seconds.

Propylene glycol monomethyl ether acetate (PGMEA) was added dropwise to the color filter obtained above, left for 120 seconds, and rinsed with running water for 10 seconds.

The spectral fluctuation of the transmittance before and after the dropping of various liquids was measured using MCPD-3000 (manufactured by OTSUKA DENKI CO., LTD.) And the color difference (DELTA E * ab) was measured. The lower the? E * ab, the better the solvent resistance.

A: The value of? E * ab is less than 10

B:? E * ab value is 10 or more

[Table 1]

As is clear from the above results, the coloring composition of the present invention was excellent in color irregularity and spectroscopic characteristics. Further, it was excellent in light transmittance, heat resistance and solvent resistance. Further, the cured products of Examples 1 to 9 were observed under an optical microscope, and they were homogeneous. In addition, the sensitivity of Example 9 tended to be higher than that of Example 1.

On the other hand, in Comparative Examples 1 to 4 using two kinds of dye multimer, color unevenness and light transmittance were inferior. Further, the cured products of Comparative Examples 1 to 4 were observed under an optical microscope, and small areas having different hues were gathered. This is presumably because the compatibility of the mixed dye multimer is poor and phase separation is performed.

&Lt; Reference Example 1 &

A coloring composition was prepared in the same manner as in Example 1 except that P-20 was used in place of P-1 as a colorant multimer in Example 1, and the spectroscopic characteristics were evaluated in the same manner as described above. In Reference Example 1, it was found that the spectral characteristics tended to be inferior.

<Reference Example 2>

A coloring composition was prepared in the same manner as in Example 1 except that P-21 was used in place of P-1 as a colorant multimer in Example 1, and the spectroscopic characteristics were evaluated in the same manner as described above. In Reference Example 2, it was found that the spectral characteristic tended to be inferior.

<Reference Example 3>

A coloring composition was prepared in the same manner as in Example 1 except that P-22 was used in place of P-1 as a colorant multimer in Example 1, and the spectroscopic characteristics were evaluated in the same manner as described above. In Reference Example 3, it was found that the spectral characteristic tended to be inferior.

&Lt; Example 10 >

A test was conducted in the same manner as in Example 1 except that the polymerizable compound was changed to KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate) in the same manner as in Example 1, The same favorable results as in Example 1 were obtained.

&Lt; Example 11 >

The same results as in Example 1 were obtained in the same manner as in Example 1 except that the photopolymerization initiator was changed to IRGACURE OXE-01 (manufactured by BASF).

Claims (18)

A dye multimer having a repeating unit a1 having a dye structure and a repeating unit a2 having a dye structure having a skeleton different from the dye structure of the repeating unit a1,
Curable compound
&Lt; / RTI &gt;
Wherein the dye structure of the repeating unit a1 and the dye structure of the repeating unit a2 are derived from a dye selected from a dipyramethine dye, a triarylmethane dye, a xanthone dye, an azo dye, and a phthalocyanine dye , Coloring composition. The method according to claim 1,
The pigment multimer having a repeating unit represented by the following general formula (a1-1) and a repeating unit represented by the following general formula (a2-1);
[Chemical Formula 1]

In the general formulas (a1-1) and (a2-1), Q ¹ and Q ² each independently represent a trivalent linking group, L ¹ and L ² each independently represent a single bond or a divalent linking group, D ¹ and D ^{2 each} represent a dye structure derived from a dye selected from a dipyramethine dye, a triarylmethane dye, a xanthine dye, an azo dye, and a phthalocyanine dye, with the proviso that D ² is different from D ¹ , And * indicates the binding hand. The method according to claim 1,
Wherein the dye multimer further comprises a repeating unit having an acid group. The method according to claim 1,
Wherein the dye multimer further comprises a repeating unit having a polymerizable group. The method according to claim 1,
Wherein the curable compound is a polymerizable compound and further contains a photopolymerization initiator. The method according to claim 1,
Wherein the colorant multimer is one kind selected from a (meth) acrylic resin, a styrene resin, and a (meth) acrylic / styrene resin. The method according to claim 1,
A coloring composition used for forming a colored layer of a color filter. A cured film obtained by curing the coloring composition according to claim 1. A color filter having the cured film according to claim 8. A step of forming a coloring composition layer by applying the coloring composition according to claim 1 on a support, a step of exposing the coloring composition layer in a pattern shape, and a step of forming a coloring pattern by developing and removing the unexposed portion / RTI &gt; A method of manufacturing a color filter, comprising the pattern forming method according to claim 10. A solid-state imaging device having the color filter according to claim 9. An image display apparatus having the color filter according to claim 9. The method according to claim 1,
Wherein the dye structure of the repeating unit a1 is a dye structure derived from a xanthan gum and the dye structure of the repeating unit a2 is a dye structure derived from a dipyramethane dye. The method according to claim 1,
The proportion of the repeating unit a1 is 10 to 90 mol% of the total repeating units constituting the dye multimer, and the proportion of the repeating unit a2 is 10 to 90 mol% of the total repeating units constituting the colorant multimer. The method according to claim 1,
The proportion of the repeating unit a1 is 20 to 80 mol% of the total repeating units constituting the dye multimer, and the proportion of the repeating unit a2 is 20 to 80 mol% of the total repeating units constituting the colorant multimer. The method according to claim 1,
The proportion of the repeating unit a1 is 25 to 75 mol% of the total repeating units constituting the dye multimer, and the proportion of the repeating unit a2 is 25 to 75 mol% of the total repeating units constituting the dye multimer. The method according to claim 1,
Wherein the dye structure of the repeating unit a2 is derived from a dye selected from a triarylmethane dye, a xanthine dye, and an azo dye.