KR102014106B1 - 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

Provided are a color composition having excellent color unevenness and spectroscopic characteristics, a cured film, a color filter, a method for producing a color filter, a solid-state image sensor, and an image display device using the colored composition.
It is a coloring composition containing the repeating unit a1 which has a pigment | dye structure, the repeating unit a2 which has a pigment | dye structure which has a pigment | dye structure which differs from the pigment | dye structure of the repeating unit a1, and a curable compound.

Description

Colored composition, cured film, color filter, pattern formation method, manufacturing method of color filter, solid-state image sensor, and image display apparatus using the same {COLORING COMPOSITION, CURED FILM USING SAME, COLOR FILTER, PATTERN FORMING METHOD, METHOD FOR PRODUCING COLOR FILTER , SOLID-STATE IMAGING ELEMENT AND IMAGE DISPLAY DEVICE}

The present invention relates to a coloring composition. In particular, it is related with the coloring composition used suitably for formation of the colored layer of a color filter. Moreover, it is related with the cured film, a color filter, a solid-state image sensor, and an image display apparatus using a coloring composition. Moreover, it also relates to the pattern formation method using a coloring composition and the manufacturing method of a color filter.

In recent years, with the development of personal computers, especially large-screen liquid crystal televisions, the demand for liquid crystal displays (LCDs), especially color liquid crystal displays, tends to increase. The demand for further high image quality has also led to the spread of organic EL displays. On the other hand, with the spread of digital cameras and camera-mounted mobile phones, the demand for solid-state imaging devices such as CCD image sensors is also greatly increased.

Color filters are used as key devices for these displays and optical elements, and the demand for cost reduction is increasing along with the demand for further high image quality. Such a color filter is normally provided with the coloring layer (pattern) of three primary colors of red (R), green (G), and blue (B), and in a display device or an image pick-up element, it carries out three primary colors of the light which passes. It acts as a fraction.

Here, the dye multimer is examined as a coloring agent which forms a colored layer in recent years.

Specifically, Patent Document 1 discloses a coloring composition containing a dye multimer having a dye skeleton derived from a dipyrromethene-based metal complex compound.

Patent Literature 2 discloses a coloring composition containing a dye multimer having an alkali-soluble group having a weight average molecular weight (Mw) of 5000 to 20000 as a coloring agent and a degree of dispersion of 1.00 to 2.50.

Patent Document 1: Japanese Unexamined Patent Publication No. 2012-46708 Patent Document 2: Japanese Unexamined Patent Publication No. 2011-213925

The demand of the coloring composition containing the above-mentioned dye multimer is increasing, and the coloring composition which can form the pattern excellent in the color nonuniformity and the spectral characteristic is calculated | required by the recent technical innovation.

As one of the methods of adjusting the spectral characteristics, there is a method of using a plurality of dye multimers in combination. As a result of the inventors' investigation, it has been found that color unevenness tends to occur depending on the combination of the dye multimers.

In view of such a situation, an object of this invention is to provide the coloring composition which is excellent in color nonuniformity and spectral characteristics.

As a result of the present inventor's examination under the said subject, when the pigment | dye structure of another frame | skeleton was introduce | transduced into a dye multimer, it discovered that the coloring composition excellent in color nonuniformity and spectral characteristics can be obtained, and completes this invention. Reached.

Specifically, by the following means <1>, Preferably, the said subject was solved by <2>-<17>.

The coloring composition containing the repeating unit a1 which has a <1> pigment | dye structure, the repeating unit a2 which has a pigment | dye structure which has a skeleton different from the pigment | dye structure of the repeating unit a1, and a curable compound.

At least one of the pigment | dye structure which a <2> repeating unit a1 has, and the pigment | dye structure which a repeating unit a2 has is a dipyrromethene pigment, a triaryl methane pigment | dye, a xanthene pigment | dye, an azo pigment | dye, a diketopyrrolopyrrole pigment | dye, and a phthalo The coloring composition as described in <1> derived from the pigment chosen from a cyanine pigment | dye, a cyanine pigment | dye, and a squarylium pigment | dye.

At least one of the pigment | dye structure which a <3> repeating unit a1 has, and the pigment | dye structure which a repeating unit a2 has are a dipyrromethene dye, a triaryl methane dye, a xanthene dye, an azo dye, a diketopyrrolopyrrole dye, and a phthalo The coloring composition as described in <1> or <2> derived from the pigment chosen from a cyanine pigment | dye.

The pigment | dye structure which a <4> repeating unit a1 has, and the pigment | dye structure which a repeating unit a2 has are a dipyrromethene pigment | dye, a triaryl methane pigment | dye, a xanthene pigment | dye, an azo dye, a diketopyrrolopyrrole pigment | dye, and a phthalocyanine pigment | dye. The coloring composition in any one of <1>-<3> derived from the pigment chosen from.

<5> Dye multimer has coloring in any one of <1>-<4> which has a repeating unit represented by the following general formula (a1-1), and a repeating unit represented by the following general formula (a2-1). Composition;

[Formula 1]

In General Formulas (a1-1) and (a2-1), Q ¹ and Q ² each independently represent a trivalent linking group, and 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 that of D ^1, and * represents a bond.

The coloring composition in any one of <1>-<5> in which a <6> dye multimer further has a repeating unit which has an acidic radical.

The coloring composition in any one of <1>-<6> in which a <7> dye multimer further has a repeating unit which has a polymeric group.

The coloring composition in any one of <1>-<7> in which a <8> curable compound is a polymeric compound and contains a photoinitiator further.

The coloring composition in any one of <1>-<8> whose <9> dye multimer is 1 type chosen from (meth) acrylic-type resin, styrene resin, and (meth) acryl / styrene-type resin.

The coloring composition in any one of <1>-<9> used for formation of the colored layer of a <10> color filter.

<11> Cured film formed by hardening | curing the coloring composition in any one of <1>-<10>.

<12> The color filter which has a cured film as described in <11>.

<13> The process of forming the coloring composition layer by applying the coloring composition in any one of <1>-<10> on a support body, the process of exposing a coloring composition layer in a pattern form, and developing and removing an unexposed part, The pattern formation method containing the process of forming a coloring pattern.

<14> The manufacturing method of a color filter containing the pattern formation method as described in <13>.

<15> Solid-state image sensor which has a color filter obtained by the color filter as described in <12>, or the manufacturing method of the color filter as described in <14>.

<16> The image display apparatus which has a color filter obtained by the color filter as described in <12>, or the manufacturing method of the color filter as described in <14>.

According to this invention, the coloring composition excellent in color nonuniformity and spectral characteristics can be provided. Moreover, it became possible to provide the cured film, the color filter, the pattern formation method, the manufacturing method of a color filter, a solid-state image sensor, and an image display apparatus using the coloring composition mentioned above.

EMBODIMENT OF THE INVENTION Below, the content of this invention is demonstrated in detail. In addition, it is used by the meaning which includes with "-" the numerical value described before and after that as a lower limit and an upper limit in this specification. In addition, the organic electroluminescent element in this invention means an organic electroluminescent element.

In this specification, a total solid means the gross mass of the component remove | excluding the solvent from the whole composition of a coloring composition. In addition, solid content means solid content in 25 degreeC.

In the description of group (atom group) in this specification, the description which is not describing substitution and unsubstitution includes what has a substituent with the thing which does not have a substituent. For example, an "alkyl group" includes not only the alkyl group (unsubstituted alkyl group) which does not have a substituent but the alkyl group (substituted alkyl group) which has a substituent.

In addition, "radiation" in this specification means the bright spectrum of a mercury lamp, the far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X rays, an electron beam, etc., for example. In addition, in this invention, light means actinic light or a radiation. Unless otherwise specified, the term "exposure" in the present specification refers to not only exposure by far ultraviolet rays, X-rays, EUV light or the like represented by mercury lamps or excimer lasers, but also drawing by exposure to particle beams such as electron beams and ion beams. Include.

In addition, in this specification, "(meth) acrylate" shows both or one of acrylate and methacrylate, and "(meth) acryl" shows both or both of acryl and methacryl, "(Meth) acryloyl" represents both or both of acryloyl and methacryloyl.

In addition, in this specification, a "monomer" and a "monomer" are synonymous. The monomer in this specification is distinguished from an oligomer and a polymer, and a weight average molecular weight says 2,000 or less compound. In the present specification, the polymerizable compound refers to a compound having a polymerizable functional group, and may be a monomer or a polymer. A polymerizable functional group means group which participates in a polymerization reaction.

In the present specification, Me 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 the term as long as the desired action of the process is achieved, even if the process is not clearly distinguishable from other processes.

This invention is made | formed in view of said situation, and an object of this invention is to provide the coloring composition excellent in the color characteristic.

In this specification, a weight average molecular weight and a number average molecular weight are defined as polystyrene conversion value by GPC measurement. In this specification, a weight average molecular weight (Mw) and a number average molecular weight (Mn) use HLC-8220 (made by Tosoh Corporation), for example, and use TSKgel Super AWM-H (made by Tosoh Corporation) as a column. , 6.0 mm ID x 15.0 cm) can be obtained by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.

The coloring composition of this invention contains the repeating unit a1 which has a pigment | dye structure, the dye multimer which has at least the repeating unit a2 which has a pigment | dye structure which has a skeleton different from the pigment | dye structure of the repeating unit a1, and a curable compound.

EMBODIMENT OF THE INVENTION Hereinafter, the detail of this invention is demonstrated.

<Pigment multimer>

The dye multimer used by this invention has at least the repeating unit a1 which has a pigment | dye structure, and the repeating unit a2 which has a pigment | dye structure which has a skeleton different from the pigment | dye structure of the repeating unit a1. Hereinafter, the repeating unit a1 which has a pigment | dye structure is also called repeating unit (a1), and the repeating unit a2 which has a pigment | dye structure is also called repeating unit (a2).

In the case of adjusting the spectral characteristics by mixing a plurality of dye multimers, color unevenness may occur due to the effect of compatibility or the like depending on the combination of the dye multimers. In particular, when the content of the dye multimer is increased in order to increase the dye concentration, the influence of compatibility increases and the color nonuniformity tends to occur, but the dye multimer used in the present invention is a repeating unit (a1) in all the repeating units. ) And at least the repeating unit (a2), there is no problem due to the compatibility, and excellent color unevenness and spectral characteristics. Moreover, even if it contains a large amount of the dye multimer used by this invention in a coloring composition, color nonuniformity can hardly generate | occur | produce and a pigment concentration can be raised.

In the present invention, the "pigment structure having another skeleton" means a pigment structure derived from pigment compounds having different mother-nucleus structures. For example, when the pigment | dye structure of a repeating unit (a1) is a pigment | dye structure derived from a dipyrromethene pigment | dye, the pigment | dye structure of a repeating unit (a2) shows the pigment | dye structure derived from dyes other than a dipyrromethene pigment | dye. Means that.

In the present invention, the dye structure of the repeating unit (a1) and the dye structure of the repeating unit (a2) may each include only one type of dye structure having the same skeleton, and the skeleton is the same, but the substituent and the center metal You may contain two or more types of pigment | dye structures from which different etc. differ. Moreover, you may further include the repeating unit (henceforth a repeating unit (a3)) which has a pigment | dye structure which has a skeleton different from the pigment | dye structure of a repeating unit (a1) and the pigment | dye structure of a repeating unit (a2).

Although a dye multimer is not specifically defined if it contains a pigment | dye structure, It is preferable that it is 1 type chosen from (meth) acrylic-type resin, styrene resin, and (meth) acryl / styrene-type resin.

In addition, (meth) acrylic-type resin means resin which contains (meth) acrylic resin as a main component. As for containing a (meth) acrylic resin as a main component, it is preferable to contain 50 mass% or more of (meth) acrylic resin in (meth) acrylic-type resin, It is more preferable to contain 60 mass% or more, More than 70 mass% It is especially preferable to contain.

In addition, styrene resin means resin containing styrene resin as a main component. As for containing styrene resin as a main component, it is preferable to contain 50 mass% or more of styrene resin in styrene resin, It is more preferable to contain 60 mass% or more, It is especially preferable to contain 70 mass% or more .

In addition, (meth) acryl / styrene resin means resin containing (meth) acrylic resin and styrene resin as a main component. It is preferable to contain (meth) acryl resin and a styrene resin in total in (meth) acryl / styrene resin, and to contain (meth) acryl / styrene resin as a main component, and it is 60 mass% It is more preferable to contain more than, and it is especially preferable to contain 70 mass% or more.

Hereinafter, the counter anion of the structure used as a skeleton of a dye multimer, a pigment structure, and the pigment structure contained as needed is demonstrated.

<< skeletal structure of repeating unit (a1) and repeating unit (a2) >>

Although it does not specifically define as skeletal structure of a repeating unit (a1) and a repeating unit (a2), General formula (A), general formula (B), and which are represented by Paragraph No. 0276 of Unexamined-Japanese-Patent No. 2013-28764-0304, and It is preferable to make at least one of the structural units represented by general formula (C) into a skeleton, or it is preferable that it is a dye multimer represented by general formula (D). Paragraph No. 0276 of Unexamined-Japanese-Patent No. 2013-28764-description of 0304 are integrated in this specification.

In this 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).

Since the ratio of the repeating unit (a1) and the ratio of the repeating unit (a2) in all the repeating units constituting the dye multimer are different depending on the required spectroscopy, there is no particular limitation. For example, it is preferable that the ratio of a repeating unit (a1) is 10-90 mol% of all the repeating units which comprise a dye multimer, 20-80 mol% is more preferable, 25-75 mol% is more desirable. It is preferable that it is 10-90 mol% of all the repeating units which comprise a dye multimer, as for the ratio of a repeating unit (a2), 20-80 mol% is more preferable, 25-75 mol% is more preferable.

Moreover, it is preferable that it is 30-100 mol%, and, as for the sum total of the repeating unit which has a pigment | dye structure in all the repeating units which comprise a dye multimer, 40-100 mol% is more preferable.

[Formula 2]

In General Formulas (a1-1) and (a2-1), Q ¹ and Q ² each independently represent a trivalent linking group, and 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 bond.

In General Formulas (a1-1) and (a2-1), Q ¹ and Q ² each independently represent a trivalent linking group. Q <^1> and Q <^2> are the coupling groups formed by superposition | polymerization, and point to the part which forms the repeating unit corresponding to the main chain formed by superposition | polymerization reaction. In addition, the site | part represented by two "*" becomes a repeating unit.

The Q ¹ and Q ² are not particularly limited as long as they are a linking group formed of a known polymerizable monomer, but in particular, a linking group represented by the following (XX-1) to (XX-24) is preferable, and (XX-1) and (XX (Meth) acrylic linkage chain represented by -2), styrene linkage chain represented by (XX-10) to (XX-17), (XX-18) and (XX-19), and also represented by (XX-24) More preferably, it is selected from a vinyl linking chain, (meth) acrylic linking chains represented by (XX-1) and (XX-2), styrene linking chains represented by (XX-10) to (XX-17), More preferably, it is selected from the vinyl linking chain represented by (XX-24), and the (meth) acrylic linking chain represented by (XX-1) and (XX-2) and the styrene linking chain represented by (XX-11). Is more preferable.

It represents ^{couple |} bonding with L <^1> or L <^2> in the site | part represented by * among (XX-1)-(XX-24). Me represents a methyl group. In addition, R in (XX-18) and (XX-19) represents a hydrogen atom, a C1-C5 alkyl group, or a phenyl group.

[Formula 3]

[Formula 4]

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

As a bivalent coupling group, a C1-C30 substituted or unsubstituted alkylene group (for example, methylene group, ethylene group, trimethylene group, a propylene group, butylene group, etc.), C6-C30 substituted or unsubstituted Arylene group (for example, phenylene group, naphthalene group, etc.), substituted or unsubstituted heterocyclic linking group, -CH = CH-, -O-, -S-, -C (= O)-, -CO _2- , -NR-, -CONR-, -O ₂ C-, -SO-, -SO ₂ -and a linking group formed by linking two or more thereof. Moreover, the structure in which L <^1> and L <^2> contain an anion is also preferable. L ¹ and L ² are more preferably a single bond or an alkylene group, and more preferably a single bond or-(CH ₂ ) n-(n is an integer of 1 to 5). Here, each R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

D ¹ and D ² represent a pigment structure derived from a coloring compound to be described later. In addition, D ² is the dye structure having a different skeleton and D ^1.

The dye multimer having a repeating unit (a1) and a repeating unit (a2) comprises (1) a method of synthesizing a monomer having a dye residue by addition polymerization, (2) an isocyanate group, an acid anhydride group or an epoxy group. It can synthesize | combine by the method of making the polymer which has high reactive functional groups, such as these, and the pigment | dye which has a functional group (hydroxyl group, a primary or secondary amino group, a carboxyl group, etc.) which can react with a high reactive group.

Known addition polymerization (radical polymerization, anionic polymerization, cationic polymerization) can be applied to the addition polymerization. Among them, synthesis by radical polymerization, in particular, is preferable because it can moderate the reaction conditions and does not decompose the pigment structure. Do. Known reaction conditions can be applied to the radical polymerization. That is, it is preferable that the dye multimer used by this invention is an addition polymer.

Especially, it is preferable that the dye multimer in this invention is a radical polymer obtained by radical polymerization using the pigment monomer which has an ethylenically unsaturated bond from a heat resistant viewpoint.

<< pigment structure >>

The pigment | dye structure used by this invention is not specifically determined, A well-known pigment | dye structure can be employ | adopted.

Specifically, dipyrromethene dye, carbonium dye (diphenylmethane dye, triaryl methane dye, xanthene dye, acridine dye, etc.), polymethane dye (oxonol dye, merocyanine dye, ah Lylidene pigments, styryl pigments, cyanine pigments, squarylium pigments, croconium pigments, etc., quinone pigments (benzoquinone pigments, naphthoquinone pigments, anthraquinone pigments, anthrapyridone pigments, etc.), azo pigments, From iketopyrrolopyrrole pigments, phthalocyanine pigments, subphthalocyanine pigments, perinone pigments, indigo pigments, thioindigo pigments, quinoxaline pigments, quinophthalone pigments, isoindolin pigments, and cyanine pigments The pigment | dye structure derived from the pigment | dye chosen, etc. are mentioned.

At least one of D ¹ and D ² is selected from a dipyrromethene dye, a triaryl methane dye, a xanthene dye, an azo dye, a diketopyrrolopyrrole dye, a phthalocyanine dye, a cyanine dye and a squarylium pigment It is preferable that it is a pigment | dye structure derived from the pigment | dye to become, and a pigment | dye structure derived from the pigment | dye chosen from a dipyrromethene pigment | dye, a triaryl methane pigment | dye, a xanthene pigment | dye, an azo pigment | dye, a diketopyrrolopyrrole pigment | dye, and a phthalocyanine pigment | dye. It is more preferable that is. More preferably, D ¹ and D ² are a dye structure derived from a dye selected from a dipyrromethene dye, a triaryl methane dye, a xanthene dye, an azo dye, a diketopyrrolopyrrole dye and a phthalocyanine dye. to be.

Among them, from the viewpoint of spectral characteristics, any one of D ¹ and D ² is a dye structure derived from a dye selected from a phthalocyanine dye, an azo dye, and a diketopyrrolopyrrole dye, and the other one, It is preferable that it is a pigment | dye structure derived from a yellow coloring agent. Examples of the yellow colorant include xanthene dyes, triaryl methane dyes, azo dyes, quinoxaline dyes, quinophthalone dyes and isoindolin dyes.

In addition, from the viewpoint of spectral characteristics, any one of D ¹ and D ² is a dye structure derived from a dipyrromethene pigment, and the other combination is a dye structure derived from a xanthene dye or a triaryl methane dye. desirable.

For specific pigment compounds that can form a pigment structure, see "New Dye Dye Handbook" (Organic Synthetic Chemistry Society; Maruzen, 1970), "Color Index" (The Society of Dyers and colourists), "Color Handbook" (Okawara) Et al., Godansha, 1986).

In the cation having a dye structure, particularly preferred dyes (pigment compounds) capable of forming a dye structure will be described in detail.

<<< dipyrromethene dye >>>

One of the aspects of the pigment | dye structure which concerns on this invention is the dipyrromethene pigment | dye structure shown below.

As a dipyrromethene pigment | dye in this invention, the dipyrromethene metal compound and the dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or a metal compound are preferable. In one place of these dipyrromethene pigment | dye structures, it couple | bonds with a polymer.

In addition, in this invention, the compound containing a dipyrromethene structure is called a dipyrromethene compound, and the complex in which the compound containing a dipyrromethene structure is arrange | positioned to a metal or a metal compound is called a dipyrromethene metal complex compound.

As a dipyrromethene metal complex compound, the dipyrromethene metal complex compound obtained from the dipyrromethene compound represented by the following general formula (M), a metal, or a metal compound, and its tautomer are preferable, Especially, as a preferable aspect, the following general formula The dipyrromethene metal complex compound represented by (7) or the dipyrromethene metal complex compound represented by following General formula (8) is mentioned, The dipyrromethene metal complex compound represented by General formula (8) is more preferable.

Dipyrromethene Metal Complex Compound Obtained from Dipyrromethene Compound and Metal or Metal Compound Represented by General Formula (M), and Tautomers thereof

One of the preferable aspects of a pigment | dye structure is the complex represented by the following general formula (M) (dipyrromethene compound) or its tautomer coordinated to a metal or a metal compound (henceforth "a specific complex" suitably). It is a pigment | dye structure containing. In the present invention, the following compound forms a cationic structure, for example, a metal such as zinc bonded to a nitrogen atom of the general formula (M) can form a cationic structure.

[Formula 5]

(In General Formula (M), R ⁴ to R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent. However, R ⁴ and R ⁹ are not bonded to each other to form a ring.)

The introduction site in the case where the compound represented by General Formula (M) is introduced into the structural units represented by General Formulas (A) to (D) is not particularly limited, but any of R ⁴ to R ^{9 may be used in view} of synthetic suitability. It is preferable to introduce in one site | part, it is more preferable to introduce in any one of R <^4> , R <^6> , R <^7> and R <^9> , and it is more preferable to introduce | transduce in either of R <^4> and R <^9> .

As a monovalent substituent in the case where R <^4> -R <^9> in general formula (M) shows a monovalent substituent, the substituent quoted by the term of the substituent group A mentioned later is mentioned.

When the monovalent substituent represented by R <^4> -R <^9> in general formula (M) is group which can be further substituted, you may further have a substituent demonstrated by R <^4> -R <^9> , and when it has 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 general formula (M) are respectively independently combining with each other and are 5-, 6-, or 7-membered cloth You may form a wreath or an unsaturated ring. However, R ⁴ and R ⁹ do not combine with each other to form a ring. When the 5-membered, 6-membered, and 7-membered ring formed is a group that can be further substituted, the substituents described in R ⁴ to R ⁹ may be substituted, and when substituted with two or more substituents, these substituents It may be 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 general formula (M) respectively independently combine with each other, the 5-membered, 6-membered which does not have a substituent, Or when forming a 7-membered saturated ring or unsaturated ring, As a 5-, 6- or 7-membered saturated ring or unsaturated ring which does not have a substituent, For example, a pyrrole ring, a furan ring, a thiophene ring, Pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexene ring, benzene ring, pyridine ring, pyrazine ring, and pyridazine ring And preferably a benzene ring or a pyridine ring.

R ¹⁰ in General Formula (M) preferably represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. As a halogen atom, an alkyl group, an aryl group, and a heterocyclic group, it is synonymous with the halogen atom of the substituent group A mentioned later, an alkyl group, an aryl group, and a heterocyclic group, respectively, and its preferable range is also the same.

When R <^10> represents an alkyl group, an aryl group, or a heterocyclic group, when an alkyl group, an aryl group, and a heterocyclic group are group which can be substituted further, you may be substituted by the substituent demonstrated by the term of the substituent group A mentioned later. And when substituted with two or more substituents, these substituents may be the same or different.

... metal or metal compound ...

The specific complex in this invention is a complex which the dipyrromethene compound represented by General formula (M) mentioned above, or its tautomer was coordinated with a metal or a metal compound.

Here, as a metal or a metal compound, any metal or metal compound which can form a complex may be sufficient, and a bivalent metal atom, a bivalent metal oxide, a bivalent metal hydroxide, or a bivalent metal chloride is contained. As the metal or metal compound, for example, in addition to metals such as Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, AlCl, InCl, FeCl, TiCl ₂ , SnCl _2, SiCl _2, GeCl _2, such as a metal chloride, metal oxides such as TiO, VO, also includes a metal hydroxide such as Si (OH) _2.

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

Next, the more preferable range of the specific complex in this invention of the compound represented by general formula (M) is demonstrated.

The preferable range of the specific complex in the present invention is that in general formula (M), R ⁴ and R ⁹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, and a hydroxyl group. Real group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, alinino group, heterocyclic amino group, carbonamide group, euraid group, imide group, Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, or 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 aryloxy group and a heterocycle Oxy, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, imide, alkoxycarbonylamino, sulfonamide, azo, alkylthio, arylthio, heterocyclic thio, alkylsulfonyl, Arylsulfonyl group or sulfamoyl group; R ⁶ and R ⁷ each independently represent 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 aryloxy group, a heterocyclic jade Period, acyl group, alkoxycarbonyl group, carbamoyl group, alinino group, carbon amide group, ureide group, imide group, alkoxycarbonylamino group, sulfonamide group, azo group, alkylthio group, arylthio group, heterocyclic thio Or 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 a range of Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or V = O.

As for the more preferable range of the specific complex in this invention, R <^4> and R <^9> respectively independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group in general formula (M), Acyl group, alkoxycarbonyl group, carbamoyl group, amino group, heterocyclic amino group, carbonamide group, ureade group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, azo group, alkylsulfonyl group, aryl Sulfonyl group or phosphinoylamino group; R ⁵ and R ⁸ are each independently alkyl, alkenyl, aryl, heterocyclic, cyano, nitro, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, imide, alkyl Sulfonyl group, arylsulfonyl group, or 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, a carbonamide group, an euraid group, or an imide group An alkoxycarbonylamino group, a sulfonamide 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; The metal or metal compound is in the range of Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or V = O.

Particularly preferred range of the specific complex in the present invention is, in general formula (M), R ⁴ and R ⁹ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, a heterocyclic amino group, and carbon Amide group, urea group, imide group, alkoxycarbonylamino group, sulfonamide group, azo group, alkylsulfonyl group, arylsulfonyl group, or 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; A metal or a metal compound is the range whose Zn, Cu, Co, or V = O.

Moreover, the dipyrromethene metal complex compound represented by General formula (7) or General formula (8) demonstrated in detail below is a especially preferable aspect of a dipyrromethene pigment | dye.

Dipyrromethene Metal Complex Compound Represented by General Formula (7)

One of the suitable aspects of the pigment | dye structure in the cation which has a pigment | dye structure is a pigment | dye structure derived from the dipyrromethene metal complex compound represented by following General formula (7). In the present invention, the following compounds form a cationic structure, for example, Ma in General Formula (7) can form a metal cation structure such as zinc.

[Formula 6]

(In General Formula (7), R ⁴ to R ⁹ each independently represent a hydrogen atom or a monovalent substituent, and R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound X ¹ represents a group capable of bonding to Ma, X ² represents a group that neutralizes the charge of Ma, and X ¹ and X ² are bonded to each other and together with Ma A five-, six-, or seven-membered ring may be formed, provided that R ⁴ and R ⁹ are not bonded to each other to form a ring.)

In addition, the dipyrromethene metal complex compound represented by General formula (7) contains 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 More preferred.

When the cation having a dye structure has an alkali-soluble group, as a method of introducing an alkali-soluble group, any one or two or more of R ⁴ to R ¹⁰ , X ¹ and X ² in General Formula (7) The method of having an alkali-soluble group can be used for a substituent. Among these substituents, any one of R ⁴ to R ⁹ and X ¹ is preferable, 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 dipyrromethene metal complex compound represented by General formula (7) may have functional groups other than alkali-soluble group, unless the effect of this invention is 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 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 divalent metal atoms, divalent metal oxides, divalent metal hydroxides, or divalent metal chlorides.

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

Among these, as a metal atom or a metal compound, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co from the viewpoint of the stability, spectral characteristics, heat resistance, light resistance, manufacturing aptitude, etc. of the complex , TiO, and V = O are preferred, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, and V = O are more preferred, and Zn, Co, V = O, and Cu are more preferred. , Zn is particularly preferred.

In 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 general formula (7), X <^1> may be any group as long as it can couple | bond with Ma, Specifically, water, alcohols (for example, methanol, ethanol, a propanol), etc., and "metal chelate" ([ 1] The compounds described in Sakaguchi Takeichi Ueno Kehei (1995 Nankodo), [2] (1996), [3] (1997), and the like. Especially, water, a carboxylic acid compound, and alcohols are preferable at the point of manufacture, and water and a carboxylic acid compound are more preferable.

Formula (7), as the "group to neutralize a charge of Ma" represented by X ^2, for example, a may be made of a halogen atom, a hydroxyl group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group such as for example, among others, manufacturing point of In this, 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 General Formula (7), X ¹ and X ² may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring with Ma. The 5-, 6-, or 7-membered rings formed may be saturated rings or unsaturated rings. In addition, the 5-membered, 6-membered, and 7-membered ring may be composed of only carbon atoms, and may form a heterocycle having at least one atom selected from a nitrogen atom, an oxygen atom, and / or a sulfur atom.

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

Dipyrromethene Metal Complex Compound Represented by General Formula (8)

One of the suitable aspects of the pigment | dye structure in the cation which has a pigment | dye structure is a pigment | dye structure derived from the dipyrromethene metal complex compound represented by following General formula (8). In the present invention, the following compounds form a cationic structure, for example, Ma in General Formula (8) can form a metal cation structure such as zinc.

[Formula 7]

(In General formula (8), R <^11> and R <^16> represents 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 each independently. R ¹² to R ¹⁵ each independently represent a hydrogen atom or a substituent, R ¹⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and Ma represents a metal atom or a metal compound. X ² and X ³ each independently represent NR (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), a nitrogen atom, Represents an oxygen atom or a sulfur atom. Y ¹ and Y ² each independently represent NR ^c (R ^c represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an aryl sulfone Diary, nitrogen atom or carbon atom R ¹¹ And Y ¹ may be bonded to each other to form a 5-, 6-, or 7-membered ring, and R ¹⁶ and Y ² may be bonded to each other to form a 5-, 6-, or 7-membered ring; X ¹ represents a group bondable with Ma, and a represents 0, 1, or 2.

In addition, the dipyrromethene metal complex compound represented by General formula (8) contains 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 It is preferable that it is any one of ¹⁷ , X <^1> , Y <^1> -Y <^2> . Among these, from the point of synthetic suitability, it is preferable to introduce in either of R <^11> -R <^16> and X <^1> , More preferably, it introduce | transduces in any of R <^11> , R <^13> , R <^14> and R <^16> . It is an aspect to become, More preferably, it is an aspect introduce | transduced in either of R <^11> and R <^16> .

When the cation having a dye structure has an alkali soluble group, any one or two or more substituents of R ¹¹ to R ¹⁷ , X ¹ , Y ¹ to Y ² in General Formula (8) have an alkali soluble group Method can be used. Among these substituents, any one of R ¹¹ to R ¹⁶ and X ¹ is preferable, 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 dipyrromethene metal complex compound represented by General formula (8) may have functional groups other than alkali-soluble group, unless the effect of this invention is impaired.

In General formula (8), R <^12> -R <^15> is synonymous with R <^5> -R <^8> in general formula (M), and its preferable aspect is also the same. R <^17> is synonymous with R <^10> in general formula (M), and its preferable aspect is also the same. Ma is synonymous with Ma in General formula (7), and its preferable range is also the same.

More specifically, in R <^12> -R <^15> in General formula (8), as R <^12> and R <^15> , an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, nitrile group , An imide group or a carbamoylsulfonyl group is preferable, and an alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, nitrile group, imide group, carbamoylsulfonyl group is more preferable, and alkoxycarbonyl group and aryl The oxycarbonyl group, carbamoyl group, nitrile group, imide group, carbamoylsulfonyl group are more preferable, and the alkoxycarbonyl group, aryloxycarbonyl group and carbamoyl group are particularly preferable.

As R ¹³ and R ¹⁴ , a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group is preferable, and more preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl It is. Here, the specific example enumerated in R <^6> and R <^7> of general formula (M) is mentioned similarly to the specific example of a more preferable alkyl group, an aryl group, and a heterocyclic group.

In general formula (8), R <^11> and R <^16> is an alkyl group (preferably C1-C36, More preferably, it is a C1-C12 linear, branched or cyclic alkyl group, For example, a methyl group, an ethyl group) , Propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group) , Alkenyl group (preferably an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, for example, a vinyl group, allyl group, 3-buten-1-yl group), and an aryl group (preferably carbon number) 6-36, More preferably, it is a C6-C18 aryl group, For example, it is a phenyl group, a naphthyl group, Heterocyclic group (preferably C1-C24, More preferably, it is a C1-C12 heterocyclic group, For example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 2-pyridyl group, 2-benzothiazolyl group, 1 -Imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group, alkoxy group (preferably an alkoxy group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms), for example, a methoxy group, Ethoxy group, propyloxy group, butoxy group, hexyloxy group, 2-ethylhexyloxy group, dodecyloxy group, cyclohexyloxy group), aryloxy group (preferably C6-C24, More preferably, it is C1-C1) It is an aryloxy group of 18, for example, a phenoxy group, a naphthyloxy group, an alkylamino group (preferably C1-C36, More preferably, it is a C1-C18 alkylamino group, For example, methylamino group, ethylamino group) , Propylamino group, butylamino group, hexylamino group, 2-ethylhexylamino group, isopropylamino group, tert-butylamino group, tert-octylamino group, cyclohexylamino group, N, N-diethylamino group, N, N-dipropylamino group, N, N-dibutylamino group, N- Butyl-N-ethylamino group) and an arylamino group (preferably an arylamino group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms), for example, a phenylamino group, a naphthylamino group, a N, N-diphenylamino group, N-ethyl-N-phenylamino group) or heterocyclic amino group (preferably C1-C24, more preferably C1-C12 heterocyclic amino group, For example, 2-aminopyrrole group, 3-aminopyra) Sol, 2-aminopyridine group, 3-aminopyridine group).

As R ¹¹ and R ¹⁶ , an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylamino group, an arylamino group, a heterocyclic amino group is preferable among the above, and an alkyl group, an alkenyl group, an aryl group, a heterocyclic group is more preferable, and an alkyl group. , Alkenyl group and aryl group are more preferable, and 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 is a group which can be further substituted. May be substituted with the substituent described in the term of the substituent group A described later, and when substituted with two or more substituents, these substituents may be the same or different.

In General Formula (8), X ² and X ³ each independently represent NR, a nitrogen atom, an oxygen atom, or a sulfur atom. Here, R is a hydrogen atom, an alkyl group (preferably a C1-C12, more preferably a C1-C12 linear, branched, or cyclic alkyl group, For example, methyl group, an ethyl group, a propyl group, iso Propyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group), alkenyl group (preferably Preferably it is C2-C24, More preferably, it is a C2-C12 alkenyl group, For example, a vinyl group, an allyl group, 3-buten- 1-yl group, an aryl group (preferably C6-C36), Preferably they are a C6-C18 aryl group, for example, a phenyl group, a naphthyl group, a heterocyclic group (preferably C1-C24, more preferably a C1-C12 heterocyclic group), for example, 2- Thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1- Midazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group, acyl group (preferably C1-C24, more preferably C2-C18 acyl group, For example, acetyl group, P Valoyl group, 2-ethylhexyl group, benzoyl group, cyclohexane oil group), alkylsulfonyl group (preferably C1-C24 alkylsulfonyl group, More preferably, it is a methylsulfonyl group), for example , Ethylsulfonyl group, isopropylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably arylsulfonyl group having 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms), for example, phenylsulfonyl group, naph Tylsulfonyl group).

In the general formula (8), Y ¹ and Y ² are, each independently, NR ^C, a nitrogen atom or a carbon atom, R ^C is, X ^2, and and R and consent of X ^3, the same is also a preferred embodiment .

In general formula (8), R <^11> and Y <^1> combine with each other, and a 5-membered ring (for example, a cyclopentane ring, a pyrrolidine ring, a tetrahydrofuran ring, a dioxolane ring, tetrahydrothiophene together with a carbon atom) Ring, pyrrole ring, furan ring, thiophene ring, indole ring, benzofuran ring, benzothiophene ring, 6-membered ring (for example, cyclohexane ring, piperidine ring, piperazine ring, morpholine ring, tetra Hydropyran ring, dioxane ring, pentamethylene sulfide ring, dicyan ring, benzene ring, pyridazine ring, quinoline ring, quinazoline ring) or 7-membered ring (for example, cycloheptane ring, hexamethyleneimine ring) You may form.

In general formula (8), R <^16> and Y <^2> couple | bond with each other, and a 5-membered ring (for example, a cyclopentane ring, a pyrrolidine ring, a tetrahydrofuran ring, a dioxolane ring, tetrahydrothiophene together with a carbon atom) Ring, pyrrole ring, furan ring, thiophene ring, indole ring, benzofuran ring, benzothiophene ring, 6-membered ring (for example, cyclohexane ring, piperidine ring, piperazine ring, morpholine ring, tetra Hydropyran ring, dioxane ring, pentamethylene sulfide ring, dicyan ring, benzene ring, pyridazine ring, quinoline ring, quinazoline ring) or 7-membered ring (for example, cycloheptane ring, hexamethyleneimine ring) You may form.

In the general formula (8), in the case of the 5-membered, 6-membered, and 7-membered ring formed by bonding of R ¹¹ and Y ¹ , and R ¹⁶ and Y ² , the ring is substitutable, It may be substituted by the substituent demonstrated and when substituted by two or more substituents, these substituents may be same or different.

In General formula (8), it is preferable that R <^11> and R <^16> are respectively independently a monovalent substituent whose -Es' value which is a stereoscopic parameter is 1.5 or more, It is more preferable that it is 2.0 or more, It is further more preferable that it is 3.5 or more, It is especially preferable that it is 5.0 or more.

Here, the steric parameter -Es' value is a parameter showing the steric bulkiness of the substituents, and is correlated with the structural activity correlation between JA Macphee, et al, Tetrahedron, Vol. 34, pp 3553 to 3652, Fujita Toshio Chemical Inc. Use the -Es' value shown in Drag Design, published February 20, 1986 (Togaku Kagaku).

In General formula (8), X <^1> represents group which can couple | bond with Ma, Specifically, the same group as X <^1> in General formula (7) is mentioned, A preferable aspect is also the same.

a represents 0, 1, or 2.

As a preferable aspect of a compound represented by General formula (8), R <^12> -R <^15> is respectively independently the preferable aspect described by description of R <^5> -R <^8> in general formula (M), and R <^17> is a general formula ( A preferred embodiment described in the description of R ¹⁰ in M), Ma is Zn, Cu, Co, or V═O, X ² is NR (R is a hydrogen atom, an alkyl group), a nitrogen atom, or an oxygen atom, X ³ is NR (R is hydrogen atom, alkyl group) or oxygen atom, Y ¹ is NR ^C (R ^C is hydrogen atom, alkyl group), nitrogen atom, or carbon atom, Y ² is nitrogen atom, or 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 which is bonded via an oxygen atom, and a is 0 or 1. R ¹¹ and Y ¹ may be bonded to each other to form a 5- or 6-membered ring, or R ¹⁶ and Y ² may be bonded to each other to form a 5- or 6-membered ring.

As a more preferable aspect of a compound represented by General formula (8), R <^12> -R <^15> is respectively a preferable aspect described by description of R <^5> -R <^8> in the compound represented by general formula (M) independently, and R ¹⁷ is a preferred embodiment described in the description of R ¹⁰ in 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 which is bonded via an oxygen atom, and a is 0 or 1. R ¹¹ and Y ¹ may be bonded to each other to form a 5- or 6-membered ring, or R ¹⁶ and Y ² may be bonded to each other to form a 5- or 6-membered ring.

It is preferable that the molar extinction coefficient of the dipyrromethene metal complex compound represented by General Formula (7) and General Formula (8) is as high as possible from a viewpoint of coloring power. Moreover, 520 nm-580 nm are preferable and, as for the maximum absorption wavelength (lambda) max, from a viewpoint of color purity improvement, 530 nm-570 nm are more preferable. By being in this area | region, the color filter with favorable color reproducibility can be manufactured using the coloring composition of this invention.

Moreover, it is preferable that the pigment | dye which has a pigment | dye structure derived from a dipyrromethene pigment | dye has absorbance of the maximum absorption wavelength ((lambda) max) 1,000 times or more with respect to the absorbance in 450 nm, It is more preferable that it is 10,000 times or more, It is 100,000 times It is more preferable that it is above. When this ratio exists in this range, especially when a blue color filter is produced using the coloring composition of this invention, a color filter with a higher transmittance | permeability can be formed. In addition, a maximum absorption wavelength and molar extinction coefficient are measured with the spectrophotometer cary5 (made by Varian).

It is preferable that the melting point of the dipyrromethene metal complex compound represented by General Formulas (7) and (8) is not too high from the viewpoint of solubility.

The dipyrromethene metal complex compounds represented by the general formulas (7) and (8) include U.S. Patent Nos. 4,774,339, 5,433,896, Japanese Patent Laid-Open Nos. 2001-240761, 2002-155052, and Japanese Patents. Publication 3614586, Aust. J. Chem, 1965, 11, 1835-1845, J. H. Boger et al, Heteroatom Chemistry, Vol. 1, No. 5, 389 (1990) or the like can be synthesized. Specifically, Paragraph 0131 of Unexamined-Japanese-Patent No. 2008-292970-the method of 0157 can be applied.

Although the specific example of a dipyrromethene pigment | dye is shown below, this invention is not limited to this. In addition, in formula, X represents an anion. In this invention, the hydrogen atom in any one of the following pigment | dye structures couple | bonds with a polymer skeleton.

[Formula 8]

[Formula 9]

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

<<< carbonium pigment >>>

Among the carbon dyes, triaryl methane dyes and xanthene dyes are preferable.

Triarylmethane pigments

One of the aspects of the cation which has a pigment | dye structure which concerns on this invention has a partial structure derived from a triaryl methane pigment | dye (triaryl methane compound). As a pigment | dye, it has the partial structure derived from the compound (triaryl methane compound) represented by the following general formula (TP) as a pigment | dye structure. In this invention, a triaryl methane compound generically refers to the compound which has a pigment | dye structure containing a triaryl methane skeleton in a molecule | numerator.

General formula (TP)

[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 Rtp ⁶ , Rtp ⁷ and Rtp ⁸ represent a substituent, a, b and c represent an integer of 0 to 4. A, b and c are 2 or more. In this case, Rtp ⁶ , Rtp ⁷ and Rtp ⁸ may be linked to each other to form a ring. X ⁻ represents an anion structure.)

About the preferable range and specific example of a compound represented by general formula (TP), Paragraph No. 0170 of Unexamined-Japanese-Patent No. 2013-28764-description of 0178 can be referred to, and these content is integrated in this specification.

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

Although the specific example of a compound represented by general formula (TP) below is shown, this invention is not limited to this. X represents an anion (Hereafter, it is the same unless it mentions specially.). In this invention, the hydrogen atom in any one of the following pigment | dye structures couple | bonds with a polymer skeleton.

Xanthene pigment

The preferable aspect of the cation which has a pigment | dye structure in this invention has a partial structure derived from a xanthene pigment | dye (xanthene compound). As a pigment | dye, it has the partial structure derived from the xanthene compound represented by the following general formula (J) as a pigment | dye structure.

[Formula 11]

(In General Formula (J), R ⁸¹ , R ⁸² , R ^83, and R ⁸⁴ each independently represent a hydrogen atom or a monovalent substituent, R ⁸⁵ each independently represents a monovalent substituent, and m is, An integer of 0 to 5. X ⁻ represents an anion or X ⁻ does not exist, and at least one of R ⁸¹ to R ⁸⁵ contains an anion.)

The introduction site in the case of introducing the compound represented by General Formula (J) into the structural units represented by General Formulas (A) to (D) is not particularly limited, but may be introduced at any one of R ⁸¹ to R ⁸⁵ . It is preferable.

Substituents which R ⁸¹ to R ⁸⁴ and R ⁸⁵ in General Formula (J) can take are the same as the substituents listed in the section of Substituent Group A described later.

R ⁸¹ and R ⁸² in formula (J), R ⁸³ and R ⁸⁴ , and R ⁸⁵ when m is 2 or more, are each independently a 5-membered, 6-membered or 7-membered saturated ring, or 5 One-, six- or seven-membered unsaturated rings may be formed. When the 5-membered, 6-membered, or 7-membered ring formed is a group which can be further substituted, the substituents described in R ⁸¹ to R ⁸⁵ may be substituted, and when substituted with two or more substituents, these substituents are the same. You may or may differ.

R ⁸¹ and R ⁸² , R ⁸³ and R ⁸⁴ in General Formula (J), and R ^{85 in the} case where m is 2 or more, are each independently a 5-membered, 6-membered, or 7-membered group having no substituents; When forming a saturated ring of 5 or 6, 6 and 7 membered unsaturated ring, as a 5, 6 and 7 membered saturated ring or 5, 6 and 7 membered unsaturated ring which does not have a substituent, For example, pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexene ring, benzene ring, pyridine A ring, a pyrazine ring, a pyridazine ring is mentioned, Preferably, a benzene ring and a pyridine ring are mentioned.

In particular, R ⁸² and R ⁸³ are hydrogen atoms or substituted or unsubstituted alkyl groups, and R ⁸¹ and R ⁸⁴ are preferably substituted or unsubstituted alkyl groups or phenyl groups. In addition, R ⁸⁵ is preferably a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group, a carboxyl group, and an amide group, and more preferably a sulfo group, a sulfonamide group, a carboxyl group, or an amide group. desirable. R ⁸⁵ is preferably bonded to an adjacent portion of the carbon linked to the xanthene ring. It is especially preferable that the substituent which the phenyl group of R <^81> and R <^84> has is a hydrogen atom, a halogen atom, a C1-C5 linear or branched alkyl group, a sulfo group, a sulfonamide group, and a carboxyl group.

The compound which has a xanthene skeleton represented by general formula (J) can be synthesize | combined by the method as described in literature. Specifically, tetrahedron letters, 2003, vol. 44, No. 23, pages 4355-4360, tetrahedron, 2005, vol. 61, no. The methods described in pages 12, 3097-3106 and the like can be applied.

When X ⁻ represents an anion, reference may be made to the description when the counter anion described later is a separate molecule, and when X ⁻ does not exist and at least one of R ⁸¹ to R ⁸⁵ includes an anion, the counter anion Reference may be made to the case where it is in this same repeating unit.

Although the specific example of a xanthene compound is shown below, this invention is not limited to this. In this invention, the hydrogen atom in any one of the following pigment | dye structures couple | bonds with a polymer skeleton.

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

<< azo dye >>

One of the pigment | dye structures which concern on this invention has a partial structure derived from an azo pigment | dye (azo compound). In the present invention, the azo compound refers generically to a compound having a dye moiety containing an N = N group in a molecule. As an azo dye, it can select from a well-known azo dye (for example, substituted azobenzene, etc.) suitably, and can apply. For example, as an azo dye, Paragraph 0084 of Unexamined-Japanese-Patent No. 2013-41097-description of 0342 and Paragraph 0029 of Unexamined-Japanese-Patent No. 2011-162760-description of 0136 can be referred to, and this content is referred to in this specification. It is used.

<< dieketopyrrolopyrrole pigment >>

One of the pigment | dye structures which concerns on this invention has a partial structure derived from a diketopyrrolopyrrole pigment | dye (diketopyrrolopyrrole compound). As a diketopyrrolopyrrole pigment | dye, the dye multimer which has the partial structure derived from the compound (diketopyrrolopyrrole compound) represented by the following general formula (DK) as a partial structure of a pigment | dye site | part is contained. In the present invention, the diketopyrrolopyrrole compound is a generic term for a compound having a dye moiety containing a diketopyrrolopyrrole skeleton in the molecule.

[Formula 16]

In General Formula (DK), R ¹¹⁰ and R ¹¹¹ each independently represent a hydrogen atom, an alkyl group or an aryl group, and R ¹¹² and R ¹¹³ each independently represent a hydrogen atom, an alkyl group or an aryl group, preferably An aryl group is shown.

<< phthalocyanine pigment >>

One of the pigment | dye structures which concerns on this invention has a partial structure derived from a phthalocyanine pigment | dye (phthalocyanine compound). As a phthalocyanine pigment | dye, the dye multimer which has the partial structure derived from the compound (phthalocyanine compound) represented by the following general formula (F) as a partial structure of a pigment | dye site | part is contained. In this invention, a phthalocyanine compound is generically the compound which has a pigment | dye site | part containing a phthalocyanine skeleton in a molecule | numerator.

[Formula 17]

In general formula (F), M <^1> represents metals, and Z <^1> , Z <^2> , Z <^3> and Z <^4> respectively independently contain the atom selected from a hydrogen atom, a carbon atom, and a nitrogen atom, 6 The group of atoms necessary to form a torus is shown.

General formula (F) is demonstrated in detail.

Examples of metals represented by M ¹ in general formula (F) include metal atoms such as Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and Fe, AlCl, InCl, FeCl, TiCl _2, SnCl _2, SiCl _2, GeCl _2, metal chloride, TiO, will include a metal oxide, and metal hydroxides such as Si (OH) _2, such as VO, in particular Cu, Zn is preferably Do.

In General Formula (F), Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent an atom necessary to form a six-membered ring including an atom selected from a hydrogen atom, a carbon atom, and a nitrogen atom Group. The 6-membered ring may be saturated, unsaturated, may be unsubstituted, or may have a substituent. As a substituent, the substituent quoted by the term of the following substituent group A is mentioned. Moreover, when a 6-membered ring has two or more substituents, these substituents may be same or different. In addition, the 6-membered ring may be condensed with another 5- or 6-membered ring. The 6-membered ring includes a benzene ring, a cyclohexane ring and the like.

Among the phthalocyanine dyes represented by General Formula (F), particularly, the phthalocyanine dyes represented by General Formula (F-1) shown below are preferable.

[Formula 18]

In general formula (F-1), M <^2> is synonymous with M <^1> in general formula (F), and its preferable aspect is also the same.

In General Formula (F-1), when R ¹⁰¹ to R ¹¹⁶ each independently represent a hydrogen atom or a substituent, and the substituent represented by R ¹⁰¹ to R ¹¹⁶ is a group which can be further substituted, the following substituent group A It may be substituted by the group demonstrated in the term, and when substituted by two or more substituents, these substituents may be same or different.

Substituents represented by R ¹⁰¹ to R ^{116 may} be a hydrogen atom, a halogen atom, or a SO ₂ NR ¹¹⁷ R ¹¹⁸ (R ¹¹⁷ and R ¹¹⁸ may have a hydrogen atom, a linear or branched C 3-20 substituent. Alkyl group) and SR ¹¹⁹ (R ¹¹⁹ is a linear or branched alkyl group which may have a C3-C20 substituent) are preferable.

<<< cyanine pigment >>>

One of the aspects of the cation which has a pigment | dye structure which concerns on this invention has a partial structure derived from a cyanine pigment | dye (cyanine compound). For details thereof, reference may be made to paragraphs 0191 to 0201 of JP-A-2013-28764, the contents of which are incorporated herein by reference.

<<< subphthalocyanine pigment >>>

One of the aspects of the cation which has a pigment | dye structure which concerns on this invention is a thing which has a subphthalocyanine pigment | dye structure. These details can refer to description of Paragraph No. 0242 of Unexamined-Japanese-Patent No. 2013-28764-0250, and these content is integrated in this specification.

<< squarylium pigment >>

The cation which has a pigment | dye structure used by this invention may have a squarylium pigment | dye structure. As for these details, Paragraph No. 0202 of Unexamined-Japanese-Patent No. 2013-28764-description of 0223 can be referred to, and these content is integrated in this specification.

As long as the pigment | dye which concerns on this invention does not deviate from the meaning of this invention, the hydrogen atom in a pigment | dye structure may be substituted by the substituent chosen from the following substituent group A.

Substituent Group A:

Examples of the substituent that the dye may have include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, and alkoxy. Group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group (including alkylamino group and alinino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxy Carbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, Acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino And silyl groups. It describes in detail below.

It is 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 it is a C1-C30 alkyl group) For example, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), cycloalkyl group (preferably 3 carbon atoms) A substituted or unsubstituted cycloalkyl group of -30, for example cyclohexyl, cyclopentyl, and the like, and a polycycloalkyl group, for example, a bicycloalkyl group (preferably, a substituted or unsubstituted carbon having 5 to 30 carbon atoms). It is a cycloalkyl group, For example, group of polycyclic structure, such as bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octan-3-yl), a tricycloalkyl group, is mentioned. Preferably monocyclic cycloalkyl group, bicycloal Group, and a cycloalkyl group of monocyclic being particularly preferred),

Linear or branched alkenyl groups (linear or branched substituted or unsubstituted alkenyl groups, preferably alkenyl groups having 2 to 30 carbon atoms, for example vinyl, allyl, prenyl, geranyl, oleyl), cyclo Alkenyl group (Preferably, it is a C3-C30 substituted or unsubstituted cycloalkenyl group, For example, 2-cyclopenten- 1-yl and 2-cyclohexen- 1-yl are mentioned, Multicycloalkene Diary, for example, a bicycloalkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, for example, bicyclo [2,2,1] hept-2-ene-1- Mono, bicyclo [2,2,2] oct-2-en-4-yl) and tricycloalkenyl groups, with monocyclic cycloalkenyl groups being particularly preferred) and alkynyl groups (preferably having 2 to 2 carbon atoms) A substituted or unsubstituted alkynyl group of 30, for example ethynyl, propargyl, trimethylsilylethynyl group),

Aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecaneoylaminophenyl), heterocyclic group (preferably Preferably it is a 5-7 membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or monocyclic heterocyclic group, More preferably, a cyclic atom is chosen from a carbon atom, a nitrogen atom, and a sulfur atom, It is a heterocyclic group which has at least one hetero atom of a nitrogen atom, an oxygen atom, and a sulfur atom, More preferably, it is a C3-C30 5- or 6-membered aromatic heterocyclic group. Furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group,

Alkoxy group (preferably a C1-C30 substituted or unsubstituted alkoxy group, for example, methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy ), An aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy, 2-methylphenoxy, 2,4-di-tert-amylphenoxy, 4 -tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecane oilaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms), for example trimethylsilyloxy, tert-butyldimethylsilyloxy), a heterocyclic oxy group (preferably, a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, the heterocyclic portion is preferably a heterocyclic portion described in the above-described heterocyclic group, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy),

Acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyl Oxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy) and a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), Alkoxycarbonyloxy group (Preferably, it is a C2-C30 substituted or unsubstituted alkoxycarbonyloxy group, For example, methoxycarbonyloxy, ethoxycarbonyloxy, tert- butoxycarbonyloxy, n-octyl Carbonyloxy), aryloxycarbonyloxy group (preferably substituted or unsubstituted aryl jade having 7 to 30 carbon atoms) A cicarbonyloxy group, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, p-n-hexadecyloxyphenoxycarbonyloxy),

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, for example, amino, methyl Amino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazin-2-ylamino), acylamino group (preferably formylamino group, C1-C1) A substituted or unsubstituted alkylcarbonylamino group of 30, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, for example carbamoylamino, N N-dimethylaminocarbonylamino, N, N- Ethylaminocarbonylamino, morpholinocarbonylamino), and alkoxycarbonylamino group (preferably substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonyl Amino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino),

Aryloxycarbonylamino group (preferably a C7-30 substituted or unsubstituted aryloxycarbonylamino group, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxy A carbonylamino) and sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms; for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octyl) Aminosulfonylamino), alkyl or arylsulfonylamino group (preferably substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, for example Methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group,

Alkylthio groups (preferably substituted or unsubstituted alkylthio groups having 1 to 30 carbon atoms, for example methylthio, ethylthio, n-hexadecylthio), arylthio (preferably carbon atoms) 6-30 substituted or unsubstituted arylthio group, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), heterocyclic thiothiodes (preferably having 2-30 carbon atoms) Substituted or unsubstituted heterocyclic thio group, heterocyclic moiety is preferably the heterocyclic moiety described in the above-described heterocyclic group, for example 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio ), Sulfamoyl group (preferably substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N- Dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), sulfo groups,

Alkyl or arylsulfinyl groups (preferably, a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30, for example methylsulfinyl, ethylsulfinyl, phenyl Sulfinyl, p-methylphenylsulfinyl), alkyl or arylsulfonyl groups (preferably, substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30, for example, For example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted to 7 to 30 carbon atoms or It is an unsubstituted arylcarbonyl group, For example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, an aryloxycarbonyl group (preferably C7-30) Substituted or unsubstituted aryloxycarbonyl group of, for example, phenoxycarbonyl, o-cle Lolophenoxycarbonyl, m-nitrophenoxycarbonyl, p-tert-butylphenoxycarbonyl),

Alkoxycarbonyl group (preferably a C2-C30 substituted or unsubstituted alkoxycarbonyl group, for example, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl) , Carbamoyl groups (preferably substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n Octyl carbamoyl, N- (methylsulfonyl) carbamoyl), aryl or heterocyclic azo group (preferably substituted or unsubstituted aryl azo groups having 6 to 30 carbon atoms, substituted or unsubstituted hetero rings having 3 to 30 carbon atoms) Azo groups (heterocyclic moieties are preferably heterocyclic moieties described in the above heterocyclic groups), for example phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazole-2- Yl azo) and an imide group (preferably a C2-C30 substituted or unsubstituted imide group, for example, N-succinimide and N-phthal) Mead), phosphino group (preferably a C2-C30 substituted or unsubstituted phosphino group, for example, dimethyl phosphino, diphenyl phosphino, methylphenoxy phosphino), phosphinyl group (preferably Preferably it is a C2-C30 substituted or unsubstituted phosphinyl group, For example, phosphinyl, dioctyloxy phosphinyl, diethoxy phosphinyl),

Phosphinyloxy group (preferably a C2-C30 substituted or unsubstituted phosphinyloxy group, for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino group (preferably Is a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), silyl group (preferably substituted or unsubstituted with 3 to 30 carbon atoms). Examples of the substituted silyl group include trimethylsilyl, tert-butyldimethylsilyl and phenyldimethylsilyl.

In said functional group, what has a hydrogen atom may replace the part of the hydrogen atom in a functional group by any one of said groups. Examples of the functional group which can be introduced as a substituent include alkylcarbonylaminosulfonyl group, arylcarbonylaminosulfonyl group, alkylsulfonylaminocarbonyl group, and arylsulfonylaminocarbonyl group. Specifically, methylsulfonylaminocarbonyl , p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl group.

<<< counter anion >>>

The counter anion in the case where the pigment | dye structure used by this invention has a cationic structure may be in the same repeating unit of a dye multimer, and may exist outside the same repeating unit. When the opposite anion is in the same repeating unit, it means the case where cation and anion are couple | bonded through the covalent bond in the repeating unit which has a pigment | dye structure. On the other hand, outside of the same repeating unit means the case of that excepting the above. For example, a cation and an anion do not couple | bond through a covalent bond, and exist when they exist as a separate compound, or a case where a cation and an anion are contained as independent repeating units of a dye multimer, respectively.

The counter anion is within the same repeating unit

1st Embodiment of the anion in this invention is a case where a counter anion exists in the same repeating unit, specifically, when a cation and an anion are couple | bonded through the covalent bond in the repeating unit which has a pigment | 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).

General formula (A1)

[Formula 19]

(In General Formula (A1), R ¹ and R ² each independently represent —SO ₂ — or —CO—.)

In General Formula (A1), at least one of R ¹ and R ² preferably represents -SO _2- , and more preferably both R ¹ and R ² represent -SO _2- .

As for said general formula (A1), it is more preferable to represent with the following general formula (A1-1).

General formula (A1-1)

[Formula 20]

(In General Formula (A1-1), R ¹ and R ² each independently represent —SO ₂ — or —CO—. X ¹ and X ² each independently represent an alkylene group or an arylene group.)

R <^1> and R <^2> is synonymous with R <^1> and R <^2> in general formula (A1) in general formula (A1-1), and its preferable range is also the same.

When X <^1> represents an alkylene group, 1-8 are preferable and, as for carbon number of an alkylene group, 1-6 are more preferable. When X <^1> represents an arylene group, 6-18 are preferable, as for carbon number of an arylene group, 6-12 are more preferable, and 6 is more preferable. When X <^1> has a substituent, it is preferable to substitute by the fluorine atom.

X <^2> represents an alkyl group or an aryl group, and an alkyl group is preferable. 1-8 are preferable, as for carbon number of an alkyl group, 1-6 are more preferable, 1-3 are more preferable, and 1 is especially preferable. When X <^2> has a substituent, it is preferable to substitute by the fluorine atom.

General formula (A2)

[Formula 21]

(In 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 this embodiment, especially when the skeleton of a dye multimer is represented by the structural unit represented by the said General formula (A), the case where a part of L <_1> contains the part represented by General formula (A1) as a preferable example is preferable. Can be mentioned. As a specific example in this case, (a-xt-1), (a-xt-5), (a-xt-6) are illustrated among the examples of the repeating unit which has a pigment | dye structure mentioned later.

Moreover, in this embodiment, when the skeleton of the dye multimer used by this invention contains the structural unit represented by general formula (B), it is mentioned as an example. As a specific example in this case, in the example of the repeating unit which has a pigment | dye structure mentioned later, (B-dp-1), (B-mp-1), (B-xt-1), (B-xt-2) Is illustrated.

The counter anion is a separate molecule

The second embodiment of the anion in the present invention is a case where the counter anion is outside the same repeating unit, and the cation and the anion do not bond through a covalent bond and exist as separate molecules.

As an anion in this case, a fluorine anion, a chlorine anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, a non-nucleophilic anion are illustrated, and a non-nucleophilic anion is preferable.

The non-nucleophilic counter anion may be an organic anion, may be an inorganic anion, and an organic anion is preferable. As an example of the counter anion used by this invention, the well-known non-nucleophilic anion described in Paragraph No. 0075 of Unexamined-Japanese-Patent No. 2007-310315 is mentioned, These content is integrated in this specification.

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 An aryl group having 6 to 10 carbon atoms, n1 represents 1 to 4) and PF _n2 R ^P _(6-n2) ^- (R ^P represents a fluorinated alkyl group having 1 to 10 carbon atoms, n2 represents an integer of 1 to 6); And bis (sulfonyl) imide anion, tris (sulfonyl) methyl anion and tetraarylborate anion, and more preferably bis (sulfonyl) imide anion. By using such non-nucleophilic counter anion, the effect of this invention tends to be exhibited more effectively.

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

[Formula 22]

(In formula (AN-1), X <^1> and X <^2> respectively independently represent a C1-C10 alkyl group which has a fluorine atom or a fluorine atom.) X <^1> and X <^2> may combine with each other and form a ring. .)

X <^1> and X <^2> respectively independently represents a C1-C10 alkyl group which has a fluorine atom or a fluorine atom, A C1-C10 alkyl group which has a fluorine atom or a fluorine atom is preferable, and is C1-C10 purple It is more preferable that it is a fluoroalkyl group, It is more preferable that it is a C1-C4 perfluoroalkyl group, and a trifluoromethyl group is especially preferable.

As a tris (sulfonyl) methyl anion which is a non-nucleophilic counter anion, the structure of following General formula (AN-2) is preferable.

[Formula 23]

(In formula (AN-2), X <^3> , X <^4> and X <^5> respectively independently represent a fluorine atom or the alkyl group which has a C1-C10 fluorine atom.)

X <^3> , X <^4> and X <^5> are synonymous with X <^1> and X <^2> respectively independently, and a preferable range is also synonymous.

It is preferable that it is a compound represented with the following general formula (AN-5) as tetraaryl borate anion which is a non-nucleophilic counteranion.

[Formula 24]

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

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and even 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. When it has 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 sulfonamide group, a nitro group, etc. are mentioned, A halogen atom and an alkyl group are mentioned. Preferably, a fluorine atom and an alkyl group are more preferable, and a fluorine atom and a C1-C4 perfluoroalkyl group are more preferable.

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

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

1-3 are preferable and, as for n1, 1-2 are more preferable.

The non-nucleophilic counter anion is further preferably -PF ₆ R ^P _(6-n2) ^- (R ^P represents a fluorinated alkyl group having 1 to 10 carbon atoms, n2 represents an integer of 1 to 6). . R ^P is preferably an alkyl group having a fluorine atom having 1 to 6 carbon atoms, more preferably an alkyl group having fluorine having 1 to 4 carbon atoms, still more preferably a perfluoroalkyl group having 1 to 3 carbon atoms.

The integer of 1-4 is preferable, and, as for n2, 1 or 2 is more preferable.

100-1,000 are preferable and, as for the mass per molecule of the non-nucleophilic counteranion used by this invention, 200-500 are more preferable.

The dye multimer of this invention may contain only one type of non-nucleophilic counteranion, and may include two or more types.

Although the specific example of the non-nucleophilic counter anion used by this invention is shown below, this invention is not limited to this.

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

Moreover, in 2nd Embodiment, a multimer may be sufficient as an anion. As a multimer in this case, the multimer which contains the structural unit containing an anion and does not contain the structural unit derived from the pigment | dye structure containing a cation is illustrated. Here, the structural unit containing an anion can mention the structural unit containing an anion demonstrated by 3rd Embodiment mentioned later as a preferable example. In addition, the multimer containing an anion may have structural units other than the structural unit containing an anion. As such a structural unit, the other repeating unit which the dye multimer used by this invention mentioned later may contain is illustrated as a preferable example.

Cations and anions are included in each other repeating unit of the dye multimer

As 3rd Embodiment in this invention, the case where a cation and an anion are contained in each independent repeating unit of a dye multimer is said.

In the case of this embodiment, an anion may have in the side chain of a dye multimer, may have in a main chain, and may have a counter anion in both a main chain and a side chain. Preferably, it is a side chain.

As a preferable example of the repeating unit containing an anion, the repeating unit represented by general formula (C) and the repeating unit represented by general formula (D) are illustrated.

General formula (C)

[Formula 30]

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

In general formula (C), X <^1> represents the main chain of a repeating unit, shows the coupling group normally formed by a polymerization reaction, For example, a (meth) acrylic-type, styrene type, vinyl type, etc. are preferable, and (meth) acrylic-type Is more preferable. In addition, the site | part represented by two * turns into a repeating unit.

When L ¹ represents a divalent linking group, an alkylene group having 1 to 30 carbon atoms (methylene group, ethylene group, trimethylene group, propylene group, butylene group, etc.), an arylene group having 6 to 30 carbon atoms (phenylene group, naphthalene group, etc.) ), Heterocyclic linking group, -CH = CH-, -O-, -S-, -C (= O)-, -CO-, -NR-, -CONR-, -OC-, -SO-, -SO _2- and a linking group in which two or more thereof are combined are preferable. Here, each R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

In particular, L ¹ is 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 (preferably phenylene group, a naphthalene _{group), -NH-, -CO 2 -,} -O- and -SO ₂ - divalent group connected to a combination of two or more is preferred.

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

General formula (D)

[Formula 31]

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

In the general 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 (= 0)-, -CO _2- , -NR-, -CONR-, -O ₂ C-, -SO-, -SO ₂ -and a linking group combining two or more thereof are preferable. Here, each R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

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

L ³ is preferably a group consisting of a combination of a C 6-12 arylene group (particularly a phenylene group) and -O-, and at least one C 6-12 arylene group is preferably substituted with a fluorine atom.

As a counter anion, the anion part demonstrated in the case where the said counter anion exists in the same structural unit is illustrated as a preferable anion.

Although the specific example of the repeating unit containing the anion in this embodiment is shown below, this invention is not limited to these.

[Formula 32]

Although the following specific example shows the state in which an anion structure is not dissociated, it goes without saying that the state in which an anion structure dissociates is also in the scope of the present invention.

[Formula 33]

[Formula 34]

[Formula 35]

[Formula 36]

[Formula 37]

Below, the example of a repeating unit (a1) and a repeating unit (a2) used preferably by this invention is shown. It goes without saying that the present invention is not limited to these. X ⁻ represents a counter anion. In addition, although some X is shown in the state which does not dissociate an anion structure, it goes without saying that a state which dissociates is also contained in this invention.

[Formula 38]

[Formula 39]

[Formula 40]

[Formula 41]

[Formula 42]

[Formula 43]

[Formula 44]

[Formula 45]

[Formula 46]

<< other functional groups and repeating units >>

The dye multimer of this invention may have another functional group in the pigment | dye structure part of the pigment multimer mentioned above. As another functional group, a polymeric group, alkali-soluble group (preferably acidic group), etc. are illustrated.

Moreover, the dye multimer of this invention may contain other repeating units other than the repeating unit containing the pigment | dye structure mentioned above. Another repeating unit may have a functional group.

Moreover, the dye multimer of this invention may contain other repeating units other than the repeating unit (a1) mentioned above and the repeating unit (a2) mentioned above. Another repeating unit may have a functional group. As another repeating unit, the repeating unit containing at least 1 sort (s) of a polymeric group and alkali-soluble group (preferably acidic group) is illustrated.

That is, the dye multimer of this invention may have another repeating unit other than the repeating unit (a1) mentioned above and the repeating unit (a2) mentioned above. Only one type may be contained in one dye multimer, and two or more types may be contained in another repeating unit.

Moreover, the dye multimer of this invention may have another functional group in a dye multimer. Hereinafter, these details are demonstrated.

<<< Polymer >>>>

The pigment | dye structure may contain the polymeric group and the other part may contain the polymeric group. In this invention, it is preferable that a pigment | dye structure contains a polymeric group. There exists a tendency for heat resistance to improve by setting it as such a structure.

Moreover, in this invention, the aspect in which other parts other than a pigment | dye structure contain a polymeric group is also preferable.

As the polymerizable group, a known polymerizable group which can be crosslinked by a radical, an acid, or a heat can be used, and examples thereof include a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetane group), and a methylol group. In particular, groups containing ethylenically unsaturated bonds are preferred, (meth) acryloyl groups are more preferred, and (meth) acrylic acid glycidyl and 3,4-epoxy-cyclohexylmethyl (meth) acrylate More preferred are meth) acryloyl groups.

It is preferable that a polymeric group is contained in a dye multimer as a repeating unit which has a polymeric group, and it is more preferable that it is contained as a repeating unit which has an ethylenically unsaturated bond. That is, an example of the preferable embodiment of the dye multimer of this invention is an aspect in which a dye multimer contains the repeating unit which contains a dye monomer, and the repeating unit which has a polymeric group, and the repeating unit and ethylenic unsaturated which contain a dye monomer It is more preferable to contain the repeating unit which has a bond.

Examples of the method of introducing the polymerizable group include (1) a method of modifying and introducing a dye multimer into a polymerizable group-containing compound, (2) a method of copolymerizing and introducing a dye monomer and a polymerizable group-containing compound. Hereinafter, it demonstrates in detail.

(1) A method of introducing a dye multimer by modifying it into a polymerizable group-containing compound:

As a method of modifying and introducing the dye multimer into the polymerizable group-containing compound, a known method can be used without particular limitation. For example, (a) a method of reacting a carboxylic acid and an unsaturated bond-containing epoxy compound possessed by the dye multimer, (b) a method of reacting an unsaturated group-containing isocyanate compound with a hydroxyl group or amino group possessed by the dye multimer, ( c) The method of making the epoxy compound which a dye multimer has, and the unsaturated bond containing carboxylic acid compound react is preferable from a manufacturing viewpoint.

(a) As an unsaturated bond containing epoxy compound in the method of making the carboxylic acid and the unsaturated bond containing epoxy compound which a dye multimer react, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3,4 -Epoxy-cyclohexylmethyl acrylate, 3,4-epoxy-cyclohexylmethyl methacrylate, and the like, in particular, methacrylic acid glycidyl and 3,4-epoxy-cyclohexylmethyl methacrylate are crosslinked. It is preferable because of its excellent properties and storage stability. Reaction conditions can use well-known conditions.

(b) Unsaturated bond-containing isocyanate compound in a method of reacting a hydroxyl group or amino group with a dye multimer with an unsaturated bond-containing isocyanate compound, 2-isocyanatoethyl methacrylate, 2 -Isocyanate ethyl acrylate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, and the like. 2-isocyanatoethyl methacrylate has a crosslinkability and storage stability. Excellent and preferred. Reaction conditions can use well-known conditions.

(c) The unsaturated bond-containing carboxylic acid compound in the method of reacting the epoxy compound of the dye multimer and the unsaturated bond-containing carboxylic acid compound can be used without particular limitation as long as it is a carboxylic acid compound having a known (meth) acryloyloxy group. Methacrylic acid and acrylic acid are preferable, and methacrylic acid is especially preferable because it is excellent in crosslinkability and storage stability. Reaction conditions can use well-known conditions.

(2) A method of copolymerizing a dye monomer and a polymerizable group-containing compound and introducing it:

(2) As a method of copolymerizing and introducing a dye monomer and a polymerizable group-containing compound, a known method can be used without particular limitation. (D) A method of copolymerizing a dye monomer capable of radical polymerization and a polymerizable group-containing compound capable of radical polymerization, (e) The method of copolymerizing the polymerizable group containing compound which can add a pigment monomer with a polyaddition is preferable.

(d) A radically polymerizable polymerizable group-containing compound in the method of copolymerizing a radically polymerizable dye monomer and a radically polymerizable polymerizable group-containing compound, particularly an allyl group-containing compound (for example, allyl (meth) acrylate), Epoxy group containing compound (for example, glycidyl (meth) acrylate, 3, 4- epoxy-cyclohexyl methyl (meth) acrylate, etc.), oxane group containing compound (for example, 3-methyl-3- jade) Cetanylmethyl (meth) acrylate, etc.) and a methylol group containing compound (for example, N- (hydroxymethyl) acrylamide etc.) are mentioned, An epoxy compound and an oxetane compound are especially preferable. Reaction conditions can use well-known conditions.

(e) An unsaturated bond-containing diol compound (for example, 2,3-dihydroxy) as a polymerizable group-containing compound which can be added in a method of copolymerizing a polyaddable dye monomer and a polymerizable group-containing compound. Propyl (meth) acrylate, etc.) is mentioned. Reaction conditions can use well-known conditions.

As the introduction method of a polymerizable group, the method of making the carboxylic acid and unsaturated bond containing epoxy compound which a dye multimer have react is especially preferable.

It is preferable that it is 0.1-2.0 mmol with respect to 1 g of dye multimers, as for the amount of polymeric groups which a dye multimer has, it is more preferable that it is 0.2-1.5 mmol, It is especially preferable that it is 0.3-1.0 mmol.

Moreover, 5-50 mol is preferable with respect to 100 mol of all the repeating units, and, as for the ratio of the repeating unit in which a dye multimer contains the repeating unit which has a polymeric group, 10-20 mol is more preferable.

As the introduction method of a polymerizable group, the method of making the carboxylic acid and unsaturated bond containing epoxy compound which a dye multimer have react is especially preferable.

As a repeating unit which has a polymeric group, the following specific examples are mentioned. However, this invention is not limited to these.

[Formula 47]

[Formula 48]

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

<<< alkali soluble group >>>

An acid group is mentioned as an example of the alkali-soluble group which may be contained in the dye multimer in this invention. As an acidic group, a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group are illustrated. In this invention, it is preferable that an acidic radical is contained in a dye multimer as a repeating unit which has an acidic radical. One type of acidic radical may be included and may be included two or more types.

In this invention, Preferably, alkali-soluble group (preferably acidic group) is contained in a dye multimer as a repeating unit which has alkali-soluble group (acidic group).

As a method of introducing the alkali-soluble group into the dye multimer, monomer ((meth) acrylic acid, caprolactone modified product of acrylic acid, (meth) acrylic acid other than the dye monomer having a alkali-soluble group and a dye monomer having an alkali-soluble group in advance Anhydrous succinic acid modified product of 2-hydroxyethyl, Phthalic anhydride modified product of 2-hydroxyethyl (meth) acrylate, 1,2-cyclohexanedicarboxylic acid anhydride modified product of 2-hydroxyethyl (meth) acrylate, Carboxylic acid-containing monomers such as styrene carboxylic acid, itaconic acid, maleic acid, norbornene carboxylic acid, phosphoric acid-containing monomers such as acid phosphoxyethyl methacrylate, vinylphosphonic acid, vinylsulfonic acid, 2-acrylamide-2-methylsulfonic acid And sulfonic acid-containing monomers) may be copolymerized, and it is more preferable to use both methods.

It is preferable that the amount of alkali-soluble groups which a dye multimer has is 0.3 mmol-2.0 mmol with respect to 1 g of dye multimers, It is more preferable that it is 0.4 mmol-1.5 mmol, It is especially preferable that it is 0.5 mmol-1.0 mmol.

Moreover, when a dye multimer contains the repeating unit containing a dye monomer, and the repeating unit which has an acidic radical, the ratio of the repeating unit containing the repeating unit which has an acidic radical is an example with respect to 100 mol of repeating units containing a dye monomer. For example, 5-70 mol is preferable and 10-50 mol is more preferable.

The dye multimer used by this invention is a repeating unit containing an alkali-soluble group, and has a repeating unit which has group which consists of repeating of 2-20 unsubstituted alkyleneoxy chain in a side chain (henceforth "(b) repeating unit"). May be used). By containing (b) a repeating unit, it can be set as the coloring composition excellent in decolorization resistance.

2-15 are preferable and, as for the number of repetitions of the alkyleneoxy chain which a repeating unit (b) has, 2-10 are more preferable.

One alkylene chain, - (CH _{2) n} appears as O-, inde n is an integer, n is 1 to 10 is preferable, and 1 to 5 is more preferred, 2 or 3 is more preferable.

In the present invention, only one kind of alkyleneoxy chain may be included or two or more kinds of the group consisting of repetition of 2 to 20 unsubstituted alkyleneoxy chains may be included.

In this invention, it is preferable that (b) repeating unit is represented with the following general formula (P).

General formula (P)

[Formula 49]

(In general formula (P), X <_1> represents the coupling group formed by superposition | polymerization, and L <_1> represents a single bond or a bivalent coupling group. P represents the group containing the group which consists of repetition of an alkyleneoxy chain.)

X <_1> and L <_1> in general formula (P) are synonymous with X <_1> and L <_1> in general formula (A), respectively, and its preferable range is also the same.

P represents group containing the group which consists of repetition of an alkyleneoxy chain, and it is more preferable that it consists of group-terminal atom or terminal group which consists of repetition of -alkyleneoxy chain.

As a terminal atom or a terminal group, a hydrogen atom, an alkyl group, an aryl group, and a hydroxyl group are preferable, A hydrogen atom, a C1-C5 alkyl group, a phenyl group, and a hydroxyl group are more preferable, A hydrogen atom, a methyl group, a phenyl group, and a hydroxyl group are more preferable. , Hydrogen atom is particularly preferred.

(b) It is preferable that the ratio of the repeating unit which has group which consists of repetition of 2-20 unsubstituted alkyleneoxy chain in a side chain is 2-20 mol% of all the repeating units which comprise the said dye multimer, 5 15 mol% is more preferable.

Hereinafter, although the example of the (b) repeating unit which can be used by this invention is shown, it goes without saying that this invention is not limited to these.

[Formula 50]

As other functional groups possessed by the dye multimers, development accelerators such as lactones, acid anhydrides, amides, -COCH ₂ CO- and cyano groups, long chain and cyclic alkyl groups, aralkyl groups, aryl groups, polyalkylene oxide groups, and hydroxyl groups Hydrophilicity regulators, such as a maleimide group and an amino group, etc. are mentioned, It can introduce | transduce suitably.

As an introduction method, the method of introduce | transducing into a pigment monomer previously, and the method of copolymerizing the monomer which has the said functional group are mentioned.

Although the specific example of the repeating unit which has alkali-soluble group or other functional group which a dye multimer may have is shown, this invention is not limited to this.

[Formula 51]

[Formula 52]

[Formula 53]

[Formula 54]

[Formula 55]

<<< structural unit which has at least one of the structures represented by Formula (1)-(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. By setting it as such a structure, when a cured film is produced, exposure sensitivity and light resistance can be made favorable. Here, the structure represented by Formula (1)-(5) contributes to the improvement of exposure sensitivity and light resistance by functioning as a light stabilizer. Moreover, adhesiveness can be improved. In addition, the development residue can be suppressed. Although this mechanism is presumed, by using the dye multimer which has at least 1 sort (s) of a pigment | dye structure and the structure represented by Formula (1)-(5) in the same molecule, it is represented by a pigment | dye structure and Formula (1)-(5). The distance of the appearing structure is closer. As a result, it is thought that exposure sensitivity and light resistance can be improved more effectively.

The structure represented by Formula (1) is named a hindered amine type generically. The structure represented by Formula (2) is named a hindered phenol type generically. The structure represented by Formula (3) is named a benzotriazole system generically. The structure represented by Formula (4) is named a hydroxy benzophenone system generically. The structure represented by Formula (5) is named a triazine system generically.

[Formula 56]

In formula (1), R <^1> represents a hydrogen atom, a C1-C18 alkyl group, an aryl group, and oxyradical. R ² and R ³ each independently represent an alkyl group having 1 to 18 carbon atoms. R ² and R ³ may be bonded to each other to represent an aliphatic ring having 4 to 12 carbon atoms. "*" Represents the bond of the structure and polymer skeleton which are represented by Formula (1).

In formula (1), R <^1> represents a hydrogen atom, a C1-C18 alkyl group, an aryl group, and oxy radicals, and a C1-C18 alkyl group is preferable.

The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, but is preferably linear. 1-12 are preferable, as for carbon number of a C1-C18 alkyl group, 1-8 are more preferable, 1-3 are more preferable, and 1 or 2 is especially preferable. 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 6-18, 6-12 may be sufficient, and 6 may be sufficient as it. Specifically, a phenyl group is mentioned.

When R <^1> in Formula (1) represents a C1-C18 alkyl group or an aryl group, a C1-C18 alkyl group and aryl group may have a substituent, and may be unsubstituted. As a substituent which you may have, the substituent selected from the substituent group A mentioned above is mentioned.

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

In Formula (1), "*" represents the bond of the structure and polymer skeleton which are represented by Formula (1). The bonding hand may be directly bonded to the polymer skeleton through a linking group, or may be bonded directly to the above-described dye structure through a linking group. In particular, it is preferable that "*" in Formula (1) couple | bonds with a polymer skeleton directly or via a coupling group.

Hereinafter, although the specific example of the structure represented by Formula (1) is shown, it is not limited to these. In the following structure, "*" represents the bond of the structure and polymer skeleton which are represented by Formula (2).

[Formula 57]

[Formula 58]

In formula (2), R <^4> represents following formula (2A), a C1-C18 alkyl group, or an aryl group. R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. "*" Represents the bond of the structure and polymer skeleton which are represented by Formula (2).

In formula (2), R <^4> represents following formula (2A), a C1-C18 alkyl group, or an aryl group, and it is preferable to represent by Formula (2A). The C1-C18 alkyl group and aryl group are synonymous with the C1-C18 alkyl group and aryl group demonstrated by R <^1> in Formula (1). "*" Is synonymous with the bond which was demonstrated in Formula (1).

[Formula 59]

In formula (2A), R <^6> represents a C1-C18 alkyl group each independently. "*" Represents the bond of the structure represented by Formula (2A), and the structure represented by Formula (2).

In formula (2A), R <^6> is synonymous with the C1-C18 alkyl group demonstrated by R <^1> in Formula (1). "*" Is synonymous with the bond which was demonstrated in Formula (1).

Hereinafter, although the specific example of the structure represented by Formula (2) is shown, it is not limited to these. In the following structure, "*" represents the bond of the structure and polymer skeleton which are represented by Formula (2).

[Formula 60]

[Formula 61]

In formula (3), R <^7> represents a C1-C18 alkyl group; n1 represents the integer of 0-3. When n1 is 2 or 3, each R <^7> may be same or different. "*" Represents the bond of the structure and polymer skeleton which are represented by Formula (3).

In formula (3), R <^7> is synonymous with the C1-C18 alkyl group demonstrated by R <^1> in Formula (1).

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

In Formula (3), "*" is synonymous with the bonding hand demonstrated in Formula (1).

Hereinafter, although the specific example of the structure represented by Formula (3) is shown, it is not limited to these. In the following structure, "*" represents the bond of the structure and polymer skeleton which are represented by Formula (3).

[Formula 62]

[Formula 63]

In formula (4), R <^8> and R <^9> respectively independently represents a C1-C18 alkyl group. n2 represents the integer of 0-3. n3 represents the integer of 0-4. When n2 is 2 or 3, each R <^8> may be same or different. When n3 represents the integer of 2-4, each R <^9> may be same or different. "*" Represents the bond of the structure and polymer skeleton which are represented by Formula (4).

In formula (4), R <^8> and R <^9> is synonymous with the C1-C18 alkyl group demonstrated by R <^1> in Formula (1).

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

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

In Formula (4), "*" is synonymous with the bonding hand demonstrated in Formula (1).

Hereinafter, although the specific example of the structure represented by Formula (4) is shown, it is not limited to these. "*" Represents the bond of the structure and polymer skeleton which are represented by Formula (4) in the following structure.

[Formula 64]

[Formula 65]

In formula (5), R <^10> -R <^12> represents a C1-C18 alkyl group or a C1-C8 alkoxy group each independently. n4-n6 represent the integer of 0-5 each independently. n7 to n9 each independently represent 0 or 1, and at least one of n7 to n9 represents 1; "*" Represents the bond of the structure and polymer skeleton which are represented by Formula (5).

When R <^10> in Formula (5) represents a C1-C18 alkyl group, it is synonymous with the C1-C18 alkyl group demonstrated by R <^1> in Formula (1), A C1-C3 alkyl group is preferable, and a methyl group is more preferable. desirable. When R <^10> represents a C1-C8 alkoxy group, 1-6 are preferable, as for carbon number of an alkoxy group, 1-5 are more preferable, and 1-4 are more preferable.

R ¹⁰ in formula (5) may further have a substituent. As a substituent which you may have, the substituent selected from the substituent group A mentioned above is mentioned.

N4 in Formula (5) represents the integer of 0-5, the integer of 1-4 is preferable, and 2 or 3 is preferable. When n4 represents the integer of 2-5, each R <^10> may be same or different.

R <^11> in Formula (5) is synonymous with R <^10> in Formula (5), and its preferable range is also the same.

N5 in Formula (5) represents the integer of 0-5, the integer of 1-3 is preferable, and 1 or 2 is preferable. When n5 represents the integer of 2-5, each R <^11> may be same or different.

R <^12> in Formula (5) is synonymous with R <^10> in Formula (5), and its preferable range is also the same.

N6 in Formula (5) represents the integer of 0-5, the integer of 0-3 is preferable, and 0 or 1 is preferable. When n6 represents the integer of 2-5, each R <^12> may be same or different.

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

In Formula (5), "*" is synonymous with the bonding hand demonstrated in Formula (1).

Hereinafter, although the specific example of the structure represented by Formula (5) is shown, it is not limited to these. In the following structure, "*" represents the bond of the structure and polymer skeleton which are represented by Formula (5).

[Formula 66]

It is preferable that the structural unit which has at least one of the structures represented by Formula (1)-(5) which the dye multimer used for this invention has is represented by a following formula (E).

Formula (E)

[Formula 67]

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

Hereinafter, although the specific example of the structural unit which has at least one of the structures represented by Formula (1)-(5) is shown, this invention is not limited to these.

[Formula 68]

Although the dye multimer does not need to have a structural unit which has at least one of the structures represented by Formula (1)-(5), when it has, when making all the structural units in a dye multimer 100 mass%, Formula (1) It is preferable that content of the structural unit which has at least one of the structures represented by)-(5) is 0.5-20 mass%, It is more preferable that it is 1-10 mass%, It is especially preferable that it is 1-5 mass%.

<<< specific terminal group >>>

It is preferable that the dye multimer used by this invention has group represented by general formula (I) or group represented by general formula (II) (henceforth a "specific terminal group"). By setting it as such a structure, solvent resistance and light resistance can be provided. Moreover, since it synthesize | combines by living radical polymerization, for example, the dispersion degree (Mw / Mn) of a dye multimer can be made small. That is, as a dye multimer, light resistance can be improved more by reducing the ratio of a high molecular weight component, and solvent resistance can be improved by reducing the ratio of a low molecular weight component. Moreover, heat resistance, applicability | paintability, and developability can be improved more.

Formula (I)

[Formula 69]

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

In General Formula (I), Z represents a monovalent substituent. Z is a hydrogen atom, a halogen atom, a carboxyl group, a cyano group, an alkyl group having 1 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, a total of 3 to 30 atoms in carbon atoms and a binary atom A heterocyclic group, -OR ¹ , -SR ¹ , -OC (= O) R ¹ , -N (R ¹ ) (R ² ), -C (= O) OR ¹ , -C (= O) N (R ¹ ) (R ² ), -P (= O) (OR ¹ ) ₂ , -P (= O) (R ¹ ) ² or monovalent group having a polymer chain are preferred, -SR ¹ , aryl group, heteroaryl It is preferably selected from an amino group, an alkoxy group, and an aryloxy group substituted with a group, an alkyl group and / or an aryl group, more preferably -SR ¹ (preferably an alkylthio group, an arylthio group), an aryl group. It is preferable that it is an alkylthio group or an aryl group, and it is especially preferable that it is an alkylthio group.

The aryl group as Z is preferably a phenyl group or a naphthyl group. The heteroaryl group as Z is preferably a nitrogen-containing 5- or 6-membered ring compound. The amino group substituted with the alkyl group and / or aryl group as Z is preferable the amino group substituted with the C1-C5 alkyl group or the 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 total number of atoms of 3 to 30 carbon atoms and a binary atom; monovalent represents a heterocyclic group, an alkyl group in the 1 to 30 carbon atoms, monovalent heterocyclic having 6 to 30 carbon atoms and monovalent aromatic hydrocarbon groups, the carbon atoms and the total number of atoms of the binary atoms 3-30 in the ventilation, R ¹ and R ^{All of 2} may be substituted and does not need to be substituted. As a substituent in the case of substitution, an alkyl group, an aryl group, etc. are illustrated.

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

General formula (II)

[Formula 70]

In General Formula (II), A and B respectively independently represent a monovalent substituent. A and B may mutually be connected and may form a ring. * Represents a 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 and an aryl group having 6 to 30 carbon atoms. As for a C1-C30 alkyl group, it is more preferable that it is C3-C10.

In particular, it is preferable that one of A and B is a C1-C30 secondary or tertiary alkyl group, and the other is a C1-C30 alkyl group or a C6-C30 aryl group, and one of A and B Silver is C1-C30 tertiary alkyl, It is more preferable that the other of A and B is a C1-C30 alkyl group, One of A and B is C1-C30 tertiary alkyl, and the other It is especially preferable that one is a C1-C30 secondary or tertiary alkyl group (more preferably, a C1-C30 secondary alkyl group).

As a substituent which the C1-C30 alkyl group may have, an aryl group is preferable and a phenyl group is more preferable. As a substituent which the aryl group may have, an aryl group is preferable. In addition, these groups may be substituted by other substituents. A and B may combine with each other and form the ring.

In the present invention, in particular, Z in General Formula (I) is —SR ¹ or an aryl group, and A and B in General Formula (II) are each a C 1-30 secondary or tertiary alkyl group. (It is preferable that A and B may be bonded to each other to form a ring).

Although the specific example of an end group is shown, this invention is not limited to this.

[Formula 71]

[Formula 72]

[Formula 73]

As a method of introducing the terminal group represented by general formula (I) or (II) into a polymer main chain, the compound represented by general formula (Ia), the compound represented by general formula (IIa), and the radical represented by general formula (IIb) In the presence of at least 1 sort (s), the method of radically polymerizing the polymeric compound which has a pigment | dye structure is preferable.

General formula (Ia)

[Formula 74]

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

General formula (IIa)

[Formula 75]

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

General formula (IIb)

[Formula 76]

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

By mix | blending such an additive, the active inactivation of the terminal at the time of radical polymerization will be in the equilibrium state, and it will be in the state which an radical does not deactivate seemingly. By polymerizing by such living radical polymerization, a multimer with a small dispersion degree is obtained.

<Pigment multimer>

It is preferable that the weight average molecular weights (Mw) of a dye multimer are 2,000-50,000, It is more preferable that it is 3,000-30,000, It is especially preferable that it is 6,000-20,000.

Moreover, it is preferable that ratio [(Mw) / (Mn)] of the weight average molecular weight (Mw) and number average molecular weight (Mn) of a dye multimer is 1.0-2.0, It is more preferable that it is 1.1-1.8, 1.1 It is especially preferable that it is -1.5.

It is preferable that it is 50 degreeC or more, and, as for the glass transition temperature (Tg) of the dye multimer which concerns on this invention, it is more preferable that it is 100 degreeC or more. Moreover, it is preferable that the 5 weight% reduction temperature by thermogravimetric analysis (TGA measurement) is 120 degreeC or more, It is more preferable that it is 150 degreeC or more, It is more preferable that it is 200 degreeC or more. By being in this area | region, when applying the coloring composition of this invention to preparation of color filters etc., it becomes possible to reduce the density | concentration change resulting from a heating process.

When the dye multimer used by this invention contains the repeating unit which has a pigment | dye structure, and another repeating unit, it is preferable that it is a random polymer of the polymeric compound containing a pigment | dye, and another polymeric compound. By setting it as a random polymer, a pigment | dye structure exists in a dye multimer at random, and the effect of this invention is exhibited more effectively.

Moreover, it is preferable that the extinction coefficient per unit weight of the dye multimer which concerns on this invention (after it is epsilon '. (Epsilon' = epsilon / average molecular weight, a unit: L / g * cm) is 30 or more, and it is 60 or more. It is more preferable, and it is more preferable that it is 100 or more. By being in this range, when producing the color filter by applying the coloring composition of this invention, the color filter with favorable color reproducibility can be produced.

It is preferable that the molar extinction coefficient of the dye multimer used for the coloring composition of this invention is as high as possible from a viewpoint of a coloring power.

It is preferable that it is 4.0-10.0, it is more preferable that it is 5.0-9.0, and, as for the reduced viscosity of the dye multimer used for the coloring composition of this invention, it is 6.0-7.0. A reduced viscosity can be measured using a Uberode type viscometer, for example.

It is preferable that the dye multimer which concerns on this invention is a compound melt | dissolved in the following organic solvents.

As the organic solvent, esters (for example, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, etc.), ethers (for example, methyl cellosolve) Acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), ketones (methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.) And aromatic hydrocarbons (for example, toluene, xylene, and the like), and it is preferable to dissolve 1% by mass or more and 50% by mass or less with respect to these solvents, and more preferably 5% by mass or more and 40% by mass. % Or less, More preferably, they are 10 mass% or more and 30 mass% or less. By being in this area | region, when applying the coloring composition of this invention to preparation of a color filter etc., it becomes possible to reduce the density | concentration fall by the suitable application surface shape and the elution after another color application | coating.

In the coloring composition of this invention, although it is preferable to use the pigment multimer in this invention mentioned above individually by 1 type, you may use together 2 or more types.

Moreover, you may use together a dye multimer (henceforth another dye multimer) other than the dye multimer in this invention mentioned above. As another dye multimer, the dye multimer which has only one of the above-mentioned repeating unit (a1) and repeating unit (a2), etc. are mentioned. 5 mass% or less is preferable in a dye multimer whole quantity, as for content of another dye multimer, 3 mass% or less is more preferable, and 1 mass% or less is especially preferable.

Content of the dye multimer in the coloring composition of this invention does not have limitation in particular. For example, when using together a dye multimer and the pigment mentioned later, it sets after considering the content ratio of a dye multimer and a pigment.

In the case of using a dye multimer and a pigment together, as mass ratio (color multimer / pigment) of the dye multimer with respect to a pigment, 0.40-1.00 are preferable, 0.45-0.80 are more preferable, 0.50-0.75 are more preferable Do.

It is preferable that it is 50-70 mass% of the total solid of a coloring composition, and, as for the coloring agent component (total of a pigment multimer, a pigment mentioned later, and other dye) in the coloring composition of this invention, it is more preferable that it is 55-65 mass%. desirable.

<Curable Compound>

The coloring composition of this invention contains a curable compound. As a curable compound, polymeric compound and alkali-soluble resin (including alkali-soluble resin containing a polymeric group) are illustrated, and it selects suitably according to a use or a manufacturing method.

<< polymerizable compound >>

As a polymeric compound, the well-known polymeric compound which can be bridge | crosslinked by a radical, an acid, and a heat can be used. For example, the polymeric compound containing ethylenically unsaturated bond, cyclic ether (epoxy, oxetane), methylol, etc. is mentioned. The polymerizable compound is suitably selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds in view of sensitivity. Especially, the polyfunctional polymerizable compound more than tetrafunctional is preferable, and the polyfunctional polymerizable compound more than 5-functional is more preferable.

Such compound groups are widely known in the industrial field of the present invention, and these compounds can be used without particular limitation. These may be, for example, any of chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers or mixtures thereof and their multimers. The polymeric compound in this invention may be used individually by 1 type, and may use 2 or more types together.

More specifically, as an example of a monomer and its prepolymer, unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), its esters, amides, and these A multimer is mentioned, Preferably, they are ester of unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and amides of unsaturated carboxylic acid and an aliphatic polyamine compound, and these multimers. Moreover, the addition reaction product of the unsaturated carboxylic ester or amide which has nucleophilic substituents, such as a hydroxyl group, an amino group, and a mercapto group, and monofunctional or polyfunctional isocyanate or epoxy, or monofunctional or polyfunctional Dehydration condensation reaction products with carboxylic acid, etc. are also used suitably. Moreover, addition reaction products of unsaturated carboxylic acid esters or amides which have electrophilic substituents, such as an isocyanate group and an epoxy group, and monofunctional or polyfunctional alcohols, amines, and thiols, and a halogen group, a tosyloxy group, etc. Substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent of and mono- or polyfunctional alcohols, amines, and thiols are also suitable. As another example, a compound group substituted with a vinylbenzene derivative such as unsaturated phosphonic acid and styrene, vinyl ether, allyl ether, or the like may be used instead of the above unsaturated carboxylic acid.

As these specific compounds, the compound described in Paragraph No. 0095-0108 of Unexamined-Japanese-Patent No. 2009-288705 can also be used suitably also in this invention.

Moreover, as a polymeric compound, the compound which has an ethylenically unsaturated group which has a boiling point of 100 degreeC or more under normal pressure which has an ethylene group which can carry out at least 1 addition polymerization is also preferable. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; Polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether (Meth) acrylated after addition of ethylene oxide or propylene oxide to polyfunctional alcohols such as tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylolethane, and Japanese Patent Publication No. 48 Urethane (meth) acrylates described in -41708, Japanese Patent Application Laid-open No. 50-6034, Japanese Patent Application Laid-open No. 51-37193, Japan The polyester acrylates described in Unexamined-Japanese-Patent No. 48-64183, Japanese Unexamined Patent Publication No. 49-43191, and Japanese Unexamined Patent Publication No. And polyfunctional acrylates and methacrylates such as acrylates, and mixtures thereof.

The polyfunctional (meth) acrylate etc. which are obtained by making the compound which has cyclic ether groups, such as glycidyl (meth) acrylate, and ethylenically unsaturated group, react with polyfunctional carboxylic acid are mentioned.

Moreover, as another preferable polymeric compound, it has a fluorene ring as described in Unexamined-Japanese-Patent No. 2010-160418, Unexamined-Japanese-Patent No. 2010-129825, Unexamined-Japanese-Patent No. 4364216, etc., and has a bifunctional ethylenically unsaturated group. The compound and cardo resin which have the above can also be used.

Moreover, the compound of Paragraph No. [0254]-[0257] of Unexamined-Japanese-Patent No. 2008-292970 is also suitable as a compound which has a boiling point of 100 degreeC or more under normal pressure, and has an ethylenically unsaturated group which can be at least 1 addition polymerization.

In addition to the above, a radically polymerizable monomer represented by the following General Formulas (MO-1) to (MO-5) can also be suitably used. In addition, in formula, when T is an oxyalkylene group, the terminal at the side of a carbon atom couple | bonds with R.

[Formula 77]

[Formula 78]

In general formula, n is 0-14 and m is 1-8. Two or more R and T in one molecule may be same or different, respectively.

In each of the polymerizable compounds represented by General Formulas (MO-1) to (MO-5), at least one of _two or more R's is -OC (= O) CH = CH ₂ , or -OC (= O) Group represented by C (CH ₃ ) = CH ₂ .

As a specific example of the polymeric compound represented by General Formula (MO-1)-(MO-5), Paragraph No. 0248-Paragraph No. 0251 of Unexamined-Japanese-Patent No. 2007-269779 is used suitably also in this invention. Can be.

Moreover, the compound which (meth) acrylated after adding ethylene oxide and a propylene oxide to the polyfunctional alcohol described with the specific example as General Formula (1) and (2) in Unexamined-Japanese-Patent No. 10-62986. Moreover, it can use as a polymeric compound.

Especially, as a polymeric compound, dipentaerythritol triacrylate (as a commercial item, KAYARAD D-330; made by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial item, KAYARAD D-320; Nippon Kayaku) (Made by KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA as a commercially available product; Nippon) The structure by which Kayaku Co., Ltd.) and these (meth) acryloyl groups interpose ethylene glycol and a propylene glycol residue is preferable. These oligomer types can also be used.

As a polymeric compound, it is a polyfunctional monomer, and may have acidic groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. If an ethylenic compound has an unreacted carboxyl group as mentioned above, this can be used as it is, but you may introduce an acidic radical by making non-aromatic carboxylic anhydride react with the hydroxyl group of the ethylenic compound mentioned above as needed. In this case, specific examples of the non-aromatic carboxylic anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a polyfunctional monomer having an acid group by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. In this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. As a commercial item, M-510, M-520, etc. are mentioned as a polybasic acid modified | denatured acrylic oligomer by Toagosei Co., Ltd., for example.

Although these monomers may be used individually by 1 type, since it is difficult to use a single compound in manufacture, you may mix and use 2 or more types. Moreover, you may use together the polyfunctional monomer which does not have an acidic radical as a monomer, and the polyfunctional monomer which has an acidic radical as needed.

As a preferable acid value of the polyfunctional monomer which has an acidic radical, it is 0.1 mgKOH / g-40 mgKOH / g, Especially preferably, it is 5 mgKOH / g-30 mgKOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are poor. If the acid value of the polyfunctional monomer is too high, manufacturing and handling become difficult, and photopolymerization performance is poor, resulting in inferior sclerosis such as surface smoothness of the pixel. Therefore, when using together 2 or more types of polyfunctional monomers of another acidic radical, or when using the polyfunctional monomer which does not have an acidic radical, it is preferable to adjust so that the acidic radical as a whole polyfunctional monomer may enter in the said range.

Moreover, it is also a preferable aspect to contain the polyfunctional monomer which has a caprolactone structure as a polymeric compound.

The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, but for example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolprop Ε-caprolactone obtained by esterifying polyhydric alcohols such as pane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, and (meth) acrylic acid and ε-caprolactone A modified polyfunctional (meth) acrylate can be mentioned. Especially, the polyfunctional monomer which has a caprolactone structure represented by the following general formula (Z-1) is preferable.

[Formula 79]

In general formula (Z-1), all 6 R is group represented by the following general formula (Z-2), or 1-5 of 6 R are group represented by the following general formula (Z-2), Residual is a group represented by the following general formula (Z-3).

[Formula 80]

In 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 bond.

[Formula 81]

In General Formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.

The polyfunctional monomer which has such a caprolactone structure is marketed as a KAYARAD DPCA series, for example from Nippon Kayaku Co., Ltd., and DPCA-20 (m = 1, Formula in said Formula (1)-(3), for example). The number of groups represented by (2) = 2 and the compound in which R ¹ is all hydrogen atoms), DPCA-30 (the same formula, m = 1, the number of groups represented by formula (2) = 3, R ¹ are all hydrogen atoms) Phosphorus compound), DPCA-60 (the same formula, m = 1, the number of groups represented by Formula (2) = 6, a compound in which R ¹ is all a hydrogen atom), DPCA-120 (m = 2 in the same formula, formula The number of groups represented by (2) = 6 and the compound in which R <^1> is all hydrogen atoms) etc. are mentioned.

In this invention, the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.

Moreover, it is preferable that it is at least 1 sort (s) chosen from the group of the compound represented by the following general formula (Z-4) or (Z-5) as a polymeric compound.

[Formula 82]

In General Formulas (Z-4) and (Z-5), each E independently represents-((CH ₂ ) yCH ₂ O)-or-((CH ₂ ) yCH (CH ₃ ) O)-. Y respectively independently represents the integer of 0-10, and X represents acryloyl group, methacryloyl group, a hydrogen atom, or a carboxyl group each independently.

In general formula (Z-4), the sum total of acryloyl group and methacryloyl group is three or four, m respectively independently represents the integer of 0-10, and the sum of each m is an integer of 0-40 to be. However, when the sum of each m is 0, any one of X is a carboxyl group.

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

In general formula (Z-4), the integer of 0-6 is preferable and, as for m, the integer of 0-4 is more preferable. Moreover, the integer of 2-40 is preferable, as for the sum total of each m, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable.

In general formula (Z-5), the integer of 0-6 is preferable and, as for n, the integer of 0-4 is more preferable.

Moreover, the integer of 3-60 is preferable, as for the sum total of each n, the integer of 3-24 is more preferable, and the integer of 6-12 is especially preferable.

The general formula (Z-4) or general formula (Z-5) of _{- ((CH 2) yCH 2} O) - or _{- ((CH 2) yCH (} CH 3) O) - , the oxygen atom side of the The form which the terminal couple | bonds with X is preferable.

The compound represented by general formula (Z-4) or general formula (Z-5) may be used individually by 1 type, and may be used together 2 or more types. In particular, in general formula (Z-5), the form whose all 6 X is acryloyl group is preferable.

Moreover, as total content in the polymeric compound of the compound represented by general formula (Z-4) or general formula (Z-5), 20 mass% or more is preferable and 50 mass% or more is more preferable.

The compound represented by general formula (Z-4) or (Z-5) binds a ring-opening skeleton by ring-opening addition reaction of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol which is a conventionally well-known process. It can synthesize | combine from the process to introduce | transduce a (meth) acryloyl group, for example by making (meth) acryloyl chloride react with the terminal hydroxyl group of a ring-opening skeleton. Each process is a well-known process, and a person skilled in the art can easily synthesize | combine the compound represented by general formula (Z-4) or (Z-5).

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

Specifically, the compound (henceforth "exemplified compound (a)-(f)") represented by following formula (a)-(f) is mentioned, Especially, exemplary compound (a), (b) , (e) and (f) are preferred.

[Formula 83]

[Formula 84]

As a commercial item of the polymeric compound represented by general formula (Z-4) and (Z-5), SR-494 and Nippon Kayaku Co., Ltd. which are tetrafunctional acrylates which have four ethyleneoxy chains made from Sartomer, for example. DPCA-60 which is a 6-functional acrylate which has six pentylene oxy chains, and TPA-330 which is a trifunctional acrylate which has three isobutylene oxy chains, etc. are mentioned.

Moreover, as a polymeric compound, it is described in Unexamined-Japanese-Patent No. 48-41708, Unexamined-Japanese-Patent No. 51-37193, Unexamined-Japanese-Patent No. 2-32293, and Unexamined-Japanese-Patent No. 2-16765. Urethane acrylates and the ethylene oxides described in JP-A-58-49860, JP-A-56-17654, JP-A-62-39417, and JP-A-62-39418. Also suitable are urethane compounds having a system skeleton. As the polymerizable compound, an addition having an amino structure or a sulfide structure in a molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-105238. By using polymeric compounds, the curable composition which is very excellent in the photosensitive speed can be obtained.

As a commercial item of a polymeric compound, a urethane oligomer UAS-10, UAB-140 (made by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (made by Shin-Nakamura Kagaku Co., Ltd.), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H , UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha), and the like.

As cyclic ether (epoxy, oxetane), for example, what has an epoxy group is a bisphenol-A epoxy resin, JER-827, JER-828, JER-834, JER-1001, JER-1002, JER-1003, Bisphenol F type epoxy resin As JER-806, JER-807, JER-4004, JER-4005, JER-4007, JER-4010 (above, Japan epoxy resin Co., Ltd.), EPICLON830, EPICLON835 (above, DIC Corporation), LCE-21, RE-602S (above, made by Nippon Kayaku Co., Ltd.) and the like, and are phenol novolac-type epoxy resins, such as JER-152, JER-154, JER-157S70, and JER-157S65 (above, Japan epoxy resins). Co., Ltd.), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, made by DIC Corporation), etc., and are cresol novolak-type epoxy resins, and are EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, made by DIC Corporation), EOCN-1020 ( In addition, as Nippon Kayaku Co., Ltd., and an aliphatic epoxy resin, ADEKA RESIN EP-4080S, copper EP-4085S, copper EP-4088S (above, made by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celock Side 2083, Celoxide 2085, EHPE-3150 (1, 2-Epoxy-4- (2-oxirayl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol), EPOLEAD PB 3600, copper PB 4700 (above, Daicel Kagaku Kogyo Co., Ltd.), Denacol EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, Nagase Chem TEX CORPORATION), ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above, ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD -1000, EPPN-501, EPPN-502 (above, made by ADEKA Corporation), JER-1031S (made by Japan Epoxy Resin Co., Ltd.), etc. are mentioned. Such a polymerizable compound is suitable when a pattern is formed by a dry etching method.

About these polymeric compounds, the detail of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of a coloring composition. For example, from the viewpoint of sensitivity, a structure containing a large amount of unsaturated groups per molecule is preferable, and in many cases, bifunctional or more is preferable. Moreover, from a viewpoint of raising the intensity | strength of the cured film formed with the coloring composition, a trifunctional or more functional thing is good, and also the number of different functional groups and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene type compound, and vinyl ether type compound) By using together, the method of adjusting both sensitivity and intensity is also effective. Moreover, it is preferable to use the polymerizable compound from which an ethylene oxide chain length differs together by trifunctional or more functional thing from the point that the developability of a coloring composition can be adjusted and the outstanding pattern formation ability is obtained.

Moreover, also about compatibility and dispersibility with other components (for example, a photoinitiator, a to-be-dispersed substance, alkali-soluble resin, etc.) contained in a coloring composition, selection and use of a polymeric compound are important factors, for example, Compatibility may be improved by using a purity compound or using 2 or more types together. Moreover, a specific structure may be selected from a viewpoint of improving adhesiveness with hard surfaces, such as a support body.

When mix | blending a polymeric compound in the coloring composition of this invention, 0.1 mass%-90 mass% are preferable with respect to the total solid in a coloring composition, and, as for content of a polymeric compound, 1.0 mass%-60 mass% are more preferable. 2.0 mass%-40 mass% are especially preferable.

The coloring composition of this invention may include only one type and may contain two or more types of polymeric compounds. When it contains two or more types, it is preferable that the total amount becomes said range.

<Multifunctional Thiol Compound>

The coloring composition of this invention may contain the polyfunctional thiol compound which has a 2 or more mercapto group in a molecule | numerator for the purpose of promoting the reaction of a polymeric compound, etc. It is preferable that it is secondary alkanes thiols, and, as for a polyfunctional thiol compound, it is especially preferable that it is a compound which has a structure represented by the following general formula (I).

Formula (I)

[Formula 85]

(In formula, n represents the integer of 2-4, and L represents the 2-4 valent coupling group.)

In said general formula (I), it is preferable that linking group L is a C2-C12 aliphatic group, n is 2 and it is especially preferable that L is a C2-C12 alkylene group. As a specific example of a polyfunctional thiol compound, the compound represented by following structural formula (II)-(IV) is mentioned, The compound represented by (II) is especially preferable. These polyfunctional thiols can be used 1 type or in combination.

[Formula 86]

About the compounding quantity of the polyfunctional thiol compound in the coloring composition of this invention, 0.3-8.9 mass% is preferable with respect to the total solid except a solvent, and 0.8-6.4 mass% is more preferable.

One type of polyfunctional thiol compound may be included and may be included two or more types. When it contains two or more types, it is preferable that the total amount becomes said range.

Moreover, you may add a polyfunctional thiol for the purpose of improvement of stability, odor, resolution, developability, adhesiveness, etc.

<Alkali Soluble Resin>

It is preferable that the coloring composition of this invention contains alkali-soluble resin further.

Although it does not specifically determine as molecular weight of alkali-soluble resin, It is preferable that Mw is 5000-100,000. Moreover, it is preferable that Mn is 1000-20,000.

As alkali-soluble resin, it is a linear organic high polymer and can be suitably selected from alkali-soluble resin which has group which promotes at least 1 alkali solubility in a molecule (preferably an acryl-type copolymer and the molecule which has a styrene-type copolymer as a main chain). . From the viewpoint of heat resistance, polyhydroxy styrene resin, polysiloxane resin, acrylic resin, acrylamide resin, acrylic / acrylamide copolymer resin are preferable, and acrylic resin and acrylamide resin from the viewpoint of developability control. And acrylic / acrylamide copolymer resins are preferred.

Examples of the group promoting alkali solubility (hereinafter also referred to as acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, and the like, which is soluble in an organic solvent and developable by a weak alkaline aqueous solution. And (meth) acrylic acid are mentioned as especially preferable. 1 type of these acid groups may be sufficient, and 2 or more types may be sufficient as them.

As a monomer which can provide an acidic radical after superposition | polymerization, the monomer which has hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, the monomer which has epoxy groups, such as glycidyl (meth) acrylate, and 2-isocysi, for example. The monomer etc. which have isocyanate groups, such as anatoethyl (meth) acrylate, are mentioned. 1 type of monomers for introducing these acid groups may be sufficient, and 2 or more types may be sufficient as it. In order to introduce an acidic radical into alkali-soluble resin, the monomer which has an acidic radical, and / or the monomer which can give an acidic radical after superposition | polymerization (Hereinafter, it may be called "monomer for introducing an acidic radical") superposes | polymerizes as a monomer component. You can do that.

Moreover, when introduce | transducing an acidic radical using the monomer which can provide an acidic radical after superposition | polymerization as a monomer component, the process for providing an acidic radical as mentioned later, for example after polymerization is needed.

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

As the linear organic polymer used as the alkali-soluble resin, a polymer having carboxylic acid in the side chain is preferable, and methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partial esterification Alkyl-soluble phenol resins, such as a maleic acid copolymer and a novolak-type resin, etc., and what added the acid anhydride to the acidic cellulose derivative which has a carboxylic acid in a side chain, and the polymer which has a hydroxyl group are mentioned. In particular, the copolymer of (meth) acrylic acid and the other monomer copolymerizable with this is suitable as alkali-soluble resin. As another monomer copolymerizable with (meth) acrylic acid, an alkyl (meth) acrylate, an aryl (meth) acrylate, a vinyl compound, etc. are mentioned. As alkyl (meth) acrylate and aryl (meth) acrylate, 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 (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate As a vinyl compound, such as cyclohexyl (meth) acrylate, styrene, (alpha) -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydro N-substituted maleimide monomers described in Japanese Patent Application Laid-open No. Hei 10-300922, such as furfuryl methacrylate, polystyrene macromonomer, and polymethylmethacrylate macromonomer , N-phenylmaleimide, N-cyclohexyl maleimide and the like. In addition, the other monomer copolymerizable with these (meth) acrylic acid may be only 1 type, or 2 or more types may be sufficient as it.

As alkali-soluble resin, the monomer component which makes the compound represented by the following general formula (ED) and / or the compound represented by the following general formula (ED2) (henceforth these compounds may be called "ether dimer") is superposed | polymerized. It is also preferable to include the polymer (a) which consists of.

[Formula 87]

In General Formula (ED), R <^1> and R <^2> respectively independently represents the C1-C25 hydrocarbon group which may have a hydrogen atom or a substituent.

General formula (ED2)

[Formula 88]

In general formula (ED2), R represents a hydrogen atom or a C1-C30 organic group. As a specific example of general formula (ED2), description of Unexamined-Japanese-Patent No. 2010-168539 can be referred.

Thereby, the coloring composition of this invention can form the cured film which was extremely excellent also in transparency with heat resistance. Although there is no restriction | limiting in particular as a C1-C25 hydrocarbon group which may have a substituent represented by R <^1> and R <^2> in general formula (ED) which shows an ether dimer, For example, methyl, ethyl, n-propyl, iso Linear or branched alkyl groups such as propyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl and 2-ethylhexyl; Aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecaneyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; Alkyl group substituted by alkoxy, such as 1-methoxyethyl and 1-ethoxyethyl; Alkyl groups substituted with aryl groups such as benzyl; Etc. can be mentioned. Among these, substituents of primary or secondary carbon, which are difficult to be detached by acid or heat, such as methyl, ethyl, cyclohexyl, benzyl, etc., are preferable in terms of heat resistance.

As a specific example of an ether dimer, for example, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate and diethyl-2,2'-[oxybis (methylene)] bis-2 -Propenoate, di (n-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] Bis-2-propenoate, di (n-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis ( Methylene)] bis-2-propenoate, di (tert-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (tert-amyl) -2,2'- [Oxybis (methylene)] bis-2-propenoate, di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 '-[Oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1-meth Methoxyethyl) -2,2 '-[oxybis (meth) Styrene)] bis-2-propenoate, di (1-ethoxyethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2'-[oxy Bis (methylene)] bis-2-propenoate, diphenyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'-[oxybis (methylene) )] Bis-2-propenoate, di (tert-butylcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2 , 2 '-[oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di Sobonyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, diamantyl-2,2'-[oxybis (methylene)] bis-2-propenoate, di ( 2-methyl-2-adamantyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, etc. are mentioned. Among these, in particular, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, Dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate are preferable. 1 type may be sufficient as these ether dimers, and 2 or more types may be sufficient as them. The structure derived from the compound represented by general formula (ED) may copolymerize another monomer.

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

[Formula 89]

(In formula (X), R <_1> represents a hydrogen atom or a methyl group, R <_2> represents a C2-C10 alkylene group, and R <_3> has a C1-C20 which may contain a hydrogen atom or a benzene ring. N represents an integer of 1 to 15.

In said Formula (X), it is preferable that carbon number of the alkylene group of R <_2> is 2-3. Moreover, although carbon number of the alkyl group of R <_3> is 1-20, More preferably, it is 1-10, and the alkyl group of R <_3> may also contain a benzene ring. As an alkyl group containing the benzene ring represented by R <_3> , a benzyl group, 2-phenyl (iso) propyl group, etc. are mentioned.

Moreover, in order to improve the crosslinking efficiency of the coloring composition in this invention, you may use alkali-soluble resin which has a polymeric group. When such alkali-soluble resin is used, there exists a tendency for the effect of this invention to improve more. Moreover, light resistance and heat resistance also tend to be more improved. As alkali-soluble resin which has a polymeric group, alkali-soluble resin etc. which contained an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in a side chain are useful. As an example of alkali-soluble resin containing the polymerizable group mentioned above, Diamond NR series (made by Mitsubishi Rayon Corporation), Photomer6173 (COOH containing polyurethane acrylic oligomer.Diamond Shamrock Co., Ltd. product), biscot R-264, KS resist 106 (all made by Osaka Yuki Kagaku Kogyo Co., Ltd.), cyclomer P series, Plascel CF200 series (all made by Daicel Kagaku Kogyo Co., Ltd.), Ebecryl3800 (made by Daicel Yusubishi Co., Ltd.) Can be mentioned. As alkali-soluble resin containing these polymerizable groups, an isocyanate group and an OH group are made to react previously, leaving one unreacted isocyanate group, and also including the compound and carboxyl group containing a (meth) acryloyl group. Urethane modified polymerizable double bond-containing acrylic resin obtained by reaction of acrylic resin, acrylic resin containing carboxyl group and unsaturated group-containing acrylic resin obtained by reaction of compound having epoxy group and polymerizable double bond together in molecule, Acid pendant type 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 Resin reacted with a compound having a compound of JP 2002-229 A Resin obtained by basic-processing resin which has an ester group which has a leaving group, such as a halogen atom or a sulfonate group, in a side chain or (beta) position described in 207 and Unexamined-Japanese-Patent No. 2003-335814 in a side chain is preferable. Moreover, acrycure RD-F8 (made by Nippon Shokubai Co., Ltd.) is also preferable.

As alkali-soluble resin, the multicomponent copolymer which consists of a benzyl (meth) acrylic-acid / (meth) acrylic acid copolymer and a benzyl (meth) acrylic acid / (meth) acrylic acid / other monomer is especially suitable. In addition, (meth) acrylic-acid benzyl / (meth) acrylic acid / (meth) acrylic-acid 2-hydroxyethyl copolymer which copolymerized 2-hydroxyethyl methacrylate, 2, described in Unexamined-Japanese-Patent No. 7-140654. -Hydroxypropyl (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 / methacryl Acid copolymer etc. are mentioned, Especially preferably, the copolymer of benzyl methacrylic acid / methacrylic acid etc. are mentioned.

As alkali-soluble resin, description after Unexamined-Japanese-Patent No. 2012-208494 Paragraph 0558-0571 (corresponding US patent application publication 2012/0235099 [0685]-[0700]) can be referred, and these content is referred to As used herein.

Furthermore, Paragraph No. 0029 of Unexamined-Japanese-Patent No. 2012-32767-the copolymer (B) of 0063, and alkali-soluble resin used by the Example, Paragraph No. 0088 of Unexamined-Japanese-Patent No. 2012-208474 Binder resin and binder resin used in Examples, Paragraph No. 0022 of Unexamined-Japanese-Patent No. 2012-137531-Binder resin used in Example, and Binder resin used in Example, Paragraph number 0132 of Unexamined-Japanese-Patent No. 2013-024934 Binder resin described in -0143 and Binder resin used in Examples, Paragraph No. 0092 of Unexamined-Japanese-Patent No. 2011-242752, and Binder resin used in Example, Paragraph No. 0030 of Unexamined-Japanese-Patent No. 2012-032770 It is preferable to use the binder resin described in -0072. These contents are incorporated herein by reference. More specifically, the following resins are preferable.

[Formula 90]

As acid value of alkali-soluble resin, Preferably it is 30 mgKOH / g-200 mgKOH / g, More preferably, it is 50 mgKOH / g-150 mgKOH / g, It is especially preferable that it is 70 mgKOH / g-120 mgKOH / g.

Moreover, as a weight average molecular weight (Mw) of alkali-soluble resin, 2,000-50,000 are preferable, 5,000-30,000 are more preferable, 7,000-20,000 are especially preferable.

When containing alkali-soluble resin in a coloring composition, as content of alkali-soluble resin, 1 mass%-15 mass% are preferable with respect to the total solid of a coloring composition, More preferably, they are 2 mass%-12 mass%. Especially preferably, they are 3 mass%-10 mass%.

The coloring composition of this invention may contain only one type of alkali-soluble resin, and may include two or more types. When it contains two or more types, it is preferable that the total amount becomes said range.

<Other components of the coloring composition>

The coloring composition of this invention may contain the other component in addition to the said dye multimer. For example, in order to adjust a color value, the coloring composition used by this invention may contain the pigment and pigment dispersant in addition to the said dye multimer and a curable compound. Moreover, when using a polymeric compound as a curable compound, you may contain the photoinitiator further.

For example, when forming a colored layer with a photoresist, the coloring composition of this invention has preferable composition containing the dye multimer in this invention, alkali-soluble resin as a curable compound, and a photoinitiator. Moreover, you may contain components, such as a pigment, a pigment dispersing agent, surfactant, and a solvent.

Moreover, when forming a colored layer by dry etching, the composition containing the dye multimer in this invention, the polymeric compound as a curable compound, and a photoinitiator is preferable. Moreover, you may contain components, such as a pigment, a pigment dispersion, surfactant, and a solvent.

Hereinafter, these details are demonstrated.

<< pigment >>

It is preferable that the coloring composition of this invention contains a pigment further.

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 organic pigments. As the pigment, one having a high transmittance is preferable.

Examples of the inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, And complex oxides of metals.

As an 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;

Etc. can be mentioned.

The following can be mentioned as a pigment which can be used preferably in this invention. However, this invention is not limited to these.

C. I. 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 individually or in various combinations in order to adjust spectral or to improve color purity. The specific example of the said combination is shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindolin yellow pigment and a quinophthalone Mixing with a system yellow pigment or a perylene system red pigment can be used. For example, CI pigment red 177 is mentioned as an anthraquinone pigment, CI pigment red 155 and CI pigment red 224 are mentioned as a perylene pigment, As a diketopyrrolopyrrole pigment, CI pigment red 254 is mentioned, and mixing with CI pigment yellow 139 is preferable at the point of color resolving power. Moreover, as for mass ratio of a red pigment and a yellow pigment, 100: 5-100: 50 are preferable. If it is 100: 4 or less, it is difficult to suppress the light transmittance of 400 nm to 500 nm, and if it is 100: 51 or more, dominant wavelength will approach short wavelength, and color resolution may not be able to be improved. Especially as said mass ratio, the range of 100: 10-100: 30 is optimal. In addition, in the case of the combination of red pigments, it can adjust to the spectroscopy calculated | required.

As the green pigment, a halogenated phthalocyanine pigment alone or a mixture of this and a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindolin 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. As for the mass ratio of a green pigment and a yellow pigment, 100: 5-100: 150 are preferable. As said mass ratio, the range of 100: 30-100: 120 is especially preferable.

As a blue pigment, a phthalocyanine type pigment can be used individually or the mixture of this and a dioxazine type purple pigment can be used. For example, a mixture of C. I. Pigment Blue 15: 6 and C. I. Pigment Violet 23 is preferred. As for mass ratio of a blue pigment and a purple pigment, 100: 0-100: 100 are preferable, More preferably, it is 100: 10 or less.

As the pigment for the black matrix, carbon, titanium black, iron oxide, titanium oxide alone or a mixture is used, and a combination of carbon and titanium black is preferable. Moreover, the mass ratio of carbon and titanium black has the preferable range of 100: 0-100: 60.

It is preferable to mix | blend pigments other than black, and, as for the coloring composition of this invention, it is more preferable to mix | blend a blue pigment.

When using as a color filter, the primary particle size of a pigment is preferably 100 nm or less from a viewpoint of color unevenness and contrast, and it is preferable that it is 5 nm or more from a viewpoint of dispersion stability. As primary particle size of a pigment, More preferably, it is 5-75 nm, More preferably, it is 5-55 nm, Especially preferably, it is 5-35 nm.

The primary particle size of a pigment can be measured by well-known methods, such as an electron microscope.

Especially, it is preferable that it is a pigment chosen from an anthraquinone pigment, a diketopyrrolopyrrole pigment, a phthalocyanine pigment, a quinophthalone pigment, an isoindolin pigment, an azomethine pigment, and a dioxazine pigment. . In particular, CI pigment red 177 (anthraquinone pigment), CI pigment red 254 (diketopyrrolopyrrole pigment), CI pigment green 7, 36, 58, CI pigment blue 15: 6 (phthalocyanine pigment) ), CI Pigment Yellow 138 (Quinophthalone Pigment), CI Pigment Yellow 139, 185 (Isoindolin Pigment), CI Pigment Yellow 150 (Azomethine Pigment), CI Pigment Violet 23 (Dioxazine Pigment) This is particularly preferred.

When mix | blending a pigment with the coloring composition of this invention, 20-50 mass% is preferable with respect to the all components except the solvent contained in a coloring composition, More preferably, it is 25-50 mass%, More preferably, it is 30-45 mass%.

The coloring composition of this invention may include only one type and may contain two or more types of pigments. When it contains two or more types, it is preferable that the total amount becomes said range.

<< pigment dispersant >>

When the coloring composition of this invention has a pigment, a pigment dispersant can be used together according to the objective.

Examples of the pigment dispersant usable in the present invention include polymer dispersants [for example, polyamideamine and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) ) Acrylates, (meth) acrylic copolymers, naphthalenesulfonic acid formalin condensates], and surfactants such as polyoxyethylene alkyl phosphate esters, polyoxyethylene alkylamines, alkanolamines, and pigment derivatives. .

Polymeric dispersants can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers from the structure.

As a terminal modified type polymer which has an anchor site with respect to a pigment surface, For example, the polymer which has a phosphoric acid group at the terminal described in Unexamined-Japanese-Patent No. 3-112992, 2003-533455, etc., Unexamined-Japanese-Patent No. 2002- The polymer which has a sulfonic acid group at the terminal described in 273191 etc., the polymer which has the partial skeleton and heterocycle of the organic pigment of Unexamined-Japanese-Patent No. 9-77994, etc. are mentioned. Moreover, the polymer which introduce | transduced the anchor site (acidic group, basic group, partial skeleton of organic pigment, heterocyclic ring, etc.) with respect to the surface of two or more pigments in the polymer terminal of Unexamined-Japanese-Patent No. 2007-277514 also has excellent dispersion stability, desirable.

As a graft type polymer which has an anchor site with respect to a pigment surface, polyester-type dispersing agent etc. are mentioned, for example, Unexamined-Japanese-Patent No. 54-37082, Unexamined-Japanese-Patent No. 8-507960, Reaction product of poly (lower alkyleneimine) and polyester described in JP-A-2009-258668, etc., reaction product of polyallylamine and polyester described in JP-A-9-169821, etc. 10-339949, Japanese Unexamined Patent Publication No. 2004-37986, International Publication No. WO2010 / 110491 and the like, a copolymer of a macromonomer and a nitrogen atom monomer, Japanese Unexamined Patent Publication No. 2003-238837, Japanese Unexamined Patent Publication No. 2008-9426 , Graft-type polymers having partial skeletons and heterocycles of organic pigments described in JP 2008-81732 A, and the macromonomers described in JP 2010-106268 A, etc .; The copolymer of an acidic radical containing monomer, etc. are mentioned. The amphoteric dispersion resin which has a basic group and an acidic group as described in Unexamined-Japanese-Patent No. 2009-203462 is especially preferable from a viewpoint of the dispersibility of a pigment dispersion, dispersion stability, and the developability which the coloring composition using a pigment dispersion shows.

As a macromonomer used when producing a graft-type polymer having an anchor site to the pigment surface by radical polymerization, a known macromonomer can be used, and macromonomer AA-6 manufactured by Toagosei Co., Ltd. Dimethyl methyl methacrylate), AS-6 (polystyrene having terminal methacryloyl group), AN-6S (copolymer of styrene and acrylonitrile whose terminal group is methacryloyl group), AB-6 ( Polyacrylic acid butyl whose terminal group is a methacryloyl group), Flaccel FM5 ((epsilon 5 mol equivalent of epsilon -caprolactone of 2-hydroxyethyl methacrylate) product made by Daicel Chemical Co., Ltd.), FA10L (acrylic acid 2) 10 mol equivalents of (epsilon) -caprolactone adduct of hydroxyethyl), the polyester-type macromonomer of Unexamined-Japanese-Patent No. 2-272009, etc. are mentioned. Among these, polyester macromonomers excellent in flexibility and affinity for solvents are particularly preferred in view of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the coloring composition using the pigment dispersion. Especially preferred are polyester-based macromonomers represented by the polyester-based macromonomers described in 2-272009.

As a block polymer which has an anchor site with respect to a pigment surface, the block polymer as described in Unexamined-Japanese-Patent No. 2003-49110, 2009-52010, etc. is preferable.

The pigment dispersant which can be used for this invention can also be obtained as a commercial item, As such a specific example, "DA-7301" by the Kusumoto Kasei Co., Ltd., "Disperbyk-101 (polyamide amine phosphate) by BYK Chemie), 107 (carboxylic acid Ester), 110, 111 (copolymer including acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) "," BYK-P104, P105 (high molecular weight) Unsaturated polycarboxylic acid) "," EFKA4047, 4050-4010-4165 (polyurethane type), EFKA4330-443 (block copolymer), 4400-4440 (modified polyacrylate), 5010 (polyester amide), 5765 by EFKA (High molecular weight polycarboxylic acid salt), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) "," Azisper PB821, PB822, PB880, PB881 "made by Ajinomoto Fine Techno Co., Ltd., Kyoe "Florene TG-710 (urethane oligomer)" made by Isha Chemical Co., Ltd., "Polyflo No. 50E, No. 300 (arc) System copolymer) "," Disparon KS-860, 873SN, 874, # 2150 (aliphatic polyhydric carboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, manufactured by Kusumoto Kasei Co., Ltd. DA-725 "," Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "by Gao Corporation," Homogenol L-18 (polymeric polycarboxylic acid) ) "," Emulgen 920, 930, 935, 985 (polyoxyethylene nonyl phenyl ether) "," acetamine 86 (stearylamine acetate) "," Solsper's 5000 (prepared by Nippon Lubrizol Co., Ltd.) Talocyanine Derivatives), 22000 (Azo Pigment Derivatives), 13240 (Polyesteramine), 3000, 17000, 27000 (Polymers with Functional Part at End), 24000, 28000, 32000, 38500 (Graft Polymer) ", Nikko Chemical Shin-Etsu Chemical Co., Ltd., such as "Nichol T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)", Kawaken Fine Chemical Co., Ltd. "Hino Act T-8000E" High School Co., Ltd. " Organosiloxane polymer KP341 ", Yusho Corporation" W001: cationic surfactant ", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl Nonionic surfactants such as phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters, and anions such as "W004, W005, W017" System surfactant, Morishita Sangyo Co., Ltd. "EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450", Sanofko Corporation "dispers Polymer dispersing agents such as ADE 6, Disperse Ade 8, Disperse Ade 15, and Disperse Ade 9100 "," ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72 "by ADEKA P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 ", and" Ionet (brand name) S-20 made by Sanyo Kasei Co., Ltd. And the like.

In addition, a block copolymer or a narrow molecular weight distribution air obtained by radical polymerization of a polymerizable unsaturated compound in the presence of a reversible addition-fragmentation chain transfer (RAFT agent) such as a dithiocarbonyl compound and a radical initiator. Coalescing may be used together as a pigment dispersant. As a specific example of such a resin, Paragraph No. 0053 of Unexamined-Japanese-Patent No. 2008-242081, Paragraph No. 0049 of 0129-176218, etc. are mentioned resin, etc., These content is integrated in this specification. do. Moreover, you may use such a block copolymer and the copolymer with narrow molecular weight distribution as alkali-soluble resin.

These pigment dispersants may be used independently and may be used in combination of 2 or more type. In this invention, it is especially preferable to use combining a pigment derivative and a polymer dispersing agent. Moreover, you may use a pigment dispersant together with alkali-soluble resin together with the terminal modified | denatured polymer | macromolecule which has an anchor site with respect to the pigment surface, a graft-type polymer, and a block type polymer. Examples of alkali-soluble resins include (meth) acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having carboxylic acid in the side chain. In particular, a (meth) acrylic acid copolymer is preferable. Moreover, the N-position substituted maleimide monomer copolymer of Unexamined-Japanese-Patent No. 10-300922, the ether dimer copolymer of Unexamined-Japanese-Patent No. 2004-300204, and the polymeric group of Unexamined-Japanese-Patent No. 7-319161. Alkali-soluble resins containing are also preferable.

In a coloring composition, when it contains a pigment dispersant, it is preferable that it is 1 mass part-80 mass parts with respect to 100 mass parts of pigments, as for total content of a pigment dispersant, 5 mass parts-70 mass parts are more preferable, 10 mass parts It is more preferable that it is part-60 mass parts. The coloring composition of this invention may include only one type, and may contain two or more types of pigment dispersants. When it contains two or more types, it is preferable that the total amount becomes said range.

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

Moreover, when using a pigment derivative together, as a usage-amount of a pigment derivative, it is preferable to exist in the range of 1 mass part-30 mass parts with respect to 100 mass parts of pigments, and to exist in the range of 3 mass parts-20 mass parts. More preferably, it is especially preferable to exist in the range of 5 mass parts-15 mass parts.

In a coloring composition, it is preferable that the sum total of content of a pigment | dye and a dispersing agent component is 50 mass% or more and 90 mass% or less with respect to the total solid which comprises a coloring composition from a viewpoint of a cure sensitivity and a color concentration, 55 mass% or more 85 It is more preferable that it is mass% or less, and it is more preferable that it is 60 mass% or more and 80 mass% or less.

<< dye >>

The coloring composition of this invention may contain well-known dye other than a dye multimer. For example, JP-A-64-90403, JP-A-64-91102, JP-A-94301, JP-A-6-11614, JP-A 2592207, and US Patent Publication No. 4808501, United States Patent Publication No. 5667920, United States Patent Publication No. 505950, Japanese Patent Application Laid-Open No. Hei 5-333207, Japanese Patent Application Laid-Open No. Hei 6-35183, Japanese Patent Application Laid-open No. Hei 6-51115, Japan Patent Publication The pigment | dye disclosed by Unexamined-Japanese-Patent No. 6-194828 etc. can be used. Examples of the chemical structure include pyrazole azo, pyrimethene, anilinoazo, triphenylmethane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridoneazo, cyanine and phenothiazine. Dyes such as pyropyrazole azomethine and the like can be used.

One type of dye may be contained and may be included two or more types.

When dye is contained in the coloring composition of this invention, it can be 0.1-5 mass% of all the coloring agents, for example.

<< photoinitiator >>

It is preferable that the coloring composition of this invention contains a photoinitiator from a viewpoint of the further sensitivity improvement.

There is no restriction | limiting in particular as a photoinitiator as long as it has the ability to start superposition | polymerization of a polymeric compound, It can select suitably from well-known photoinitiators. For example, it is preferable to have photosensitivity to visible light from an ultraviolet range. Moreover, the active agent which produces | generates some action with a photoexcited sensitizer and produces | generates an active radical may be sufficient, and the initiator which starts cationic polymerization according to the kind of monomer may be sufficient.

Moreover, it is preferable that a photoinitiator contains the compound which has at least about 50 molecular extinction coefficient in the range of about 300 nm-800 nm (330 nm-500 nm are more preferable) at least 1 sort (s).

As a photoinitiator, For example, acyl phosphine compounds, such as a halogenated hydrocarbon derivative (for example, a triazine skeleton, an oxadiazole skeleton), an acyl phosphine oxide, hexaaryl biimi Oxime compounds, such as a dazole and an oxime derivative, an organic peroxide, a thio compound, a ketone compound, an aromatic onium salt, a ketoxime ether, an amino acetophenone compound, a hydroxyacetophenone, etc. are mentioned, An oxime compound is preferable.

Moreover, from a viewpoint of exposure sensitivity, a trihalomethyl triazine compound, a benzyl dimethyl ketal compound, the (alpha)-hydroxy ketone compound, the (alpha)-amino ketone compound, an acyl phosphine compound, a phosphine oxide compound, a metallocene compound, Oxime compound, triallylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, halomethyloxadiazole compound, 3 Preferred are compounds selected from the group consisting of -aryl substituted coumarin compounds.

More preferably, trihalomethyltriazine compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triallylimidazole dimer, triarylimidazole compound, benzimidazole compound , Onium compound, benzophenone compound, acetophenone compound, trihalomethyltriazine compound, α-aminoketone compound, oxime compound, triallylimidazole compound, benzophenone compound, triarylimidazole compound, benzoimimi Particularly preferred is at least one compound selected from the group consisting of doazole compounds. Moreover, the mixture with a benzoimidazole may be sufficient as a triaryl imidazole compound.

Specifically as a trihalomethyl triazine compound, the following compounds are illustrated. In addition, Ph is a phenyl group.

[Formula 91]

Examples of the triarylimidazole compound and the benzimidazole compound include the following compounds.

[Formula 92]

As a trihalomethyl triazine compound, a commercial item can also be used, for example, TAZ-107 (made by Midori Chemical Co., Ltd.) can also be used.

In particular, when using the coloring composition of this invention for manufacture of the color filter with which a solid-state image sensor is equipped, since it is necessary to form a fine pattern in a sharp shape, it is important that it develops without residue in a unexposed part with sclerosis | hardenability. Do. From such a viewpoint, it is especially preferable to use an oxime compound as a polymerization initiator. In particular, in the case of forming a fine pattern in a solid-state imaging device, stepper exposure is used for exposure for curing, but since this exposure machine may be damaged by halogen, the amount of addition of the polymerization initiator needs to be kept low. In view of such a point, it is particularly preferable to use an oxime compound as the (D) photopolymerization initiator in order to form a fine pattern such as a solid-state imaging device.

As a halogenated hydrocarbon compound which has a triazine frame | skeleton, Wakabayashi et al., Bull. Chem. Soc. J according to the compound described in Japan, 42, 2924 (1969), the compound described in British Patent Publication No. 1388492, the compound described in Japanese Patent Application Laid-open No. 53-133428, the compound described in German Patent Publication No. 3337024, FC Schaefer and the like. Org. Chem .; 29, 1527 (1964), the compound of JP-A-62-58241, the compound of JP-A-5-281728, the compound of JP-A-5-34920, United States The compound described in Unexamined-Japanese-Patent No. 4212976, especially the compound of Paragraph No. 0075 of Unexamined-Japanese-Patent No. 2013-077009, etc. are mentioned.

Moreover, an acridine derivative is illustrated as a photoinitiator of that excepting the above. Specifically, the compound of Paragraph No. 0076 of Unexamined-Japanese-Patent No. 2013-077009, etc. are mentioned, These content is integrated in this specification.

As a ketone compound, the compound of Paragraph No. 0077 of Unexamined-Japanese-Patent No. 2013-077009, etc. are mentioned, for example, These content is integrated in this specification.

As a photoinitiator, a hydroxy acetophenone compound, an amino acetophenone compound, and an acyl phosphine compound can also be used suitably. More specifically, the amino acetophenone series initiator of Unexamined-Japanese-Patent No. 10-291969, and the acyl phosphine oxide type initiator of Unexamined-Japanese-Patent No. 4225898 can also be used, for example.

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF Corporation) can be used. As the aminoacetophenone-based initiator, commercially available IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Corporation) can be used. As an aminoacetophenone type initiator, the compound of Unexamined-Japanese-Patent No. 2009-191179 by which absorption wavelength was matched to long-wavelength light sources, such as 365 nm or 405 nm, can also be used. Moreover, as an acyl phosphine type initiator, IRGACURE-819 which is a commercial item, DAROCUR-TPO (brand name: are all made by BASF Corporation), TAZ series (for example, TAZ-107, TAZ-110, TAZ-104) made by Midori Kagaku Co., Ltd. , TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123).

As a photoinitiator, More preferably, an oxime compound is mentioned. As a specific example of an oxime compound, the compound of Unexamined-Japanese-Patent No. 2001-233842, the compound of Unexamined-Japanese-Patent No. 2000-80068, and the compound of Unexamined-Japanese-Patent No. 2006-342166 can be used.

As an oxime compound, such as an oxime derivative suitably used as a photoinitiator in this invention, 3-benzoyloxy iminobutan-2-one, 3-acetoxy iminobutan-2-one, 3-propionyloxy is mentioned, for example. Minobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, etc. are mentioned.

As the oxime compound, J. C. S. Perkin II (1979) pp. 1653-1660, J. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, the compound of Unexamined-Japanese-Patent No. 2000-66385, the compound of Unexamined-Japanese-Patent No. 2000-80068, Unexamined-Japanese-Patent No. 2004-534797, Unexamined-Japanese-Patent No. 2006-342166, etc. are mentioned. Can be.

As a commercial item, IRGACURE-OXE01 (made by BASF Corporation), IRGACURE-OXE02 (made by BASF Corporation), TR-PBG-304 (made by Changzhou Tronly New Electronic Materials Co., Ltd.) suitably is also suitable. Is used.

Moreover, as an oxime compound other than the said description, the compound of Unexamined-Japanese-Patent No. 2009-519904 with an oxime connected to carbazole N, and the compound and pigment | dye structure of US Patent No.7626957 in which the hetero substituent was introduce | transduced into the benzophenone site | part Compounds described in Japanese Unexamined Patent Publication No. 2010-15025 and US Patent Publication No. 2009-292039, ketoxime compounds described in International Publication No. 2009-131189, triazine skeleton and oxime skeleton having a nitro group introduced into the same molecule The compound described in US Patent Publication No. 7556910, the compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and having a good sensitivity to a g-ray light source may be used.

Preferably, it can also use suitably also about the cyclic oxime compound of Unexamined-Japanese-Patent No. 2007-231000 and 2007-322744. Among the cyclic oxime compounds, in particular, the cyclic oxime compounds cyclized to the carbazole dyes described in JP 2010-32985 and JP 2010-185072 are preferable in view of high sensitivity.

Moreover, the compound of Unexamined-Japanese-Patent No. 2009-242469 which has an unsaturated bond in the specific site of an oxime compound can also achieve high sensitivity by regenerating an active radical from a polymerization inert radical, and can be used suitably.

Especially preferably, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-269779, and the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061 are mentioned.

Specifically, as an oxime compound which is a photoinitiator, the compound represented by the following general formula (OX-1) is preferable. Moreover, the oxime compound of (E) body may be sufficient as the N-O bond of oxime, the oxime compound of (Z) body may be sufficient, and the mixture of (E) body and (Z) body may be sufficient as it.

[Formula 93]

In 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.

It is preferable that it is a monovalent nonmetallic atom group as monovalent substituent represented by R in general formula (OX-1).

Examples of the monovalent nonmetallic atom group include alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heterocyclic groups, alkylthiocarbonyl groups, and arylthiocarbonyl groups. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be substituted by the other substituent further.

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, an aryl group, and the like.

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

[Formula 94]

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

In terms of sensitivity, the oxime compound has a molar extinction coefficient at 365 nm or 405 nm, preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000.

Although the well-known method can be used for the molar extinction coefficient of a compound, Specifically, it is the ultraviolet visible spectrophotometer (Cary-5 spectrophotometer by Varian company), for example, in the density | concentration of 0.01 g / L using ethyl acetate solvent. It is preferable to measure.

When a photoinitiator is contained in the coloring composition of this invention, it is preferable that content of a photoinitiator is 0.1 mass% or more and 50 mass% or less with respect to the total solid of a coloring composition, More preferably, it is 0.5 mass% or more and 30 mass% or less More preferably, they are 1 mass% or more and 20 mass% or less. In this range, better sensitivity and pattern formability are obtained.

The coloring composition of this invention may include only one type, and may contain two or more types of photoinitiators. When it contains two or more types, it is preferable that the total amount becomes said range.

<Other ingredients>

The coloring composition of this invention contains other components, such as an organic solvent, a crosslinking agent, a polymerization inhibitor, surfactant, organic carboxylic acid, and an organic carboxylic anhydride, in addition to each component mentioned above in the range which does not impair the effect of this invention. You may do it.

<< organic solvent >>

The coloring composition of this invention may contain the organic solvent.

The organic solvent is not particularly limited as long as it satisfies the solubility of each component and the applicability of the coloring composition. However, the organic solvent is preferably selected in consideration of solubility, coatability, and safety of an ultraviolet absorber, an alkali-soluble resin, a dispersant, and the like. . Moreover, when preparing the coloring composition in this invention, it is preferable to contain at least 2 type of organic solvent.

As the organic solvent, for example, ethyl acetate, acetic acid-n-butyl acetate, isobutyl acetate, cyclohexyl acetate, formic acid amyl, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyrate , Methyl lactate, ethyl lactate, alkyl oxyacetate (e.g. methyl oxyacetic acid, ethyl oxyacetate, oxyacetic acid (e.g. methyl methoxyacetate, methoxyacetic acid ethyl, methoxyacetic acid butyl, ethoxyacetic acid, Ethyl oxyacetate, etc.), 3-oxypropionic acid alkyl esters (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate, and the like (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-) Methyl ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-oxypropionic acid alkyl esters (e.g. methyl 2-oxypropionate, 2-oxypropionate) Ethyl onion, 2-oxypropionic acid propyl, and the like (e.g., methyl 2-methoxypropionate, 2-methoxy ethylpropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate) Methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), pyruvic acid As methyl, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like, for example, diethylene glycol dimethylether, tetra Hydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glass As propylene monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and ketones, For example, toluene, xylene, etc. are mentioned suitably as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc., and aromatic hydrocarbons.

It is also preferable that these organic solvents mix 2 or more types from a viewpoint of the solubility of an ultraviolet absorber and alkali-soluble resin, improvement of a coated surface shape, etc. In this case, Especially preferably, said 3-ethoxy propionate methyl, 3-ethoxy propionate ethyl, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxy Mixed solution composed of two or more 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.

It is preferable to make content in the coloring composition of the organic solvent into the quantity which becomes 5 mass%-80 mass% of total solid content concentration of a composition from a coating property, 5 mass%-60 mass% are more preferable, 10 mass%-50 mass% are especially preferable.

The coloring composition of this invention may contain only one type, and may contain two or more types of organic solvents. When it contains two or more types, it is preferable that the total amount becomes said range.

<< cross-linking system >>

The coloring composition of this invention may contain a crosslinking agent. By containing a crosslinking agent, the hardness of the cured film formed by hardening | curing a coloring composition can be raised more.

The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. Examples of the crosslinking agent include at least one substituent selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Phenol compound, Naphthol compound or Hyde substituted with at least one substituent selected from a melamine compound, guanamine compound, glycoluril compound or urea compound, (c) methylol group, alkoxymethyl group, and acyloxymethyl group A loxanthracene compound is mentioned. Especially, polyfunctional epoxy resin is preferable.

For details, such as the specific example of a crosslinking agent, Paragraph 0134 of Unexamined-Japanese-Patent No. 2004-295116-description of 0147 can be referred.

When the coloring composition of this invention contains a crosslinking agent, content of a crosslinking agent is not specifically determined, 2-30 mass% of the total solid of a coloring composition is preferable, and its 3-20 mass% is more preferable.

The coloring composition of this invention may include only one type and may contain two or more types of crosslinking agents. When it contains two or more types, it is preferable that the total amount becomes said range.

<< polymerization inhibitor >>

In the coloring composition of this invention, in order to prevent unnecessary thermal polymerization of a polymeric compound, it is preferable to add a small amount of polymerization inhibitors during manufacture or storage of a coloring composition.

As a polymerization inhibitor which can be used for this invention, hydroquinone, p-methoxyphenol, di-tert- butyl- p-cresol, pyrogallol, tert- butylcatechol, benzoquinone, 4,4'- thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine 1st cerium salt, etc. are mentioned. have.

When it contains a polymerization inhibitor in the coloring composition of this invention, 0.01 mass%-5 mass% are preferable with respect to mass of the whole composition, content of a polymerization inhibitor.

The coloring composition of this invention may include only one type and may contain two or more types of polymerization inhibitors. When it contains two or more types, it is preferable that the total amount becomes said range.

<< surfactant >>

You may add various surfactant to the coloring composition of this invention from a viewpoint of further improving applicability | paintability. As surfactant, various surfactant, such as a fluorochemical surfactant, nonionic surfactant, cationic surfactant, anionic surfactant, silicone type surfactant, can be used.

In particular, the coloring composition of this invention contains the fluorine-type surfactant, and since the liquid characteristic (particularly fluidity) at the time of preparation as a coating liquid improves more, the uniformity of coating thickness and liquid-liquidity are applied. Can be further improved.

That is, when forming a film using the coating liquid to which the coloring composition containing a fluorine-type surfactant was applied, wettability with respect to a to-be-coated surface is improved by reducing the interfacial tension of a to-be-coated surface and a coating liquid, and apply | coating to a to-be-coated surface. Sex is improved. For this reason, even when a thin film of several micrometers is formed with a small amount of liquid, it is effective at the point which can form the film of uniform thickness with a small thickness variation more suitably.

3 mass%-40 mass% are suitable for the fluorine content rate in a fluorine-type surfactant, More preferably, they are 5 mass%-30 mass%, Especially preferably, they are 7 mass%-25 mass%. The fluorine-type surfactant whose fluorine content rate exists in this range is effective at the point of the uniformity of the thickness of a coating film, or liquid-liquid solution, and the solubility in a coloring composition is also favorable.

As a fluorine type surfactant, Megapak F171, copper F172, copper F173, copper F176, copper F177, copper F141, copper F142, copper F143, copper F144, copper R30, copper F437, copper F475, copper F479, copper F482 , Copper F554, copper F780, copper F781 (above, made by DIC Corporation), fluoride FC430, copper FC431, copper FC171 (or more, manufactured by Sumitomo 3M, Inc.), surflon S-382, copper SC-101, East SC-103, East SC-104, East SC-105, East SC1068, East SC-381, East SC-383, East S393, East KH-40 (above, manufactured by Asahi Glass Co., Ltd.) have.

Specific examples of the nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerin ethoxylate, etc.) and polyoxy. Ethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol Distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 made from BASF Corporation), Solsper 20000 (Nihon Lu Brisol Co., Ltd.) etc. are mentioned.

Specifically as a cationic surfactant, a phthalocyanine derivative (brand name: EFKA-745, the Morishita Sangyo Co., Ltd. product), organosiloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.), (meth) Acrylic acid (co) polymer polyflo no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Corporation), and the like.

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

As a silicone type surfactant, Toray Dow Corning Co., Ltd. "Toray Silicon DC3PA", "Toray Silicon SH7PA", "Toray Silicon DC11PA", "Toray Silicon SH28PA", "Toray Silicon SH28PA", "Toray Silicon SH29PA" "," Toray Silicon SH30PA "," Toray Silicon SH8400 "," TSF-4440 "," TSF-4300 "," TSF-4445 "," TSF-4460 "," TSF-4452 "made by Momentive Performance Materials "KP341", "KF6001", "KF6002", "BYK307", "BYK323", "BYK330" by the company made from Shin-Etsu Silicone Co., Ltd., etc. are mentioned.

When surfactant is contained in the coloring composition of this invention, 0.001 mass%-2.0 mass% are preferable with respect to the total mass of a coloring composition, More preferably, they are 0.005 mass%-1.0 mass%. .

The composition of this invention may contain only one type and may contain two or more types of surfactant. When it contains two or more types, it is preferable that the total amount becomes said range.

<< organic carboxylic acid, organic carboxylic anhydride >>

The coloring composition of this invention may contain the organic carboxylic acid and / or organic carboxylic anhydride of molecular weight 1000 or less.

As an organic carboxylic acid compound, aliphatic carboxylic acid or aromatic carboxylic acid is mentioned specifically ,. Examples of the aliphatic carboxylic acids 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 and glutaric acid. And dicarboxylic acids such as adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, and tricarboxylic acids such as tricavallylic acid and aconitic acid. have. Moreover, as aromatic carboxylic acid, the carboxylic acid which the carboxyl group couple | bonded with the phenyl group, such as benzoic acid and phthalic acid, directly, and the carboxylic acid which the carboxyl group couple | bonded through the carbon bond from the phenyl group are mentioned, for example. In these, especially the thing of molecular weight 600 or less, especially the molecular weight 50-500, specifically, maleic acid, malonic acid, succinic acid, itaconic acid are preferable.

Examples of the organic carboxylic anhydride include aliphatic carboxylic anhydride and aromatic carboxylic anhydride. Specific examples thereof include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, Maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic acid anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic acid Aliphatic carboxylic anhydride is mentioned. As aromatic carboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, naphthalic anhydride etc. are mentioned, for example. Among these, especially those having a molecular weight of 600 or less, particularly those having a molecular weight of 50 to 500, specifically, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferable.

When organic carboxylic acid and organic carboxylic anhydride are contained in the coloring composition of this invention, the addition amount of organic carboxylic acid and / or organic carboxylic anhydride is 0.01-10 weight% normally in total solid, Preferably it is 0.03-5 mass%, More preferably Preferably it is 0.05-3 mass%.

The coloring composition of this invention may contain only one type, and may contain two or more types of organic carboxylic acid and / or organic carboxylic anhydride, respectively. When it contains two or more types, it is preferable that the total amount becomes said range.

By adding these organic carboxylic acids and / or organic carboxylic anhydrides having a molecular weight of 1,000 or less, it is possible to further reduce the remaining of undissolved substances in the coloring composition while maintaining high pattern adhesion.

In addition to the above, in the coloring composition, various additives, for example, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents and the like can be blended, if necessary. As these additives, Paragraph 0155 of Unexamined-Japanese-Patent No. 2004-295116-the thing of 0156 are mentioned, These content is integrated in this specification.

In the coloring composition of this invention, the sensitizer and light stabilizer of Paragraph 0078 of Unexamined-Japanese-Patent No. 2004-295116, and the thermal polymerization inhibitor of Paragraph 0081 of this publication can be contained.

The coloring composition of this invention may include only one type, and may contain two or more types of said components, respectively. When it contains two or more types, it is preferable that the total amount becomes said range.

<Preparation method of a coloring composition>

The coloring composition of this invention is prepared by mixing the above-mentioned component.

In addition, at the time of preparation of a coloring composition, you may mix | blend each component which comprises a coloring composition, and you may mix | blend sequentially, after melt | dissolving and dispersing each component in a solvent. In addition, the addition order and working conditions at the time of compounding are not restrict | limited. For example, a composition may be prepared by dissolving and dispersing all the components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions and dispersions. You may prepare as.

The coloring composition prepared as mentioned above, Preferably, it can provide for use, after filtering-separating using the filter etc. about 0.01 micrometer-3.0 micrometers of pore diameters, More preferably, about 0.05 micrometers-0.5 micrometers of pore diameters. have.

The coloring composition of this invention is used suitably for the coloring layer formation of a color filter. More specifically, since the colored composition of this invention can form the cured film excellent in color nonuniformity and spectral characteristics, it is used suitably in order to form the coloring pattern (colored layer) of a color filter. Moreover, the coloring composition of this invention can be conveniently used for coloring pattern formation, such as color filters used for image pickup apparatuses, such as a solid-state image sensor (for example, CCD, CMOS, etc.), and a liquid crystal display device (LCD). Can be. Moreover, it can use suitably also for manufacturing uses, such as printing ink, an inkjet ink, and a coating material. Especially, the color filter for solid-state image sensors, such as CCD and CMOS, can be used suitably as a manufacturing use.

<Cured film, pattern formation method, color filter, and manufacturing method of color filter>

Next, the cured film, the pattern formation method, and the color filter in this invention are demonstrated in detail through the manufacturing method. Moreover, the manufacturing method of the color filter using the pattern formation method of this invention is also demonstrated.

The cured film of this invention hardens the coloring composition of this invention. Such a cured film is used suitably for a color filter.

The pattern formation method of this invention applies the coloring composition of this invention on a support body, forms a coloring composition layer, removes an unnecessary part, and forms a coloring pattern.

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

The coloring composition of this invention may form a pattern by what is called a photolithographic method, may manufacture a color filter, and may form a pattern by the dry etching method.

That is, as a 1st embodiment of the pattern formation method of this invention, the process of forming a coloring composition layer by applying a coloring composition on a support body, the process of exposing a coloring composition layer in a pattern shape, and developing and removing an unexposed part, The pattern formation method including the process of forming a coloring pattern is illustrated.

Moreover, as 2nd Embodiment of the pattern formation method of this invention, the process of forming a coloring composition layer by apply | coating a coloring composition on a support body, hardening | curing and forming a colored layer, and forming a photoresist layer on a colored layer And a pattern formation method including the process of patterning a photoresist layer by exposing and developing, and obtaining a resist pattern, and the process of dry-etching a colored layer using a resist pattern as an etching mask.

Such a pattern formation method is used for manufacture of the colored layer of a color filter. That is, this invention also discloses the manufacturing method of the color filter containing the pattern formation method of this invention.

These details will be described below.

Hereinafter, although each process in the pattern formation method of this invention is demonstrated in detail through the manufacturing method of the color filter for solid-state image sensors, this invention is not limited to this method. Hereinafter, the color filter for solid-state image sensors may only be called "color filter."

<< process >> which forms coloring composition layer >>

In the process of forming a coloring composition layer, the coloring composition layer of this invention is applied to a support body, and a coloring composition layer is formed.

As a support body which can be used for this process, for example, solid-state imaging in which an imaging element (light receiving element) such as a charge coupled device (CCD) or a complementary metal-oxide semiconductor (CMOS) is provided on a substrate (for example, a silicon substrate). Element substrates can be used.

The coloring pattern in this invention may be formed in the imaging element formation surface side (surface) of the board | substrate for solid-state image sensors, and may be formed in the imaging element non-formation surface side (rear surface).

A light shielding film may be provided between the coloring patterns in a solid-state image sensor, and the back surface of the board | substrate for solid-state image sensors.

Moreover, on the support body, you may provide an undercoat layer as needed, in order to improve adhesiveness with an upper layer, to prevent diffusion of a substance, or to planarize a substrate surface. A solvent, alkali-soluble resin, a polymeric compound, a polymerization inhibitor, surfactant, a photoinitiator, etc. can be mix | blended with an undercoat layer, These each component is suitably selected from the component mix | blended with the coloring composition of this invention mentioned above. It is preferable.

As a method of applying the coloring composition of the present invention onto a support, various coating methods such as slit coating, ink jet method, rotary coating, cast coating, roll coating, and screen printing can be applied.

Drying (prebaking) of the coloring composition layer apply | coated on the support body can be performed in 10 second-300 second at the temperature of 50 degreeC-140 degreeC with a hotplate, oven, etc.

<Step of Forming Pattern by Photolithography>

<< process to expose >>

In an exposure process, the coloring composition layer formed in the coloring composition layer forming process is pattern-exposed through the mask which has a predetermined | prescribed mask pattern using exposure apparatuses, such as a stepper, for example. Thereby, a cured film is obtained.

As radiation (light) which can be used at the time of exposure, especially ultraviolet rays, such as g line | wire and i line | wire, are preferably used (especially i line | wire). 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.

It is preferable that the film thickness of a cured film (colored film) is 1.0 micrometer or less, It is more preferable that it is 0.1 micrometer-0.9 micrometer, It is more preferable that it is 0.2 micrometer-0.8 micrometer.

Since the high resolution and high adhesiveness can be obtained by making a film thickness into 1.0 micrometer or less, it is preferable.

Moreover, in this process, the cured film which has a thin film thickness of 0.7 micrometer or less can also be formed suitably, and developing cured film in the pattern formation process mentioned later is developed, and it is a thin film, but developability and surface roughness suppression are carried out. And the coloring pattern excellent in the pattern shape can be obtained.

<< Development process >>

Subsequently, by performing an alkali image development process, the coloring composition layer of the non-irradiated part in an exposure process elutes in aqueous alkali solution, and only the photocured part remains.

As a developing solution, the organic alkali developing solution which does not cause damage to an underlying image pick-up element, a circuit, etc. is preferable. As image development temperature, it was 20 degreeC-30 degreeC normally, and developing time was 20 second-90 second conventionally. In order to remove a residue more, 120 second-180 second may be performed recently. Furthermore, in order to improve residue removal property, the process which shakes off a developing solution every 60 second and newly supplies a developing solution may be repeated several times.

As an alkaline agent used for a developing solution, for example, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide And organic alkaline compounds such as benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo- [5,4,0] -7-undecene. An alkaline aqueous solution diluted with pure water is preferably used as the developer so that the concentration is 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass.

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

In addition, when the developing solution which consists of such alkaline aqueous solution is used, it generally wash | cleans (rinses) with pure water after image development.

Subsequently, it is preferable to perform heat processing (post-baking) after drying. If it forms a multicolored coloring pattern, a cured film can be manufactured by repeating the above-mentioned process in order for every color. As a result, a color filter is obtained.

Post-baking is the heat processing after image development for making hardening perfect, and usually heat-processes 100 degreeC-240 degreeC, Preferably 200 degreeC-240 degreeC.

This post-baking process can be performed continuously or batchwise using the heating means, such as a hotplate, a convection oven (hot air circulation type dryer), and a high frequency heater, so that the coating film after image development may be said conditions.

When forming a pattern by dry etching, description of Unexamined-Japanese-Patent No. 2013-64993 can be referred, and these content is integrated in this specification.

In addition, the manufacturing method of this invention may have a well-known process as a manufacturing method of the color filter for solid-state image sensors as a process of that excepting the above as needed. For example, after performing the coloring composition layer forming process, exposure process, and pattern formation process which were mentioned above, you may include the hardening process which hardens the formed coloring pattern by heating and / or exposure as needed.

Moreover, when using the coloring composition which concerns on this invention, the clogging of the nozzle of a coating device discharge part, a piping part, contamination by adhesion, sedimentation, drying of a coloring composition and pigment in an applicator, etc. may arise, for example. Therefore, in order to wash | clean the contamination caused by the coloring composition of this invention efficiently, it is preferable to use the solvent concerning this composition described above as a washing | cleaning liquid. In addition, JP-A-7-128867, JP-A-7-146562, JP-A-8-278637, JP-A 2000-273370, JP-A-2006-85140, The cleaning liquids described in JP 2006-291191, JP 2007-2101, JP 2007-2102, JP 2007-281523, and the like are also suitable as a rinse removal liquid of the coloring composition according to the present invention. Available.

Among the above, alkylene glycol monoalkyl ether carboxylates and alkylene glycol monoalkyl ethers are preferable.

These solvents may be used alone or in combination of two or more thereof. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group and the solvent not having a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 80/20. As a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), it is especially preferable that the ratio is 60/40. Moreover, in order to improve the permeability of the washing | cleaning liquid to a contaminant, you may add surfactant to the washing | cleaning liquid which concerns on this composition described above.

Since the color filter of this invention uses the coloring composition of this invention, while being excellent in exposure margin, the formed coloring pattern (colored pixel) is excellent in pattern shape, and the pattern surface becomes rough Since the residue in the developing part is suppressed, the color characteristic is excellent.

The color filter of this invention can be used suitably for solid-state image sensors, such as CCD and CMOS, and is especially suitable for high resolution CCD, CMOS, etc. over 1 million pixels. The color filter for solid-state image sensors of this invention can be used as a color filter arrange | positioned, for example between the light-receiving part of each pixel which comprises CCD or CMOS, and a micro lens for condensing.

Moreover, as a film thickness of the coloring pattern (color pixel) in the color filter of this invention, 2.0 micrometers or less are preferable, 1.0 micrometer or less is more preferable, 0.7 micrometer or less is more preferable.

Moreover, as a size (pattern width) of a coloring pattern (color pixel), 2.5 micrometers or less are preferable, 2.0 micrometers or less are more preferable, 1.7 micrometers or less are especially preferable.

<Solid State Imaging Device>

The solid-state imaging device of the present invention includes the color filter of the present invention described above. As a structure of the solid-state image sensor of this invention, if it is a structure with which the color filter in this invention was equipped, and it is a structure which functions as a solid-state image sensor, it will not specifically limit, For example, the following structures are mentioned.

On the support body, it has the transfer electrode which consists of several photodiodes, polysilicon, etc. which comprise the light receiving area of a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.), and only the light-receiving part of a photodiode on a photodiode and a transfer electrode is carried out. It has a light shielding film which consists of tungsten etc. which were opened, has a device protective film which consists of silicon nitride etc. formed on the light shielding film so that the light shielding film whole surface and a photodiode light-receiving part may be covered, and has a color filter for solid-state image sensors of this invention on a device protective film. Configuration.

Moreover, the structure which has light concentrating means (for example, a microlens etc .. same below) on a device protective film and under a color filter (side close to a support body), the structure which has a light converging means on a color filter, etc. may be sufficient.

<Image display device>

The color filter of this invention can be used not only for a solid-state image sensor but for image display apparatuses, such as a liquid crystal display device and an organic electroluminescence display, and is especially suitable for the use of a liquid crystal display device. The liquid crystal display device provided with the color filter of this invention can display the high quality image which was excellent in the display characteristic by the favorable hue of a display image.

For the definition of the display device and the details of each display device, for example, "Electronic display device (Aki Sasaki by Co., Ltd., Kosago Co., Ltd., 1990)", "Display device (by Ibuki Sumiaki, by Sangyo Tosho (Note) ) Issued in the first year of Heisei). Moreover, about a liquid crystal display device, it describes in "next-generation liquid crystal display technology (Datsuo Uchida editing, Kosago Co., Ltd. 1994 issuance)." There is no restriction | limiting in particular in the liquid crystal display device which can apply this invention, For example, it can apply to the liquid crystal display device of various systems described in said "next-generation liquid crystal display technology."

You may use the color filter of this invention for the liquid crystal display device of a color TFT system. About the liquid crystal display device of a color TFT system, it describes, for example in "a color TFT liquid crystal display (Kyoritsu Shooting Co., Ltd. 1996 issuance)." In addition, the present invention can be applied to liquid crystal display devices having an enlarged viewing angle such as transverse electric field driving methods such as IPS and pixel division methods such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. .

Moreover, the color filter in this invention can also be used also for a bright high definition color-filter on array (COA) system. In the COA type liquid crystal display device, the required characteristics for the color filter layer may require the required characteristics for the interlayer insulating film, that is, low dielectric constant and peeling liquid resistance, in addition to the usual required characteristics as described above. In the color filter of the present invention, since a color having excellent color is used, color purity, light transmittance, and the like are good, and the color pattern (pixel) is excellent in color. Therefore, a COA type liquid crystal display device having high resolution and excellent long-term durability is provided. Can provide. Moreover, in order to satisfy the required characteristic of low dielectric constant, you may provide a resin film on a color filter layer.

These image display methods are described, for example, on page 43 of "EL, PDP, LCD Display Technology and the Latest Trends in the Market-(Published by Toray Research Center Research Division 2001)."

The liquid crystal display device provided with the color filter in this invention is comprised from various members, such as an electrode substrate, a polarizing film, retardation film, a backlight, a spacer, a viewing angle compensation film, in addition to the color filter in this invention. The color filter of this invention can be applied to the liquid crystal display device comprised from these well-known members. About these members, for example, "The market of liquid crystal display peripheral materials and chemicals (issued in 1994 by Shima Gentaro CMC)", "The present conditions and future prospects of the 2003 liquid crystal-related market (the lower volume) (Ryomoto Omote) Fuji Chimera Soken Co., Ltd., issued in 2003).

As for the backlight, I list it in SID meeting Digest 1380 (2005) (A. Konno et al.), Pages 18-24 (Yamashiro Hiroshima), page 25-30 (Yagi Takaaki) of the December, 2005 issue of the monthly display It is.

When the color filter in this invention is used for a liquid crystal display device, when combined with the triwave tube of a conventionally known cold cathode tube, high contrast can be realized, and red, green, and blue LED light source (RGB-LED) is back By using light, a liquid crystal display device having high luminance and good color reproducibility can be provided.

Example

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the meaning is exceeded. In addition, "%" and "part" are mass references | standards unless there is particular notice.

Synthesis Example 1 Synthesis of Dye Multimer P-1

[Formula 95]

Monomer 1 (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 neck flask, and Heated to ° C. Monomer 1 (1.41 g), monomer 2 (1.10 g), methacrylic acid (0.52 g), dodecyl mercaptan (0.07 g), 2,2'-azobis (isobutyric acid) dimethyl in this solution. : V601, Wako Junyaku Kogyo Co., Ltd. product] (0.30 g) and cyclohexanone (7.05 g) were mixed dropwise for 1 hour. After stirring for 4 hours after that, the mixture was left to cool to obtain a cyclohexanone solution of (PM-1). Next, methacrylic acid glycidyl (0.90 g), tetrabutylammonium bromide (0.16 g) and p-methoxyphenol (70 mg) were added, and it heated at 100 degreeC for 6 hours under air atmosphere, and methacrylic acid It confirmed that glycidyl was lost. After cooling, the mixture was added dropwise to acetonitrile / ion exchange water mixed solvent and reprecipitated to obtain 6.15 g of a dye multimer (P-1).

When the composition ratio (molar ratio) of the obtained pigment multimer was confirmed by ¹ H-NMR, the repeating unit which has a pigment | dye structure derived from a dipyrromethene pigment | dye (derived from monomer 1): Repetition which has a pigment | dye structure derived from a xanthene pigment | dye (derived from monomer 2). 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).

Synthesis Example 2: Synthesis of Dye Multimer P-2

[Formula 96]

N-methyl-2-pyrrolidone (hereinafter also referred to as "NMP") (2.00 g) was added to the three-necked flask, and it heated at 90 degreeC under nitrogen atmosphere. To this solution, 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) dimethyl : V601, Wako Junyaku Kogyo Co., Ltd. product] (0.34 g) and the mixed solution of NMP (12.10 g) were dripped for 1 hour. After stirring for 4 hours after that, the mixture was left to cool to obtain an NMP solution of (PM-2). Next, methacrylic acid glycidyl (0.90 g), tetrabutylammonium bromide (0.16 g) and p-methoxyphenol (70 mg) were added, and it heated at 100 degreeC for 15 hours in air atmosphere, and methacrylic acid It confirmed that glycidyl was lost. After cooling, the mixture was dropped into acetonitrile / ion exchange water mixed solvent and reprecipitated to obtain 5.11 g of a dye multimer (P-2).

When the composition ratio (molar ratio) of the obtained pigment multimer was confirmed by <^1> H-NMR, the repeating unit which has a pigment | dye structure derived from a triaryl methane pigment | dye (derived from monomer 3): Having a pigment | dye structure derived from a xanthene pigment | dye (derived from 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).

Synthesis Example 3: Synthesis of Dye Multimer P-3

[Formula 97]

NMP (2.00 g) was added to the three neck flask, and it heated at 90 degreeC by nitrogen atmosphere. In this solution, monomer 5 (2.92 g), monomer 6 (2.08 g), methacrylic acid (0.80 g), dodecyl mercaptan (0.12 g), 2,2'- azobis (isobutyric acid) dimethyl : V601, Wako Junyaku Kogyo Co., Ltd. product] (0.26 g) and the mixed solution of NMP (15.40 g) were dripped for 1 hour. After stirring for 4 hours after that, the mixture was left to cool to obtain an NMP solution of (PM-3). Next, methacrylic acid glycidyl (0.49 g), tetrabutylammonium bromide (0.09 g) and p-methoxyphenol (63 mg) were added, and it heated at 100 degreeC for 15 hours under air atmosphere, and methacrylic acid It confirmed that glycidyl was lost. After cooling, the mixture was dropped into acetonitrile / ion exchange water mixed solvent and reprecipitated to obtain 5.44 g of a dye multimer (P-3).

When the composition ratio (molar ratio) of the obtained pigment multimer was confirmed by <^1> H-NMR, the repeating unit which has a pigment | dye structure derived from triaryl methane pigment | dye (derived from monomer 5): pigment | dye derived from a phthalocyanine pigment | dye (derived from monomer 6). Repeating unit having a structure: 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).

Synthesis Example 4: Synthesis of Dye Multimer P-4

[Formula 98]

N-ethyl-2-pyrrolidone (hereinafter also referred to as "NEP") (2.00 g) was added to the three-necked flask, and it heated at 90 degreeC under nitrogen atmosphere. To this solution, Monomer 6 (4.20 g), Monomer 7 (0.80 g), Methacrylic acid (1.04 g), Dodecyl mercaptan (0.13 g), 2,2'-azobis (isobutyric acid) dimethyl : V601, Wako Junyaku Kogyo Co., Ltd. product] (0.30 g) and NEP (16.12 g) were mixed dropwise for 1 hour. After stirring for 4 hours after that, the mixture was left to cool to obtain an NEP solution of (PM-4). Next, glycidyl methacrylate (0.72 g), tetrabutylammonium bromide (0.13 g) and p-methoxyphenol (70 mg) were added, and it heated at 100 degreeC for 15 hours in air atmosphere, and it was methacrylic acid. It confirmed that glycidyl was lost. After cooling, the mixture was added dropwise to acetonitrile / ion exchange water mixed solvent and reprecipitated to obtain 6.07 g of a dye multimer (P-4).

When the composition ratio (molar ratio) of the obtained pigment multimer was confirmed by <^1> H-NMR, the repeating unit which has a pigment | dye structure derived from phthalocyanine pigment | dye (derived from monomer 6): Pigment structure derived from azomethine pigment | dye (derived from monomer 7) Repeating unit having: Repeating unit having acidic group: Repeating unit having polymerizable group = 18: 8: 44: 30. The weight average molecular weight (Mw) was 13,600 (GPC).

Synthesis Example 5 Synthesis of Dye Multimer P-5

[Formula 99]

NMP (2.00 g) was added to the three neck flask, and it heated at 80 degreeC by nitrogen atmosphere. Monomer 8 (3.09 g), monomer 7 (1.91 g), methacrylic acid (0.74 g), dodecyl mercaptan (0.13 g), 2,2'-azobis (isobutyric acid) dimethyl in this solution. : V601, Wako Junyaku Kogyo Co., Ltd. product] (0.31 g) and NMP (15.40 g) were mixed dropwise for 1 hour. After stirring for 4 hours after that, the mixture was left to cool to obtain an NMP solution of (PM-5). Next, methacrylic acid glycidyl (0.43 g), tetrabutylammonium bromide (0.08 g) and p-methoxyphenol (62 mg) were added, and it heated at 100 degreeC for 15 hours in air atmosphere, and the methacrylic acid It confirmed that glycidyl was lost. After cooling, the mixture was added dropwise to methanol / ion exchange water mixed solvent and reprecipitated to obtain 4.73 g of a dye multimer (P-5).

When the composition ratio (molar ratio) of the obtained dye multimer was confirmed by ¹ H-NMR, the repeating unit which has a pigment | dye structure derived from an azo dye (derived from monomer 8): The repeat which has a pigment | dye structure derived from azomethine pigment | dye (derived from monomer 7). 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).

Synthesis Example 6 Synthesis of Dye Multimer P-6

[Formula 100]

Cyclohexanone (2.00 g) was added to the three neck flask, and it heated at 90 degreeC by nitrogen atmosphere. In this solution, Monomer 6 (4.35 g), Monomer 7 (0.65 g), 2-methacryloyloxyethyl succinic acid (1.49 g), dodecyl mercaptan (0.09 g), 2,2'-azobis (iso) Butyric acid) dimethyl [trade name: V601, manufactured by Wako Junyaku Kogyo Co., Ltd.] (0.20 g) and cyclohexanone (44.30 g) were added dropwise for 1 hour. After stirring for 4 hours after that, the mixture was left to cool to obtain a cyclohexanone solution of (PM-6).

When the composition ratio (molar ratio) of the obtained pigment multimer was confirmed by <^1> H-NMR, the repeating unit which has a pigment | dye structure derived from phthalocyanine pigment | dye (derived from monomer 6): Pigment structure derived from azomethine pigment | dye (derived from monomer 7) Repeating unit having an acidic repeating unit: 29:10:61. The weight average molecular weight (Mw) was 9,900 (GPC).

Synthesis Example 7: Synthesis of Dye Multimer P-7

[Formula 101]

In a three neck flask, Monomer 1 (1.41 g), Monomer 2 (1.10 g), Methacrylic acid (0.52 g), Dodecyl mercaptan (0.07 g), Polyethylene glycol monomethacrylate [Brand name: Blemmer PE- 90, Nichiyu Co., Ltd. product] (0.12g) and cyclohexanone (7.05g) were added, and it heated at 90 degreeC by nitrogen atmosphere. In this solution, Monomer 1 (1.41 g), Monomer 2 (1.10 g), Methacrylic acid (0.52 g), Dodecyl mercaptan (0.07 g), Blemmer PE-90 (0.12 g), 2,2'-Azo Bis (isobutyric acid) dimethyl (trade name: V601, manufactured by Wako Junyaku Kogyo Co., Ltd.) (0.30 g) and cyclohexanone (7.05 g) were added dropwise for 1 hour. After stirring for 4 hours after that, the mixture was left to cool to obtain a cyclohexanone solution of (PM-7). Others were carried out similarly to the synthesis example 1, and obtained 6.01g of dye multimers (P-7).

When the composition ratio (molar ratio) of the obtained pigment multimer was confirmed by ¹ H-NMR, the repeating unit which has a pigment | dye structure derived from a dipyrromethene pigment | dye (derived from monomer 1): Repetition which has a pigment | dye structure derived from a xanthene pigment | dye (derived from monomer 2). Unit: repeating unit having an acid group: repeating unit having a polymerizable group: repeating unit derived from Blemmer PE-90 = 11: 12: 35: 34: 8. The weight average molecular weight (Mw) was 10,400 (GPC).

Synthesis Example 8: Synthesis of Dye Multimer P-8

[Formula 102]

In a three neck flask, Monomer 1 (2.81 g), Monomer 2 (2.19 g), Methacrylic acid (1.04 g), 2-Cyano-2-propyldodecyl trithiocarbonate (0.28 g), and cyclohexanone ( 14.09 g) was added and heated to 85 ° C under a nitrogen stream. To this solution was added 2,2'-azobisisobutyronitrile (trade name: V60, manufactured by Wako Junyaku Kogyo Co., Ltd.) (0.13 g), and stirred at 85 ° C for 6 hours, followed by A cyclohexanone solution of PM-8) was obtained. Next, methacrylic acid glycidyl (0.90 g), tetrabutylammonium bromide (0.16 g) and p-methoxyphenol (70 mg) were added, and it heated at 100 degreeC for 6 hours under air atmosphere, and methacrylic acid It confirmed that glycidyl was lost. After cooling, the mixture was added dropwise to acetonitrile / ion exchange water mixed solvent and reprecipitated to obtain 6.35 g of a dye multimer (P-8).

When the composition ratio (molar ratio) of the obtained pigment multimer was confirmed by ¹ H-NMR, the repeating unit which has a pigment | dye structure derived from a dipyrromethene pigment | dye (derived from monomer 1): Repetition which has a pigment | dye structure derived from a xanthene pigment | dye (derived from monomer 2). 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).

Synthesis Example 9: Synthesis of Dye Multimer P-9

[Formula 103]

In a three-neck flask, Monomer 1 (1.41 g), Monomer 2 (1.10 g), Methacrylic acid (0.52 g), Dodecyl mercaptan (0.07 g), Pentamethylpiperidinyl methacrylate [trade name: Pancryl FA- 711MM, the Hitachi Kasei Co., Ltd. product] (0.12g) and cyclohexanone (7.05g) were added, and it heated at 90 degreeC by nitrogen atmosphere. In this solution, Monomer 1 (1.41 g), Monomer 2 (1.10 g), Methacrylic acid (0.52 g), Dodecyl mercaptan (0.07 g), Pancryl FA-711MM (0.12 g), 2,2'-Azo Bis (isobutyric acid) dimethyl (trade name: V601, manufactured by Wako Junyaku Kogyo Co., Ltd.) (0.30 g) and cyclohexanone (7.05 g) were added dropwise for 1 hour. After stirring for 4 hours after that, the mixture was left to cool to obtain a cyclohexanone solution of (PM-9). Others were carried out similarly to the synthesis example 1, and obtained 5.40g of dye multimers (P-9).

When the composition ratio (molar ratio) of the obtained pigment multimer was confirmed by ¹ H-NMR, the repeating unit which has a pigment | dye structure derived from a dipyrromethene pigment | dye (derived from monomer 1): Repetition which has a pigment | dye structure derived from a xanthene pigment | dye (derived from monomer 2). Unit: repeating unit having an acid group: repeating unit having a polymerizable group: The repeating unit derived from pancryl FA-711MM was 12: 12: 35: 34: 7. The weight average molecular weight (Mw) was 10,100 (GPC).

Synthesis Example 1 Synthesis of Dye Multimer P-20

[Formula 104]

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

When the composition ratio (molar ratio) of the obtained dye multimer was confirmed by ¹ H-NMR, the repeating unit which has a pigment | dye structure derived from a dipyrromethene pigment | dye (derived from monomer 1): The repeating unit which has an acidic radical: The repeating unit which has a polymeric group = 30 : 48: 22. The weight average molecular weight (Mw) was 11,500 (GPC).

Synthesis Example 2 Synthesis of Dye Multimer P-21

[Formula 105]

Cyclohexanone (2.00 g) was added to the three neck flask, and it heated at 90 degreeC by nitrogen atmosphere. To this solution, Monomer 2 (5.00 g), methacrylic acid (1.04 g), dodecyl mercaptan (0.15 g), 2,2'-azobis (isobutyric acid) dimethyl [trade name: V601, Wako Junyaku Kogyo Corporation] (0.34 g) and cyclohexanone (12.10 g) were dripped for 1 hour. After stirring for 4 hours after that, the mixture was left to cool to obtain a cyclohexanone solution of (PM-21). Next, methacrylic acid glycidyl (0.90 g), tetrabutylammonium bromide (0.16 g) and p-methoxyphenol (70 mg) were added, and it heated at 100 degreeC for 6 hours under air atmosphere, and methacrylic acid It confirmed that glycidyl was lost. After cooling, the mixture was added dropwise to acetonitrile / ion exchange water mixed solvent and reprecipitated to obtain 5.88 g of a dye multimer (P-21).

When the composition ratio (molar ratio) of the obtained dye multimer was confirmed by ¹ H-NMR, the repeating unit which has a pigment | dye structure derived from a xanthene dye (derived from monomer 2): The repeating unit which has an acidic radical: The repeating unit which has a polymeric group = 29:36 : 35. The weight average molecular weight (Mw) was 10,800 (GPC).

Synthesis Example 3 Synthesis of Dye Multimer P-22

[Formula 106]

A dye multimer (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.

When the composition ratio (molar ratio) of the obtained dye multimer was confirmed by ¹ H-NMR, the repeating unit which has a pigment | dye structure derived from a xanthene dye (derived from monomer 3): The repeating unit which has an acidic radical: The repeating unit which has a polymeric group = 36:33 : 31. The weight average molecular weight (Mw) was 13,900 (GPC).

Synthesis Example 4 Synthesis of Dye Multimer P-23

[Formula 107]

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

When the composition ratio (molar ratio) of the obtained dye multimer was confirmed by ¹ H-NMR, the repeating unit which has a pigment | dye structure derived from a triaryl methane pigment | dye (derived from monomer 4): The repeating unit which has an acidic radical: The repeating unit which has a polymeric group = 31:34:34. The weight average molecular weight (Mw) was 10,100 (GPC).

Synthesis Example 5 Synthesis of Dye Multimer P-25

[Formula 108]

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

When the composition ratio (molar ratio) of the obtained dye multimer was confirmed by ¹ H-NMR, the repeating unit which has a pigment | dye structure derived from a phthalocyanine pigment | dye (derived from monomer 5): The repeating unit which has an acidic radical: The repeating unit which has a polymeric group = 28:47:25. The weight average molecular weight (Mw) was 12,500 (GPC).

Synthesis Example 6 Synthesis of Dye Multimer P-26

[Formula 109]

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

When the composition ratio (molar ratio) of the obtained dye multimer was confirmed by ¹ H-NMR, the repeating unit which has a pigment | dye structure derived from an azo dye (derived from monomer 8): The repeating unit which has an acidic radical: The repeating unit which has a polymeric group = 50:33 : 17 The weight average molecular weight (Mw) was 9,200 (GPC).

Synthesis Example 7 Synthesis of Dye Multimer P-28

[Formula 110]

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

When the composition ratio (molar ratio) of the obtained dye multimer was confirmed by ¹ H-NMR, the repeating unit which has a pigment | dye structure derived from an azomethine pigment | dye (derived from monomer 7): The repeating unit which has an acidic radical: The repeating unit which has a polymeric group = 48 : 35: 17. The weight average molecular weight (Mw) was 9,900 (GPC).

1. Preparation of resist liquid

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

Composition of resist liquid for undercoat layer

Solvent: 19.20 parts of propylene glycol monomethyl ether acetate

Solvent: 36.67 parts of ethyl lactate

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

Ethylenic unsaturated double bond-containing compound: 12.20 parts of dipentaerythritol hexaacrylate

Polymerization inhibitor: 0.0061 parts of p-methoxyphenol

Fluorine-based surfactant: F-475, DIC Corporation 0.83 parts

Photoinitiator: Trihalomethyl triazine type photoinitiator

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

2. Fabrication of Silicon Wafer Substrate with Undercoat Layer

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

On an 8-inch silicon wafer, CT-4000L (manufactured by FUJIFILM Materials) was uniformly coated with a spin coat to form a coating film, and the formed coating film was treated with an oven at 220 ° C. for 1 hour to cure the coating film. It was made into the undercoat layer. In addition, the application | coating rotation speed of a spin coat was adjusted so that the film thickness of the coating film after the said heat processing might be about 0.1 micrometer.

3. Preparation of coloring composition

(Coloring Composition 1)

Each following component was mixed, disperse | distributed, and dissolved, and the coloring composition 1 was obtained.

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 (accuracy RD-F8 (made by Nippon Shokubai Corporation)): 0.23 parts

Photoinitiator I-2 (IRGACURE OXE-02): 0.975 parts

Cyclohexanone solution of the dye multimer (solid concentration 12.3%): 73.96 parts

Polymerizable compound (dipentaerythritol hexaacrylate, NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)): 1.96 parts

Polymerization inhibitor (p-methoxyphenol): 0.0007 parts

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

(Preparation of coloring composition 2)

Each following component was mixed, disperse | distributed, and dissolved, and the coloring composition 2 was obtained.

Organic solvent (cyclohexanone): 17.12 parts

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

Cyclohexanone solution of the dye multimer (solid concentration 12.3%): 73.96 parts

Polymerization inhibitor (p-methoxyphenol): 0.0007 parts

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

4. Production of color filter (coloring pattern)

4-1: Preparation of Color Filter by Photolithography

The coloring composition 1 prepared above was apply | coated on the undercoat layer of the silicon wafer with an undercoat layer produced above, and the coloring layer (coating film) was formed. And heat processing (prebaking) was performed for 120 second using the 100 degreeC hotplate so that the dry film thickness of this coating film might be set to 1 micrometer.

Subsequently, the i-ray stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Co., Ltd.) was exposed at various exposure doses of 50 to 1200 mJ / cm ² through an Island pattern mask having a pattern of 1.0 μm square at a wavelength of 365 nm.

Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotating table of a spin shower developer (DW-30 type, manufactured by Chemitronics Co., Ltd.), and then CD-2000 (Fujifilm Electronics Materials) Puddle development was performed at 23 degreeC for 60 second using the product), and the coloring pattern was formed on the undercoat layer of the silicon wafer with an undercoat layer.

The silicon wafer on which the coloring pattern is formed is fixed to the horizontal rotating table by a vacuum chuck method, and pure water is supplied from the jet nozzle to the shower shape while rotating the silicon wafer at a rotation speed of 50 rpm by a rotating device. The rinse treatment was carried out, followed by spray drying, post-baking on a hot plate at 200 ° C. for 300 seconds to obtain a transparent pattern (cured film) having a film thickness of 1 μm on a silicon wafer.

By the above, the coloring pattern formation silicon wafer of the structure by which the coloring pattern (color filter) was provided on the undercoat layer of the silicon wafer with an undercoat layer was obtained.

Then, the size of the coloring pattern was measured using length measurement SEM "S-9260A" (made by Hitachi High Technologies, Ltd.).

Pattern formation, image development residue, and roughness (color nonuniformity) were evaluated using the coloring pattern of the exposure amount whose pattern size is 1.0 micrometer.

4-2: Preparation of Color Filter by Dry Etching Method

The coloring composition 2 obtained above is apply | coated using a spin coater so that a film thickness may be set to 0.5 micrometer on the glass substrate of 7.5 cm x 7.5 cm, and it heats at 200 degreeC for 5 minutes using a hotplate, and apply | coats The film was cured to prepare a colored layer. The film thickness of this colored layer was 0.5 micrometer.

Subsequently, a positive photoresist "FHi622BC" (manufactured by FUJIFILM Materials) was applied and prebaked at 90 ° C. for 1 minute to form a photoresist layer having a film thickness of 0.8 μm.

Subsequently, the photoresist layer is pattern-exposed at an exposure dose of 350 mJ / cm ² using an i-line stepper (manufactured by Canon Corporation), and for 1 minute at a temperature at which the temperature or the ambient temperature of the photoresist layer becomes 90 ° C Heat treatment was performed. Thereafter, the developer solution "FHD-5" (manufactured by FUJIFILM Materials) was used for 1 minute, followed by 1 minute post-baking at 110 ° C to form a resist pattern. The size of this resist pattern was formed in 1.0 micrometer of one side in consideration of the etching conversion difference (reduction of the pattern width by etching).

Next, the obtained glass substrate was affixed on an 8-inch silicon wafer, and RF power: 800 W, antenna bias: 400 W, wafer bias: 200 W, internal pressure of the chamber, in a dry etching apparatus (U-621, manufactured by Hitachi High Technologies, Inc.). 4.0 Pa, substrate temperature: 50 ° C., gas species and flow rate of the mixed gas were CF ₄ : 80 mL / min, O ₂ : 40 mL / min, Ar: 800 mL / min. did.

Subsequently, in the same etching chamber, RF power: 600 W, antenna bias: 100 W, wafer bias: 250 W, internal pressure of the chamber: 2.0 Pa, substrate temperature: 50 ° C., gas species and flow rate of the mixed gas were N ₂ : 500 mL / min. , O ₂ : 50 mL / min, Ar: 500 mL / min (N ₂ / O ₂ / Ar = 10/1/10), and a second step etching treatment and over etching treatment for 28 seconds were performed.

After performing dry etching on the said conditions, using the photoresist stripping liquid "MS230C" (made by Fujifilm Electronics), the peeling process was performed at 50 degreeC for 120 second, the resist was removed and the green coloring pattern was formed. . Furthermore, washing | cleaning with pure water and spin drying were performed, and the dehydration baking process was performed for 2 minutes at 100 degreeC after that. The color filter was obtained by the above.

5. Evaluation

5-1. Spectral characteristics

A color pattern was produced in the same manner as the color filter by the photolithography method except that an island pattern mask having a square of 7.0 μm was used, and the absorbance in the wavelength range of 400 to 700 nm in the formed color pattern was measured by a microscopic spectrometer ( It measured by Otsuka Denshi Co., Ltd. LCF-1500M), and evaluated according to the following evaluation criteria.

A: The absorbance of the maximum absorption wavelength [lambda] max is 1.0 or more, and the absorbance of the maximum absorption wavelength [lambda] max is 200 times or more with respect to the absorbance at the minimum absorption wavelength [lambda] min.

B: The absorbance of the maximum absorption wavelength lambda max is 1.0 or more, and the absorbance of the maximum absorption wavelength lambda max is less than 200 times with respect to the absorbance at the minimum absorption wavelength lambda min.

5-2. Color unevenness

A substrate for evaluation was created in the same manner as the method for forming a color filter colored pattern by the photolithography method, except that the glass substrate was used instead of the undercoat layer and directly exposed without using a mask. The luminance distribution was analyzed by the following method, and based on the ratio of pixels in which the deviation from the average was within ± 5% to the total number of pixels.

The measuring method of luminance distribution is demonstrated. First, the image which image | photographed the brightness distribution of the glass plate with a colored layer with the microscope MX-50 (made by Olympus) was analyzed.

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

-Evaluation standard-

A: The pixel whose deviation from the average is within ± 5% is 99% or more of the total number of pixels

B: Pixels with a deviation from the average within ± 5% are 98% or more but less than 99% of the total number of pixels

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

D: Pixels with deviations from the average within ± 5% are 95% or more and less than 97% of the total number of pixels

E: Pixels with deviations from the average within ± 5% are less than 95% of the total number of pixels

5-3. Light transmittance

A color pattern was produced in the same manner as the color filter according to the photolithography method except that an island pattern mask having a square of 7.0 μm was used, and the absorbance in the wavelength range of 200 to 700 nm in the formed color pattern was measured by a microscopic spectrometer ( It measured by Otsuka Denshi Co., Ltd. LCF-1500M), and evaluated the transmittance | permeability in the maximum transmission wavelength according to the following evaluation criteria.

A: transmittance is 80% or more

B: transmittance is 70% or more but less than 80%

C: transmittance is less than 70%

5-4. Heat resistance

The glass substrate to which the coloring composition was apply | coated was mounted on the 200 degreeC hotplate so that it might contact on a board | substrate surface, and it heated for 1 hour, and then color difference (ΔE *) before and after heating with colorimeter MCPD-1000 (made by Otsuka Denshi Co., Ltd.) ab value) was measured and evaluated according to the following criterion as an index for evaluating thermal fastness. ΔE * ab value indicates that the smaller the value, the better the heat resistance. In addition, the ΔE * ab value is a value obtained from the following color difference formula using the CIE1976 (L *, a *, b *) spatial colorimeter (Japanese Society for Coloring Studies, First Edition Color Science Handbook (Showa 60) p. 266) ).

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

A: ΔE * ab is less than 10

B: ΔE * ab value is 10 or more but less than 20

C: ΔE * ab value is 20 or more

5-5. Solvent resistance

The coloring composition was apply | coated using a spin coater so that the film thickness after drying might be set to 0.6 micrometer on the glass wafer, and it heated for 300 second with the 200 degreeC hotplate.

About the color filter obtained above, propylene glycol monomethyl ether acetate (PGMEA) was dripped, and it left to stand for 120 second, and rinsed with running water for 10 second.

Spectral fluctuations in the transmittance before and after dropping of various liquids were measured using MCPD-3000 (manufactured by Otsuka Denshi Co., Ltd.), and the color difference (ΔE * ab) was measured. The lower ΔE * ab means that the solvent resistance is excellent.

A: ΔE * ab is less than 10

B: ΔE * ab value is 10 or more

TABLE 1

As is clear from the above results, the colored composition of the present invention was excellent in color irregularity and spectral characteristics. Furthermore, the light transmittance, heat resistance, and solvent resistance were excellent. Moreover, when the hardened | cured material of Examples 1-9 was expanded and observed with the optical microscope, it was homogeneous. Moreover, Example 9 showed the tendency which is higher than Example 1.

On the other hand, Comparative Examples 1-4 using two types of dye multimers were inferior in color nonuniformity and light transmittance. Moreover, when the hardened | cured material of Comparative Examples 1-4 was expanded and observed with the optical microscope, the micro site | parts from which a color differs were collected. This can be assumed to be phase separation due to poor compatibility of the mixed dye multimer.

Reference Example 1

In Example 1, the coloring composition was prepared like Example 1 except having used P-20 instead of P-1 as a dye multimer, and the spectral characteristic was evaluated by the same method as the above. It turned out that the reference example 1 tends to be inferior in spectral characteristics.

Reference Example 2

In Example 1, except having used P-21 instead of P-1 as a dye multimer, the coloring composition was prepared like Example 1, and the spectral characteristic was evaluated by the same method as the above. It turned out that the reference example 2 tends to be inferior in spectral characteristics.

Reference Example 3

In Example 1, the coloring composition was prepared like Example 1 except having used P-22 instead of P-1 as a dye multimer, and evaluated the spectral characteristic by the same method as the above. It turned out that the reference example 3 tends to be inferior in spectral characteristics.

<Example 10>

In Example 1, the polymeric compound was changed to KAYARAD DPHA (made by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate) of the same mass, and the test was carried out similarly to Example 1, and it carried out. The same preferable result as Example 1 was obtained.

<Example 11>

In Example 1, the photoinitiator was changed to IRGACURE OXE-01 (manufactured by BASF), and the test was carried out in the same manner as in Example 1, whereby the same preferred results as in Example 1 were obtained.

Claims (21)

Dye multimer which has a repeating unit a1 represented by the following general formula (a1-1), and a repeating unit a2 represented by the following general formula (a2-1),
Curable compound
It contains a coloring composition.

In General Formulas (a1-1) and (a2-1), Q ¹ and Q ² each independently represent a trivalent linking group, and L ¹ and L ² each independently represent a single bond or a divalent linking group,
D ¹ represents a dye structure derived from a dipyrromethene dye, and D ² represents a dye structure derived from a xanthene dye;
D ¹ represents a dye structure derived from a triarylmethane dye, and D ² represents a dye structure derived from a xanthene dye;
D ¹ represents a dye structure derived from a triarylmethane dye, and D ² represents a dye structure derived from a phthalocyanine dye;
D ¹ represents a dye structure derived from a phthalocyanine dye, and D ² represents a dye structure derived from an azomethine dye; or
D ¹ represents a dye structure derived from an azo dye, D ² represents a dye structure derived from an azomethine dye,
* Represents a bonding hand. delete The method according to claim 1,
The said dye multimer has a coloring unit which has an acidic radical further. The method according to claim 1,
The coloring composition in which the said dye multimer further has a repeating unit which has a polymeric group. The method according to claim 1,
The said curable compound is a polymeric compound, The coloring composition which contains a photoinitiator further. The method according to claim 1,
The coloring composition whose said dye multimer is 1 type chosen from (meth) acrylic-type resin, styrene-type resin, and (meth) acrylic / styrene-type resin. The method according to claim 1,
The coloring composition used for formation of the colored layer of a color filter. Cured film formed by hardening | curing the coloring composition of Claim 1. The color filter which has a cured film of Claim 8. A pattern including a step of applying the coloring composition according to claim 1 to a support to form a coloring composition layer, a step of exposing the coloring composition layer in a pattern shape, and a step of developing and removing the unexposed part to form a colored pattern. Forming method. The manufacturing method of a color filter containing the pattern formation method of Claim 10. The solid-state image sensor which has the color filter of Claim 9. An image display device having the color filter according to claim 9. delete The method according to claim 1,
The coloring composition whose ratio of repeating unit a1 is 10-90 mol% of all the repeating units which comprise a dye multimer, and the ratio of repeating unit a2 is 10-90 mol% of all the repeating units which comprise a dye multimer. The method according to claim 1,
The coloring composition whose ratio of repeating unit a1 is 20-80 mol% of all the repeating units which comprise a dye multimer, and the ratio of repeating unit a2 is 20-80 mol% of all the repeating units which comprise a dye multimer. The method according to claim 1,
The coloring composition whose ratio of repeating unit a1 is 25-75 mol% of all the repeating units which comprise a dye multimer, and the ratio of repeating unit a2 is 25-75 mol% of all the repeating units which comprise a dye multimer. delete The method according to claim 1,
The coloring composition in which the said dye multimer further has a repeating unit which has at least one of the structures represented by following formula (1)-(5).

In formula (1), R <^1> represents a hydrogen atom, a C1-C18 alkyl group, a C6-C18 aryl group, or oxyradical. R ² and R ³ each independently represent an alkyl group having 1 to 18 carbon atoms. R ² and R ³ may be bonded to each other to represent an aliphatic ring having 4 to 12 carbon atoms. "*" Represents the bond of the structure and polymer skeleton which are represented by Formula (1).

In formula (2), R <^4> represents following formula (2A), a C1-C18 alkyl group, or a C6-C18 aryl group. R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. "*" Represents the bond of the structure and polymer skeleton which are represented by Formula (2).

In formula (2A), R <^6> represents a C1-C18 alkyl group each independently. "*" Represents the bond of the structure represented by Formula (2A), and the structure represented by Formula (2).

In formula (3), R <^7> represents a C1-C18 alkyl group. n1 represents the integer of 0-3. When n1 is 2 or 3, each R <^7> may be same or different. "*" Represents the bond of the structure and polymer skeleton which are represented by Formula (3).

In formula (4), R <^8> and R <^9> respectively independently represents a C1-C18 alkyl group. n2 represents the integer of 0-3. n3 represents the integer of 0-4. When n2 is 2 or 3, each R <^8> may be same or different. When n3 represents the integer of 2-4, each R <^9> may be same or different. "*" Represents the bond of the structure and polymer skeleton which are represented by Formula (4).

In formula (5), R <^10> -R <^12> represents a C1-C18 alkyl group or a C1-C8 alkoxy group each independently. n4-n6 represent the integer of 0-5 each independently. n7 to n9 each independently represent 0 or 1, and at least one of n7 to n9 represents 1; When n4 represents the integer of 2-5, each R <^10> may be same or different. When n5 represents the integer of 2-5, each R <^11> may be same or different. When n6 represents the integer of 2-5, each R <^12> may be same or different. "*" Represents the bond of the structure and polymer skeleton which are represented by Formula (5). delete The method according to claim 1,
D <^1> in the said general formula (a1-1) shows the pigment | dye structure derived from a dipyrromethene pigment | dye, and D <^2> in the said general formula (a2-1) shows the pigment | dye structure derived from a xanthene pigment | dye; or
The general formula (a1-1) of D ¹ is a tri-aryl methane dye represents a structure derived from the dye, the above-mentioned general formula (a2-1) of the D ² represents a pigment structure derived from a xanthene dye, a colored composition.