KR20210080243A - Colored composition, colored cured film and manufacturing method thereof, color filter, display device, light receiving element, and curable composition - Google Patents

Abstract

The present invention relates to a colored composition, a colored cured film, a manufacturing method thereof, a color filter, a display element, a light receiving element, and a curable composition. The colored composition comprises: a colorant (A); a polymer (B) (the colorant (A) is excluded); and a polymerizable compound (C) (the colorant (A) and the polymer (B) are excluded), wherein at least one chosen from a group which consists of the colorant (A), the polymer (B), and the polymerizable compound (C) has a partial structure represented by formula (1), and at least one chosen from a group which consists of the colorant (A), the polymer (B), and the polymerizable compound (C) has a hydroxyl group. In formula (1): R^1 and R^2 are each independently C1-C4 alkyl group; L^1 is a divalent organic group; X^1 is a divalent coupling group which has an electron withdrawing property; n1 and n2 are each independently an integer of 0 to 2; and * represents a bond.

Description

A coloring composition, a colored cured film, its manufacturing method, a color filter, a display element, a light receiving element, and a curable composition TECHNICAL FIELD

TECHNICAL FIELD This invention relates to a coloring composition, a colored cured film, its manufacturing method, a color filter, a display element, a light receiving element, and a curable composition.

As a manufacturing method of colored cured films, such as a color filter, the inkjet system, the electrodeposition method, the printing method, the photolithography method, etc. are known. Among these, the photolithography method has become mainstream in recent years. When a color filter is manufactured by the photolithography method, for example, after apply|coating a colored curable composition on a board|substrate to form a coating film, it exposes through the photomask which has a predetermined opening pattern, and then develops and unexposed part. The method of forming a pattern by dissolving and removing is employ|adopted (for example, refer patent document 1). After pattern formation, curing of a coating film is accelerated|stimulated by post-baking at the temperature of 200-250 degreeC for about 30-60 minutes normally, and improving film hardness, solvent resistance of a film|membrane, etc. are performed.

Japanese Laid-Open Patent Publication No. 2-144502

As a colorant contained in the colored cured film, the dye can increase the color and luminance of a displayed image upon image display by the color purity of the dye itself or the vividness of its color, and reduction of coarse particles derived from the pigment Therefore, it is considered to be effective in improving the contrast.

However, there is a problem that dyes are generally inferior in heat resistance. Therefore, it is difficult to heat the coating film formed using the coloring composition containing dye at the post-baking temperature of 200-250 degreeC. Moreover, with the expansion of uses, such as a display element, as a board|substrate, the replacement with the flexible plastic board|substrate from the conventional glass substrate is examined. However, since plastic substrates generally have low heat resistance, when a coating film made of a coloring composition is formed on a plastic substrate and heated at a post-baking temperature of 200 to 250° C., there is concern that elongation or shrinkage of the plastic substrate occurs. .

For this problem, it is considered to perform post-baking at a temperature as low as possible. However, when post-baking is performed at low temperature, hardening of a film|membrane cannot fully be performed, and there exists a possibility that problems, such as a fall of solvent resistance, may arise. Moreover, the curable composition which is highly sensitive at low temperature generally tends to be inferior to storage stability.

This invention was made|formed in view of the said subject, and it is excellent in storage stability and low temperature curability, and makes it one objective to provide the coloring composition from which the cured film excellent in solvent resistance can be obtained. Another object of the present invention is to provide a curable composition from which a cured film excellent in storage stability and low temperature curability and excellent solvent resistance can be obtained.

In order to solve the said subject, according to this invention, the manufacturing method of the following coloring composition, a colored cured film, a color filter, a display element, a light receiving element, a colored cured film, and curable composition are provided.

[1] (A) a colorant, (B) a polymer (with the proviso that the above (A) colorant is excluded), and (C) a polymerizable compound (with the proviso that the above (A) colorant and the above (B) polymer are excluded. ), wherein at least one selected from the group consisting of the (A) colorant, the (B) polymer, and the (C) polymerizable compound has a partial structure represented by the following formula (1), The coloring composition in which at least 1 sort(s) chosen from the group which consists of said (A) coloring agent, said (B) polymer, and said (C) polymeric compound has a hydroxyl group.

(In formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms. L ¹ is a divalent organic group. X ¹ is a divalent linking group having electron withdrawing property. n1 and n2 are each independently an integer of 0 to 2. "*" represents a bond.)

[2] A colored cured film formed using the colored composition of the above [1].

[3] A color filter formed using the coloring composition of [1] above.

[4] A display element provided with the colored cured film according to [2] above.

[5] A light-receiving element provided with the colored cured film according to [2] above.

[6] A method for producing a colored cured film, comprising a step of forming a coating film by applying the coloring composition of the above [1] on a substrate, and a step of removing a solvent from the coating film.

[7] A curable composition comprising (B) a polymer (with the proviso that the colorant is excluded) and (C) a polymerizable compound (with the proviso that the above-mentioned colorant and the (B) polymer are excluded), wherein the (B) polymer and at least one selected from the group consisting of the (C) polymerizable compound has a partial structure represented by the following formula (1), and is selected from the group consisting of the (B) polymer and the (C) polymerizable compound At least 1 type of curable composition has a hydroxyl group.

According to the coloring composition of this invention, at least 1 sort(s) selected from the group which consists of (A) a coloring agent, (B) a polymer, and (C) a polymeric compound has a partial structure represented by said Formula (1), (A) a coloring agent, (B) When at least 1 sort(s) chosen from the group which consists of a polymer and (C) polymeric compound has a hydroxyl group, even when it post-baking at low temperature, the colored cured film excellent in solvent resistance can be formed. Moreover, there are few temporal changes of a viscosity, and the coloring composition of this invention has favorable storage stability. Therefore, the coloring composition of this invention is useful as a material of various color filters, such as a display element and a light receiving element.

Moreover, according to the curable composition of this invention, at least 1 sort(s) selected from the group which consists of (B) polymer and (C) polymeric compound has a partial structure represented by said Formula (1), (B) polymer and (C) When at least 1 sort(s) selected from the group which consists of a polymeric compound has a hydroxyl group, even when it post-baking at low temperature, the cured film excellent in solvent resistance can be formed. Moreover, the curable composition of this invention has few changes with time of a viscosity, and storage stability is favorable. Therefore, the curable composition of this invention is useful as a protective film material, a spacer material, and an insulating film material.

(Form for implementing the invention)

Hereinafter, matters related to the embodiment will be described in detail. In addition, in this specification, the numerical range described using "-" is a meaning including the numerical value described before and after "-" as a lower limit and an upper limit. A "structural unit" is a unit mainly constituting the main chain structure, and refers to a unit contained in at least two or more in the main chain structure.

[Coloring composition]

A coloring composition is a composition used in order to form colored layers, such as each color pixel used for a color filter, a black matrix, a black spacer. The coloring composition of the present disclosure comprises (A) a colorant, (B) a polymer (with the proviso that (A) a colorant is excluded. Hereinafter the same), (C) a polymerizable compound (provided that (A) a colorant and (B) Except for polymers, the same hereinafter) is contained. In particular, the coloring composition of the present disclosure contains the following formula (1) in the same molecule or in a different molecule in at least one selected from the group consisting of (A) a colorant, (B) a polymer, and (C) a polymerizable compound ) and a hydroxyl group. That is, in the coloring composition of this indication, at least 1 sort(s) chosen from the group which consists of (A) a coloring agent, (B) a polymer, and a (C) polymeric compound has a partial structure represented by following formula (1), (A) ) At least 1 sort(s) chosen from the group which consists of a coloring agent, a (B) polymer, and a (C) polymeric compound has a hydroxyl group. In addition, the partial structure and hydroxyl group represented by following formula (1) may exist in the same molecule|numerator, and may exist in a different molecule|numerator.

(In formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms. L ¹ is a divalent organic group. X ¹ is a divalent linking group having electron withdrawing property. n1 and n2 are each independently an integer of 0 to 2. "*" represents a bond.)

Here, in the coloring composition of the present disclosure, "in the same molecule or in a different molecule in at least 1 sort(s) selected from the group which consists of (A) a colorant, (B) a polymer, and (C) a polymeric compound, a formula The partial structure represented by (1) and a hydroxyl group" may be an aspect in which the partial structure represented by Formula (1) and a hydroxyl group exist in the same component, or the partial structure represented by Formula (1) and The aspect in which a hydroxyl group exists in a heterogeneous component may be sufficient. For example, (A) A coloring agent is good also as a coloring composition containing the partial structure and hydroxyl group represented by Formula (1) by having the partial structure and hydroxyl group represented by Formula (1). Or when (A) a coloring agent has the partial structure represented by Formula (1), and (B) polymer has a hydroxyl group, it is good also as a coloring composition containing the partial structure and hydroxyl group represented by Formula (1).

In the coloring composition of the present disclosure, the content rate of the partial structure represented by the formula (1) is preferably 0.5% by mass or more with respect to the total amount of the total solid content of the coloring composition from the viewpoint of obtaining a colored cured film having high solvent resistance, , more preferably 2 mass % or more, and still more preferably 5 mass % or more. In addition, the content rate of the partial structure represented by the formula (1) is preferably 50 mass% or less, preferably 35 mass% or less, with respect to the total amount of the total solid content of the coloring composition from the viewpoint of improving fairness, It is more preferable that it is 20 mass % or less.

Further, in the coloring composition of the present disclosure, the content of hydroxyl groups is preferably 0.3% by mass or more, and more preferably 1% by mass or more with respect to the total amount of the total solid content of the coloring composition from the viewpoint of obtaining a colored cured film having high solvent resistance. It is preferable, and it is still more preferable that it is 3 mass % or more. Moreover, it is preferable that it is 35 mass % or less, and, as for the content rate of a hydroxyl group, it is preferable that it is 25 mass % or less with respect to the total amount of the total solid of a coloring composition from a viewpoint of making fairness favorable, It is more preferable that it is 15 mass % or less. .

In addition, in this specification, "solid content" means components other than the (E) solvent contained in a coloring composition. Therefore, "total solid content" refers to those other than (A) colorant, (B) polymer, and (C) polymerizable compound, (A) colorant, (B) polymer, (C) polymerizable compound, and (E) solvent. It means an ingredient that combines external ingredients. For example, even if it is a liquid photopolymerizable compound and additive component (surfactant etc.), these shall be contained in solid content.

(Compound having a partial structure represented by Formula (1) above)

In the formula (1), the alkyl group having 1 to 4 carbon atoms for ^{R 1} and R ^{2 may be linear or branched. R 1} and R ² are preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, from the viewpoint of allowing the reaction product between the partial structure represented by the formula (1) and the hydroxyl group to be discharged to the outside of the film. .

Since n1 and n2 can make reaction efficiency with a hydroxyl group higher, Preferably it is 0 or 1, More preferably, it is 0.

X<^1> should just be a bivalent coupling group which has an electron withdrawing property, and is not specifically limited. Here, the "bivalent coupling group which has an electron withdrawing property" means the group formed as a new bond by removing a hydrogen atom from the arbitrary position of an electron withdrawing group. In this case, it is thought that electron withdrawing property is shown in a bond different from a new bond. In addition, an electron withdrawing group is a substituent whose Hammett's substituent constant (sigma)p value is 0.15 or more, More preferably, it is a substituent 0.2 or more. Regarding Hammett's substituent constant, it follows Journal of Medicinal Chemistry, 1973, Vol.16, No.11, 1207-1216.

X ¹ is a carbonyl group (-CO-), an amide group (-CONR ⁴ -* ¹ ), an imide group (-CONR ⁴ CO-), an ester group ( -CO-O-* ¹ ), a sulfonyl group (-SO ₂ -), a sulfinyl group (-SO-), a thiocarbonyl group (-CS-), and a carbonimidyl group (-C (=NH)-) At least one selected from the group ^{consisting of (provided that R 4} is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and “* ¹ ” represents a bond bonded to ^{L 1} in the formula (1) above. ) is preferred. Among these, an amide group, a carbonyl group, or an ester group is more preferable, and, as for X<^{1>, an amide group or a carbonyl group is still more preferable.}

As a ^{divalent organic group of L<1>} , -O-, -CO-, -COO-, -NH-, - between the carbon-carbon bonds of a C1-C20 alkanediyl group and a C1-C20 alkanediyl group. The group etc. which have CONH- etc. are mentioned.

The compound having a partial structure represented by the formula (1) (hereinafter also referred to as “specific compound”) may be a low-molecular compound having no repeating unit (hereinafter simply referred to as “low-molecular compound”) or a polymer. In addition, in this specification, a "low molecular weight compound" does not have molecular weight distribution, and molecular weight is preferably a compound of 1,000 or less. It is preferable that a specific compound is a polymer at the point which can obtain the colored film excellent in solvent resistance, and it is preferable that it is a polymer containing the structural unit (a) which has a partial structure specifically specifically represented by said Formula (1). When a specific compound is a polymer, the (A) coloring agent may be sufficient as the said specific compound, and the (B) polymer may be sufficient as it. Moreover, as a specific compound, the (A) coloring agent and the (B) polymer may be contained in the coloring composition.

The structural unit (a) should just have a partial structure represented by said Formula (1), and another partial structure is not specifically limited. Since the partial structure represented by the formula (1) is easily introduced into the side chain of the polymer, the structural unit (a) is a structural unit derived from a monomer having an ethylenically unsaturated group (hereinafter also referred to as “ethylenically unsaturated monomer”). It is preferable, and it is more preferable that it is a structural unit derived from at least 1 sort(s) chosen from the group which consists of a (meth)acrylic-type monomer, a styrene-type monomer, and a maleimide-type monomer. Among these, it is preferable that it is a structural unit derived from a (meth)acrylic-type monomer, and, as for a structural unit (a), it is especially preferable that it is a structural unit represented by following formula (1-2). In addition, in this specification, "(meth)acryl" is a concept containing acryl and methacryl.

(In Formula (1-2), R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ¹ , R ² , L ¹ , X ¹ , n1 and n2 each have the same meaning as in Formula (1) above. to be.)

In the above formula (1-2), the description of the above formula (1) applies to the description of specific examples and preferred examples of ^{R 1} , R ² , L ¹ , X ^{1 , n1 and n2.}

R ³ is preferably a hydrogen atom or a methyl group. Since the colored film excellent in solvent resistance can be obtained, C1-C10 is preferable, as for ^{L<1>, C1-C5 is more preferable, and C1-C3 is still more preferable.}

(Hydroxy group-containing compound)

The compound having a hydroxyl group (hereinafter also referred to as a “hydroxyl group-containing compound”) may be a compound having at least one hydroxyl group in one molecule. A low molecular weight compound may be sufficient as this hydroxyl-containing compound, and a polymer may be sufficient as it. In addition, the compound containing a hydroxyl group may be the same compound as a specific compound, or a different compound may be sufficient as it. When a hydroxyl-containing compound and a specific compound are the same compound, the said compound has the partial structure and hydroxyl group represented by said Formula (1) in 1 molecule. In this case, although a hydroxyl group may be included in the partial structure represented by said Formula (1), it is preferable that the partial structure and hydroxyl group represented by said Formula (1) exist in a different site|part (that is, in a different structural unit).

Here, in the composition of the present disclosure, including a partial structure with a hydroxyl group represented by the above formula (1), the formula (1) group "OR ^1" and the group at least one of the transesterification of the hydroxyl group of the "OR ^2" in It is thought that a reaction occurs, whereby a cross-linked structure is formed within or between molecules to cure. This transesterification reaction is a reversible reaction, and the progress of the transesterification reaction is suppressed in a state in which equilibrium is maintained. Thereby, in the state in which the equilibrium before heating was maintained, the coloring composition does not harden|cure, but it is thought that the mixed state of (A) coloring agent, (B) polymer, and (C) polymeric compound is maintained stably.

On the other hand, when the composition is coated and heated to cause an equilibrium shift, a transesterification reaction between at least one ^{of the group “OR 1} ” and the group “OR ^{2 ” in the formula (1) and a hydroxyl group occurs.} It is thought that the transesterified "HO-R ¹ ” or “H-OR ² ” is discharged to the outside of the system and equilibrium shift occurs, thereby forming a cross-linked structure between the specific compound and the hydroxyl group-containing compound and curing the composition. Moreover, this transesterification reaction advances at low temperature of 180 degrees C or less, for example, and it is possible to generate film hardening. By using such a transesterification reaction, according to the coloring composition of this indication, it is estimated that storage stability and low temperature sclerosis|hardenability are compatible.

(Formulation of the coloring composition)

The coloring composition of this indication has the partial structure which at least 1 sort(s) chosen from the group which consists of (A) coloring agent, (B) polymer, and (C) polymeric compound is represented by said Formula (1), and (A) coloring agent As long as at least 1 sort(s) selected from the group which consists of (B) a polymer and (C) a polymeric compound has a hydroxyl group, the compounding aspect is not specifically limited. That is, any of the (A) coloring agent, (B) polymer, and (C) polymeric compound may be sufficient as a specific compound, and 2 or more types of these may be sufficient as it. Similarly, any of (A) coloring agent, (B) polymer, and (C) polymeric compound may be sufficient as a hydroxyl-containing compound, and 2 or more types of these may be sufficient as it. Moreover, at least any one of (A) coloring agent, (B) polymer, and (C) polymeric compound may contain the compound which has the partial structure and hydroxyl group represented by said Formula (1).

As a specific aspect of the composition of a coloring composition, the compounding aspect of the following [1]-[8] is mentioned, for example.

[1] (A) contains a polymer having a partial structure and a hydroxyl group represented by the formula (1) as a colorant, and (B) contains a polymer having a hydroxyl group and not having a partial structure represented by the formula (1) as a polymer, (C) The aspect containing the compound which has a hydroxyl group and does not have the partial structure represented by said Formula (1) as a polymeric compound.

[2] (B) a polymer containing a polymer having a partial structure and a hydroxyl group represented by the formula (1) as a polymer, and (C) a compound having a hydroxyl group as a polymerizable compound and not having a partial structure represented by the formula (1) containing sun. However, (A) coloring agent does not have the partial structure and hydroxyl group represented by said Formula (1).

[3] (A) containing a compound having a hydroxyl group as a colorant and not having a partial structure represented by the formula (1), and (B) a polymer having a partial structure represented by the formula (1) as a polymer and not having a hydroxyl group (C) The aspect containing the compound which has a hydroxyl group as a polymeric compound and does not have the partial structure represented by said Formula (1).

[4] (B) a polymer having a partial structure represented by the formula (1) and not having a hydroxyl group as the polymer; (C) a polymerizable compound having a hydroxyl group and not having a partial structure represented by the formula (1) Aspects containing the compound. However, (A) coloring agent does not have the partial structure and hydroxyl group represented by said Formula (1).

[5] (A) contains a polymer having a partial structure and a hydroxyl group represented by the formula (1) as a colorant, (B) contains a polymer having a partial structure and a hydroxyl group represented by the formula (1) as a polymer, ( C) The aspect containing the compound which has a hydroxyl group and does not have the partial structure represented by said Formula (1) as a polymeric compound.

[6] (A) containing a polymer having a partial structure and a hydroxyl group represented by the above formula (1) as a colorant, and (B) a polymer containing a hydroxyl group as a polymer and not having a partial structure represented by the above formula (1) Sun. However, (C) polymeric compound does not have the partial structure and hydroxyl group represented by said Formula (1).

[7] (A) containing a polymer having a hydroxyl group as a colorant and not having a partial structure represented by the above formula (1), and (B) a polymer having a partial structure represented by the above formula (1) as a polymer and not having a hydroxyl group (C) The aspect containing the compound which has a hydroxyl group as a polymeric compound and does not have the partial structure represented by said Formula (1).

[8] (A) containing a polymer having a hydroxyl group as a colorant, (B) containing a polymer having a hydroxyl group as a polymer, and (C) containing a compound having a partial structure represented by Formula (1) as a polymerizable compound Sun. However, at least one of (A) a coloring agent and (B) polymer may further have the partial structure represented by said Formula (1).

Hereinafter, each component contained in the coloring composition of this indication and the component contained as needed are demonstrated in detail.

<(A) Colorant>

(A) A color and a kind are suitably selected according to a use for a coloring agent. (A) As a colorant, any of a pigment, dye, a quantum dot, and a natural dye can be used. It is preferable that it is at least any one of a pigment and dye, and, as for (A) a coloring agent, it is especially preferable that it is a point which can obtain the pixel with high brightness|luminance and color purity, and it is especially preferable that dye is included. It is preferable that the pigment and dye mix|blended with a coloring composition are organic substances. (A) As a coloring agent, the other coloring agent which does not have a specific compound, a hydroxyl-containing compound, and the partial structure and hydroxyl group represented by said Formula (1) is mentioned.

(for specific compounds)

One aspect of the coloring composition of this indication WHEREIN: (A) The coloring agent contains a specific compound. (A) The specific compound as a coloring agent should just have the partial structure represented by said Formula (1), and is not specifically limited. When the specific compound is a polymer, a polymer having a partial structure represented by the formula (1) can be obtained relatively easily using a conventional polymerization method, (A) The specific compound as a colorant contains a structural unit (a ) and a polymer (hereinafter, also referred to as "polymer (A1)") containing a structural unit (b) having a dye structure is preferable.

Here, in this specification, a "dye structure" is a partial structure derived from a pigment|dye, and is a chromophore. The dye structure may have an electric charge. When the dye structure has an electric charge, the dye structure may be in any form of an intramolecular salt or an intermolecular salt. It is possible to employ|adopt the structure derived from a well-known pigment|dye, and a pigment|dye structure is not specifically limited. Specifically, for example, dipyrromethene dye, diarylmethane dye, triarylmethane dye, xanthene dye, acridine dye, anthraquinone dye, azo dye, quinoneimine dye, polymethine dye (oxonol dye, a structure derived from a pigment selected from melocyanine pigment, arylidene pigment, styryl pigment, cyanine pigment, squarylium pigment, croconium pigment, etc.), phthalocyanine pigment, subphthalocyanine pigment, and these metal complex pigments can be heard Among them, from the viewpoint of color characteristics, a structure derived from a dye selected from the group consisting of triarylmethane dyes, xanthene dyes, anthraquinone dyes, azo dyes, quinoneimine dyes, polymethine dyes, subphthalocyanine dyes and phthalocyanine dyes is Preferably, a structure derived from a dye selected from the group consisting of a triarylmethane dye, a xanthene dye, a quinoneimine dye, and a polymethine dye is more preferable, and a triarylmethane dye, a xanthene dye, a quinoneimine dye and a cyanine dye. The structure derived from the pigment|dye chosen from the group is more preferable. In addition, for specific dyes capable of forming a dye structure, "New Edition Dye Handbook" (compiled by the Association of Organic Synthetic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colourists), "Dye Handbook" ( Compiled by Ogawara et al.; Kodansha, 1986) et al.

The dye structure may be constituted by a cation moiety or an anion moiety, and examples thereof include a salt of a cationic chromophore and a counter anion, and a salt of an anionic chromophore and a counter cation. An organic ion may be sufficient as a counter ion, and an inorganic ion may be sufficient as it. As used herein, the term "cationic chromophore" refers to an atomic group having an electrostatic charge. Incidentally, when the atomic group has a functional group having a positive charge and a functional group having a negative charge, and the total of these charges becomes a positive charge, it is included in the cationic chromophore. An "anionic chromophore" refers to an atomic group having a negative charge. Incidentally, when the atomic group has a functional group having a positive charge and a functional group having a negative charge, and the total of these charges becomes a negative charge, it is included in the anionic chromophore. In addition, an electrically neutral chromophore may be sufficient as a dye structure. "Electrically neutral chromophore" is an atomic group that is neither a cationic chromophore nor an anionic chromophore, and does not have a functional group having a positive charge and a functional group having a negative charge, or a functional group having a positive charge and a negative charge. Even if it has a functional group to have, the total number of positive charges and the total number of negative charges are the same, and it refers to an atomic group which is electrically neutral as a whole.

The structural unit (a) is preferably a structural unit derived from a compound represented by the following formula (a1) from the viewpoint that a polymer having a partial structure represented by the formula (1) can be obtained relatively easily. Specific examples of the compound represented by the following formula (a1) include compounds represented by each of the following formulas (a1-1) to (a1-9).

(In formula (a1), R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ¹ , R ² , L ¹ , X ¹ , n1 and n2 have the same meanings as in the formula (1), respectively. )

(In formulas (a1-1) to (a1-9), R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

In a polymer (A1), it is preferable that the content rate of a structural unit (a) is 5 mass % or more with respect to all the structural units which a polymer (A1) has from the point which can make the solvent resistance of a cured film sufficiently high, It is more preferable that it is 10 mass % or more, and it is still more preferable that it is 15 mass % or more. Moreover, it is preferable that the content rate of a structural unit (a) is 50 mass % or less with respect to all the structural units which a polymer (A1) has at the point which can maintain workability|operativity and favorable colorability at the time of preparing a coloring composition, It is more preferable that it is 45 mass % or less, and it is still more preferable that it is 40 mass % or less.

It is preferable that a structural unit (b) is a structural unit derived from the ethylenically unsaturated monomer which has a pigment|dye structure. It is preferable that the dye structure which a structural unit (b) has is a structure derived from the dye chosen from the group which consists of an ionic dye and a nonionic dye from the point which can obtain a pixel with high brightness|luminance and color purity. Here, in this specification, the ionic dye in which the chromophore has an acidic group is called "anionic dye". Anionic dye is a meaning including the ionic dye which has formed the acidic group and the salt. Similarly, an ionic dye in which the chromophore has a basic group is called a “cationic dye”. The cationic dye is meant to include an ionic dye forming a salt with a basic group. "Nonionic dyes" are dyes other than cationic dyes and anionic dyes.

The structural unit (b) is at least one selected from the group consisting of (meth)acrylic monomers, styrene-based monomers, and maleimide-based monomers among ethylenically unsaturated monomers from the viewpoint of easy introduction of the dye structure into the side chain of the polymer. It is preferable that it is a structural unit derived from Among these, it is preferable that it is a structural unit derived from a (meth)acrylic-type monomer, and it is especially preferable that it is a structural unit represented by a following formula (b1).

(In formula (b1), R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. L ² is a single bond or a divalent organic group, and Y ¹ is a structure derived from an ionic dye or a nonionic dye. It is a monovalent group with

In the formula (b1), as the ^{divalent organic group of L 2} , the methylene group of an alkanediyl group having 1 to 20 carbon atoms and an alkanediyl group having 1 to 20 carbon atoms is -O-, -CO-, -COO-, - and groups substituted with NH-, -CONH-, -S-, -O-CO-Ph-CO-O- (Ph is a phenylene group), and the like.

In Y ¹ , examples of the structure derived from the nonionic dye include triarylmethane dyes, cyanine dyes, xanthene dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, quinophthalone dyes, coumarin dyes, and pyrazolones. The structure derived from well-known dyes, such as dye, a quinoline dye, a nitro dye, a quinoneimine dye, a phthalocyanine dye, and a squarylium dye, is mentioned. Among them, from the viewpoint of heat resistance, the structure derived from the nonionic dye is a structure derived from a triarylmethane dye, a cyanine dye, a xanthene dye, an anthraquinone dye, a dipyrromethene dye, a squarylium dye, or a phthalocyanine dye. desirable.

In Y ¹ , specific examples of the structure derived from the ionic dye include a structure composed of a cationic chromophore and a counter anion, and a structure composed of an anionic chromophore and a counter cation. In the formula (b1), the bond between the dye structure of ^{Y 1 and L 2 is, when the dye structure of Y 1} has a structure comprising a cationic chromophore and a counter anion, any of a cationic chromophore and a counter anion is directly Or it is formed by bonding ^{to L 2} through a divalent linking group. In addition, ^{when the dye structure of Y 1} is a structure comprising an anionic chromophore and a counter cation, the binding between the dye structure of ^{Y 1 and L 2} is that either the anionic chromophore or the counter cation is directly or via a divalent linking group. formed by binding to L ^{2 .}

Examples of the cationic chromophore include triarylmethane chromophore, cyanine chromophore, xanthene chromophore, polymethine chromophore, azo chromophore, diarylmethane chromophore, quinoneimine chromophore, anthraquinone chromophore, phthalocyanine chromophore, squarylium chromophore, quinope. Talon chromophore and the like. Of these, the cationic chromophore is preferably a triarylmethane chromophore, a cyanine chromophore, a xanthene chromophore, a polymethine chromophore, or an azo chromophore, and more preferably a triarylmethane chromophore or a cyanine chromophore. As the cationic chromophore, in the color index (C.I.; published by The Society of Dyers and Colorists), a cationic moiety of a dye classified as C.I. Basic may be used.

In the structure comprising a cationic chromophore and a counter anion, the counter anion is not particularly limited, and examples thereof include the anion described in Paragraph 0034 of JP-A-2015-129263. Among these, a sulfonate anion, an imide anion, or a carboxylate anion is preferable, an imide anion is more preferable, and a sulfonylimide anion is still more preferable.

Examples of the anionic chromophore include triarylmethane chromophore, polymethine chromophore, azo chromophore, diarylmethane chromophore, quinoneimine chromophore, anthraquinone chromophore, phthalocyanine chromophore, xanthene chromophore, squarylium chromophore, quinophthalone chromophore, and the like. can be heard Among them, the anionic chromophore is preferably a triarylmethane chromophore, an azo chromophore, a phthalocyanine chromophore or a xanthene chromophore, _{and having at least one substituent of -SO 3} - and -CO ₂ - triarylmethane chromophore, azo chromophore, A phthalocyanine chromophore or a xanthene chromophore is more preferable. As the anionic chromophore, an anion moiety of a dye classified as CI acid in the color index may be used.

In the structure comprising an anionic chromophore and a counter cation, examples of the counter cation include an ammonium cation, a phosphonium cation, a sulfonium cation, an iodonium cation, and a diazonium cation. Among these, an ammonium cation or a phosphonium cation is preferable and, as for a counter cation, an ammonium cation is more preferable.

In a polymer (A1), it is preferable that the content rate of a structural unit (b) is 30 mass % or more with respect to all the structural units which a polymer (A1) has from a viewpoint of obtaining the coloring agent which shows favorable colorability, and it is 40 mass % It is more preferable that it is more than it, and it is still more preferable that it is 50 mass % or more. Moreover, it is preferable that the content rate of a structural unit (b) is 99 mass % or less with respect to all the structural units which a polymer (A1) has from a viewpoint of ensuring the developer solubility of a polymer (A1), and it is 98 mass % or less It is more preferable, and it is still more preferable that it is 95 mass % or less.

The polymer (A1) may have only the structural unit (a) and the structural unit (b), but from the viewpoint of improving solvent resistance, heat resistance, and dispersibility, any of the partial structure and the dye structure represented by the formula (1) It is preferable to further have a structural unit (c) which does not have any. The structural unit (c) is preferably a structural unit derived from an ethylenically unsaturated monomer, and a structural unit derived from at least one selected from the group consisting of (meth)acrylic monomers, styrenic monomers, and maleimide monomers. It is more preferable that

As a specific example of the monomer (hereinafter also referred to as "other monomers") forming the structural unit (c), for example, alkyl (meth) acrylate, alkenyl (meth) acrylate, aryl (meth) acrylate, Hydroxyalkyl (meth) acrylate, primary amino group-containing alkyl (meth) acrylate, secondary amino group-containing alkyl (meth) acrylate, tertiary amino group-containing alkyl (meth) acrylate, alicyclic hydrocarbon group (meth) Acrylic acid esters, aromatic vinyl compounds, (meth)acrylic acid esters of polyhydric alcohols, N-substituted maleimides, vinyl ethers, ethylenically unsaturated monomers having an oxygen-containing saturated heterocycle, mono (meth) at the end of the polymer molecular chain The macromonomer etc. which have an acryloyl group are mentioned. The polymer (A1) may have only 1 type of structural unit (c), and may have 2 or more types.

As other monomers, by using a monomer having a hydroxyl group (hereinafter also referred to as a “hydroxyl group-containing monomer”), (A) as a colorant, a polymer having a partial structure represented by the formula (1) and a hydroxyl group and a dye structure (hereinafter, "Polymer (A1-1)") can be obtained. By using such a polymer (A1-1) as a (A) coloring agent, a crosslinked structure is formed between molecules of a polymer (A1-1), and it is preferable at the point which can fully suppress the elution of the coloring agent from a cured film. In addition, the polymer (A1-1) is also a specific compound and a hydroxyl-containing compound. The hydroxyl group-containing monomer is preferably an ethylenically unsaturated monomer, more preferably at least one selected from the group consisting of a (meth)acrylic monomer, a styrene monomer, and a maleimide monomer, and a (meth)acrylic monomer and styrene It is more preferable that it is at least 1 sort(s) chosen from the group which consists of a system monomer, and it is especially preferable that it is a (meth)acrylic-type monomer.

As a specific example of the (meth)acrylic-type monomer which has a hydroxyl group, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylic acid hydroxyalkyl esters such as (meth)acrylate and 8-hydroxyoctyl (meth)acrylate; caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (meth)acrylate; oxyalkylene-modified monomers such as diethylene glycol (meth) acrylate and polyethylene glycol (meth) acrylate; Primary hydroxyl group and secondary hydroxyl group containing monomers, such as glycerol mono(meth)acrylate;

Side chain glycerides such as 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, and glycidyl (meth) acrylate A monomer in which an acid monomer such as (meth)acrylic acid is added to a cidyl group, a monomer in which a side chain glycidyl group such as glycidyl (meth)acrylate is added to an acid monomer such as (meth)acrylic acid, 3,4 - A monomer to which an acid monomer such as (meth)acrylic acid is added to an alicyclic epoxy group of a side chain such as epoxycyclohexylmethyl (meth)acrylate, or 3,4-epoxycyclohexylmethyl to an acid monomer such as (meth)acrylic acid A monomer to which an alicyclic epoxy group of a side chain such as (meth)acrylate is added, and a side chain oxetanyl group such as (3-ethyl-3-oxetanyl)methoxymethyl (meth)acrylate (meth)acrylic acid 2, such as a monomer to which an acid monomer is added, and a monomer to which a side chain oxetanyl group such as (3-ethyl-3-oxetanyl)methoxymethyl (meth)acrylate is added to an acid monomer such as (meth)acrylic acid a monomer containing a hydroxyl group;

Tertiary hydroxyl-containing monomers, such as 2, 2- dimethyl- 2-hydroxyethyl (meth)acrylate, etc. are mentioned. As a hydroxyl-containing monomer, 1 type may be used individually, and 2 or more types may be used together.

The hydroxyl group-containing monomer used for the synthesis of the polymer (A1-1) ^{has excellent reactivity with the group “OR 1} ” and the group “OR ² ” of the partial structure represented by the formula (1), and therefore is a primary in the polymer side chain. and/or a monomer having a secondary alcoholic hydroxyl group is preferable. Among them, the hydroxyl group-containing monomer is preferably at least one selected from the group consisting of a primary hydroxyl group-containing monomer, a primary hydroxyl group and secondary hydroxyl group-containing monomer, and a secondary hydroxyl group-containing monomer. Examples of the primary hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate. (meth)acrylic acid hydroxyalkyl esters, such as 8-hydroxyoctyl (meth)acrylate, are especially preferable. As a primary hydroxyl group and secondary hydroxyl group containing monomer, glycerol mono(meth)acrylate is especially preferable. Examples of the secondary hydroxyl group-containing monomer include a monomer obtained by adding an acid monomer such as (meth)acrylic acid to a side chain glycidyl group such as glycidyl (meth)acrylate, and glycidyl to an acid monomer such as (meth)acrylic acid. A monomer to which a glycidyl group of a side chain such as (meth)acrylate is added, an acid monomer such as (meth)acrylic acid is added to an alicyclic epoxy group of a side chain such as 3,4-epoxycyclohexylmethyl (meth)acrylate Monomer, a monomer obtained by adding an alicyclic epoxy group of a side chain such as 3,4-epoxycyclohexylmethyl (meth)acrylate to an acid monomer such as (meth)acrylic acid, (3-ethyl-3-oxetanyl)methoxy A monomer obtained by adding an acid monomer such as (meth)acrylic acid to a side chain oxetanyl group such as methyl (meth)acrylate, and (3-ethyl-3-oxetanyl)methyl to an acid monomer such as (meth)acrylic acid A monomer to which a side chain oxetanyl group such as oxymethyl (meth)acrylate is added is particularly preferable.

As a method for obtaining the polymer (A1-1), in addition to the method of polymerization (method [1a]) using the above-mentioned hydroxyl group-containing monomer, a specific group-containing monomer, and a monomer having a dye structure as a raw material monomer, the following method [2a] to [4a] are mentioned.

Method [2a]: A polymer having an epoxy group in a side chain is obtained by polymerizing an epoxy group-containing monomer (or a carboxyl group-containing monomer), a specific group-containing monomer, and a monomer having a dye structure as a raw material monomer, and then the polymer and the carboxyl group A method of introducing a hydroxyl group (more specifically, a secondary hydroxyl group) into a side chain by reacting a group-containing compound (or an epoxy group-containing compound).

Method [3a]: Using a polymerization initiator having a hydroxyl group (for example, 2,2'-azobis(2-methyl-N-(2-hydroxyethyl)propionamide), etc.), a specific group-containing monomer and A method of polymerizing a raw material monomer containing a monomer having a dye structure.

Method [4a]: a specific group-containing monomer and a dye using a chain transfer agent containing a hydroxyl group (eg, monoethanolamine thioglycolic acid, 2,3-dihydroxy-1,4-butanedithiol, etc.) A method of polymerizing a raw material monomer comprising a monomer having a structure.

Among these, according to method [1a] and method [2a], the polymer which has a hydroxyl group in a side chain can be obtained. Further, according to the method [3a] and the method [4a], a polymer having a hydroxyl group at the end of the main chain can be obtained. Here, in this specification, "having a hydroxyl group at the end of a main chain" means that a bond is formed with respect to the structural unit which does not form a bond with the adjacent structural unit in the main chain structure.

In the method [2a], the epoxy group-containing monomer is preferably a (meth)acrylic monomer, for example, an oxiranyl group-containing (meth)acrylic monomer such as glycidyl (meth)acrylate; alicyclic epoxy group-containing (meth)acrylic monomers such as 3,4-epoxycyclohexylmethyl (meth)acrylate; (3-ethyl-3-oxetanyl) oxetanyl group containing (meth)acrylic monomers, such as methoxymethyl (meth)acrylate, etc. are mentioned. As a carboxy group containing compound, the compound which has a carboxy group and an ethylenically unsaturated bond is preferable, (meth)acrylic-type compound is more preferable, (meth)acrylic acid is especially preferable. The polymer (A1-1) is preferably a polymer having a hydroxyl group in at least a side chain from the viewpoint of easy adjustment of the amount of the hydroxyl group in the polymer and the ability to obtain a hydroxyl group-containing polymer relatively easily.

In a polymer (A1-1), it is preferable that the content rate of the structural unit which has a hydroxyl group is 0.5 mass % or more with respect to all the structural units which a polymer (A1-1) has from a viewpoint of obtaining a colored cured film with high solvent resistance. And it is more preferable that it is 1 mass % or more, and it is still more preferable that it is 5 mass % or more. Moreover, it is preferable that it is 50 mass % or less with respect to all the structural units which a polymer (A1-1) has from a viewpoint of making storage stability favorable, and, as for the content rate of the structural unit which has a hydroxyl group, it is more preferable that it is 45 mass % or less. And it is more preferable that it is 40 mass % or less.

In addition, the method of obtaining a polymer (A1) is not specifically limited. The polymer (A1) can be produced, for example, by radical polymerization, anionic polymerization, cationic polymerization, living radical polymerization, living anionic polymerization, living cationic polymerization, and the like using the above monomers. In the case where the polymer (A1-1) is produced by the above method [2a], the reaction between the epoxy group-containing monomer and the carboxy group-containing compound can be carried out according to a known method, for example, in a solution.

(About hydroxyl-containing compounds)

One aspect of the coloring composition of this indication WHEREIN: (A) A coloring agent contains a hydroxyl-containing compound. (A) A low molecular weight compound may be sufficient as the hydroxyl-containing compound as a coloring agent, and a polymer may be sufficient as it. (A) When using a low-molecular compound having a hydroxyl group as a colorant, the low-molecular compound is a dye (hereinafter also referred to as “hydroxyl group-containing dye (A2-1)”) from the viewpoint that a colored cured film having high luminance and color purity can be obtained. ) is preferred. The hydroxyl group-containing dye (A2-1) may be any of a nonionic dye and an ionic dye, and in the case of an ionic dye, any of an anionic dye and a cationic dye may be sufficient as it.

From a viewpoint of making solvent resistance and storage stability compatible, 1-10 pieces are preferable, and, as for the number of the hydroxyl groups which hydroxyl-containing dye (A2-1) has, it is more preferable that it is 2-8 pieces.

As a hydroxyl-containing dye (A2-1), the hydroxyl-containing dye of Unexamined-Japanese-Patent No. 2013-173850, the international publication 2014/192973 pamphlet etc. is mentioned, for example. Moreover, it can manufacture by a well-known method using the well-known dye illustrated above as a raw material. As for the hydroxyl-containing dye (A2-1), 1 type may be used individually, and 2 or more types may be used.

(A) When using the polymer which has a hydroxyl group as a coloring agent, as said polymer, other than the said polymer (A1-1), it has a hydroxyl group and a pigment|dye structure, and does not have the partial structure represented by said Formula (1) (the following) , also referred to as "hydroxyl group-containing polymer (A2-2)"). The hydroxyl group-containing polymer (A2-2) should just have a hydroxyl group and a pigment|dye structure, and the position of a hydroxyl group, etc. are not specifically limited. That is, the hydroxyl group-containing polymer (A2-2) may have a hydroxyl group in the side chain, may have it in the main chain terminal, and may have it in both the side chain and the main chain terminal. As a method for obtaining the hydroxyl group-containing polymer (A2-2), in the methods [1a] to [4a] described for the polymer (A1-1), a method of polymerization without using a specific group-containing monomer is exemplified. In addition, when manufacturing a hydroxyl-containing polymer (A2-2), only 1 type of these methods may be used, or 2 or more types may be combined. The polymer (A2-2) is preferably a polymer having a hydroxyl group in at least a side chain from the viewpoint of facilitating adjustment of the amount of the hydroxyl group and relatively easily obtaining a hydroxyl group-containing polymer.

In a polymer (A2-2), it is preferable that the content rate of the structural unit which has a hydroxyl group is 0.5 mass % or more with respect to all the structural units which a polymer (A2-2) has from a viewpoint of obtaining a colored cured film with high solvent resistance. And it is more preferable that it is 1 mass % or more, It is still more preferable that it is 3 mass % or more, It is still more preferable that it is 5 mass % or more. In addition, the content rate of the structural unit having a hydroxyl group is preferably 70 mass % or less, more preferably 60 mass % or less, with respect to the total structural units of the polymer (A2-2) from the viewpoint of obtaining good colorability, It is more preferable that it is 50 mass % or less.

(A) When a coloring agent is a polymer, it is preferable that the weight average molecular weights (Mw) of the said polymer measured by gel permeation chromatography (GPC) are 1,000-100,000. Mw becomes like this. Preferably it is 3,000 or more. Moreover, Mw becomes like this. Preferably it is 50,000 or less. If Mw is 1,000 or more, it is preferable at the point which a pattern shape becomes favorable, and if it is 100,000 or less, resolution time does not become too long, but it is preferable from a viewpoint of ensuring fairness. Moreover, when (A) a coloring agent is a polymer, ratio (Mw/Mn) of Mw of the said polymer to a number average molecular weight (Mn) becomes like this. Preferably it is 1.0-5.0, More preferably, it is 1.0-3.0.

(other colorants)

The coloring composition may contain at least one of a specific compound and a hydroxyl group-containing compound as the (A) coloring agent, but a coloring agent having neither a partial structure nor a hydroxyl group represented by the formula (1) (hereinafter also referred to as "other coloring agents") ) may be used together. Moreover, when the partial structure and hydroxyl group represented by said Formula (1) are included in at least 1 sort(s) of component chosen from the group which consists of (B) polymer and (C) polymeric compound, a coloring composition is (A) coloring agent As such, it may contain only other colorants.

The other coloring agent is not specifically limited, A color and a kind can be suitably selected according to a use. As another colorant, any of a pigment, dye, quantum dot, and natural dye can be used. When the coloring composition of the present disclosure is used for formation of each color pixel constituting a color filter, since pixels with high luminance and color purity can be obtained, the other colorant is at least one selected from the group consisting of pigments and dyes. The species is preferred, and at least one selected from the group consisting of organic pigments and organic dyes is more preferred.

As an organic pigment, the compound classified as a pigment in the color index (CI; issued by The Society of Dyers and Colorists), ie, the thing to which the following color index (CI) name is attached is mentioned, The following organic pigments can be preferably used.

C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 264, C.I. red pigments such as Pigment Red 279;

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Green pigments, such as Pigment Green 59;

C.I. Pigment Blue 15:6, C.I. Pigment Blue 16, C.I. Pigment Blue 79, C.I. Pigment Blue 80, C.I. Blue pigments, such as Pigment Blue 60;

C.I. Pigment Yellow 83, C.I. Pigment Yellow 129, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 179, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, C.I. Pigment Yellow 211, C.I. Pigment Yellow 215, C.I. Yellow pigments, such as Pigment Yellow 231;

C.I. Orange pigments, such as Pigment Orange 38; C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. purple pigments, such as pigment violet 29; Black pigments, such as a lactam type black pigment and a perylene type black pigment.

Moreover, as an organic pigment, other than the above, the brominated diketopyrrolopyrrole pigment represented by Formula (Ic) of Unexamined-Japanese-Patent No. 2011-523433 can also be used.

Carbon black, titanium black, etc. are mentioned as an inorganic pigment. In addition, as an inorganic pigment, Unexamined-Japanese-Patent No. 2001-081348, Unexamined-Japanese-Patent No. 2010-026334, Unexamined-Japanese-Patent No. 2010-237384, Unexamined-Japanese-Patent No. 2010-237569, Unexamined-Japanese-Patent No. 2011-006602 and lake pigments described in Japanese Patent Application Laid-Open No. 2011-145346 and the like.

Moreover, when using a pigment, you may refine|purify and use a pigment by the recrystallization method, the reprecipitation method, the solvent washing|cleaning method, the sublimation method, the vacuum heating method, or these combination. Moreover, if desired, you may modify|reform the particle|grain surface of a pigment with resin, and may use it. In addition, when using an organic pigment, you may refine|miniaturize and use a primary particle by so-called salt milling. As a method of salt milling, the method of Unexamined-Japanese-Patent No. 08-179111 is employable, for example.

It does not specifically limit as dye, For example, in addition to the compound classified as Dye in the said color index, well-known dye can be used. As such a dye, the well-known dye illustrated above is mentioned. Among the above, from the viewpoint of heat resistance, triarylmethane dyes, cyanine dyes, xanthene dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, and phthalocyanine dyes are preferable.

The dye may be composed of a cation moiety and an anion moiety. Examples of such a dye include a salt of a cationic chromophore and a counter anion, or a salt of an anionic chromophore and a counter cation. For examples of cationic chromophores, counter anions, anionic chromophores and counter cations, the above description applies.

As for the coloring composition of this indication, a dispersing agent may be mix|blended with (A) coloring agent as needed. Moreover, you may make the coloring composition contain a dispersing auxiliary agent with a dispersing agent. A well-known thing can be used as a dispersing agent and a dispersing auxiliary agent. Specifically, as the dispersing agent, for example, a urethane-based dispersant, a polyethyleneimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene alkylphenyl ether-based dispersant, a polyethylene glycol diester-based dispersant, a sorbitan fatty acid ester-based dispersant, and a poly ester-based dispersants, acrylic-based dispersants, and the like; As a dispersing aid, a pigment derivative etc. are mentioned, respectively, for example.

As a specific example of a dispersing agent, As a basic dispersing agent, For example, Solsperse 11200, Solsperse 13240, Solsperse 13650, Solsperse 13940, Solsperse 16000, Solsperse 17000, Solsperse 18000, Solsperse 20000, Solsperse 24000SG, Solsperse 24000SG, Solsperse. 24000GR, solspurs 28000, solspurs 31845, solspurs 32000, solspurs 32500, solspurs 32550, solsperse 32600, solspurs 33000, solspurs 34750, solsperth 35100, solsperth 35200, solspurs 37500, solspurs 38500, Solsperse 39000, Solsperse 56000, Solsperse 71000, Solsperse 76400, Solsperse 76500, Solsperse X300, Solsperse 9000, Solsperse J200 (above, manufactured by Lubrizol), DISPERBYK-108, DISPERBYK-109, DISPERBYK- 112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-182, DISPERBYK-183, DISPERBYK-184, DISPERBYK-185, DISPERBYK-2000, DISPERBYK-2008, DISPERBYK-2009, DISPERBYK-2022, DISPERBYK-2050, DISPERBYK-2150, DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164, BYK-9077 (above, manufactured by Big Chem.) , Ajisper PB821, PB822, PB823, PB824, PB827 (above, manufactured by Ajinomoto Fine Techno) and the like.

Examples of the acid dispersant include solsperse 3000, solsperse 21000, solsperse 26000, solsperse 36600, solspurs 41000, solsperse 41090, solsperse 43000, solsperth 44000, solsperse 46000, solsperse 47000, solsperse 55000 (above, Lubrizol Corporation), DISPERBYK-102, DISPERBYK-111, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-2096, BYK-P104, BYK-P104S, BYK-P105, BYK-220S (above, Big Chemis) manufacture) and the like. A dispersing agent may be used individually by 1 type, or 2 or more types may be combined and used for it.

(A) The content rate of a coloring agent can be suitably selected according to a use etc. From a viewpoint of forming a pixel with high brightness|luminance and excellent in color purity, and a viewpoint of forming the black matrix excellent in light-shielding property, the content rate of (A) coloring agent with respect to the total amount of the total solid of a coloring composition, Preferably 5- 70 mass %. (A) To [ the content rate of a coloring agent / the total amount of the total solid of a coloring composition ], More preferably, it is 8 mass % or more, More preferably, it is 10 mass % or more, Especially preferably, it is 12 mass % or more. Moreover, (A) The content rate of a coloring agent with respect to the total amount of the total solid of a coloring composition, More preferably, it is 60 mass % or less, More preferably, it is 55 mass % or less, Especially preferably, it is 45 mass % or less. .

(A) It is preferable that the content rate of dye in a coloring agent shall be 5 mass % or more with respect to the total amount of (A) coloring agent. Generally, since dye is inferior in heat resistance, when forming a cured film using the coloring composition containing dye, it is difficult to heat a coating film at the post-baking temperature of 200 degreeC or more. On the other hand, the coloring composition of this indication is less than 200 degreeC, Preferably, even when it post-baking at the temperature of 180 degrees C or less, the cured film excellent in solvent resistance can be formed. Therefore, the coloring composition of this indication can increase the content rate of dye, and can be used suitably for preparation of various color filters. From the viewpoint of obtaining a colored cured film having high brightness and color purity, the content ratio of the dye is more preferably 10 mass % or more, more preferably 20 mass % or more, and 30 mass % or more with respect to the total amount of the (A) colorant. This is particularly preferred.

<(B) Polymer>

(B) The polymer is contained in the coloring composition for the purpose of dispersing, dyeing or permeating the (A) coloring agent, or as a binder resin. When obtaining the coloring composition for alkali developing type cured film formation, it is preferable to make (B) polymer into an alkali-soluble polymer. Moreover, (B) polymer differs from polymers, such as dye resin which are (A) coloring agents, at the point which does not have a pigment|dye structure.

(B) When the polymer is an alkali-soluble polymer, the (B) polymer may be soluble in an alkali solution and is not particularly limited, but it is preferably a polymer having an acidic functional group such as a carboxy group or a phenolic hydroxyl group. (B) It is preferable that a polymer is a polymer (henceforth a "carboxy group containing polymer") which has a carboxy group among these. As the carboxyl group-containing polymer, for example, an ethylenically unsaturated monomer having one or more carboxy groups (hereinafter also referred to as "unsaturated monomer (b1)") and an ethylenically unsaturated monomer copolymerizable with the unsaturated monomer (b1) (hereinafter, copolymers with "unsaturated monomers (b2)") are mentioned.

Examples of the unsaturated monomer (b1) include (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono[2-(meth)acryloyloxyethyl], ω-carboxypolycaprolactone mono(meth)acrylate, p -Vinyl benzoic acid, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalic acid, etc. are mentioned. The carboxy group containing polymer may have only 1 type of structural unit derived from an unsaturated monomer (b1), and may have it in combination of 2 or more type.

The said copolymer WHEREIN: The content rate of the structural unit derived from an unsaturated monomer (b1) is 5 mass % with respect to all the structural units which the (B) polymer has from the point which can obtain the colored cured film excellent in alkali developability. It is preferable that it is more than it, and it is more preferable that it is 8 mass % or more. Moreover, it is preferable that the content rate of the structural unit derived from an unsaturated monomer (b1) is 30 mass % or less with respect to all the structural units which the said copolymer has at the point which makes solubility with a solvent favorable, and is 20 mass %. It is more preferable that it is the following.

An unsaturated monomer (b2) can be suitably selected according to a use etc., and is not specifically limited. (B) at the time of polymer synthesis, by using an ethylenically unsaturated monomer having a partial structure represented by the formula (1) as the unsaturated monomer (b2) (hereinafter also referred to as a “specific group-containing monomer”), (B) Certain compounds can be obtained as polymers. Moreover, a hydroxyl-containing compound can be obtained as (B) polymer by using the ethylenically unsaturated monomer which has a hydroxyl group as an unsaturated monomer (b2).

(for specific compounds)

One aspect of the coloring composition of this indication WHEREIN: (B) The polymer contains a specific compound. (B) The specific compound as a polymer is a polymer (hereinafter also referred to as "polymer (B1)") which has a structural unit (a) from the point which it is easy to synthesize|combine the polymer which has the partial structure represented by said Formula (1) in a side chain. It is preferable to be About the illustration and preferable example of the specific group containing monomer used in order to have a structural unit (a), description of (A) coloring agent applies.

In a polymer (B1), it is preferable that the content rate of a structural unit (a) is 2 mass % or more with respect to all the structural units which a polymer (B1) has from the point which can make the solvent resistance of a cured film sufficiently high, It is more preferable that it is 5 mass % or more, and it is still more preferable that it is 10 mass % or more. Moreover, it is preferable that the content rate of a structural unit (a) is 80 mass % or less with respect to all the structural units which a polymer (B1) has from the point which can preserve the storage stability of a coloring composition, and it is 70 mass % or less It is more preferable, and it is still more preferable that it is 60 mass % or less.

In the synthesis of the polymer (B1), by using a hydroxyl group-containing monomer as the unsaturated monomer (b2), as the (B) polymer, a polymer having a partial structure and a hydroxyl group represented by the formula (1) above (hereinafter referred to as “polymer (B1)” -1)”) can be obtained. By containing a polymer (B1-1) in a coloring composition, a crosslinked structure is formed between polymers (B1-1) comrades, and it is suitable at the point which can obtain the more excellent cured film in solvent resistance. In addition, the polymer (B1-1) is also a specific compound and is also a hydroxyl-containing compound. For the examples and preferred examples of the hydroxyl group-containing monomer used in the synthesis of the polymer (B1), the description of the (A) colorant applies.

As a method of obtaining the polymer (B1-1), the following methods [2b] to [4b] are mentioned in addition to the method of polymerization (method [1b]) using a hydroxyl group-containing monomer and a specific group-containing monomer as a raw material monomer. can

Method [2b]: A polymer having an epoxy group in a side chain is obtained by polymerization using an epoxy group-containing monomer (or a carboxyl group-containing monomer) and a specific group-containing monomer as a raw material monomer, and then the polymer and a carboxy group-containing compound (or an epoxy group-containing compound) compound) to introduce a hydroxyl group (more specifically, a secondary hydroxyl group) into the side chain.

Method [3b]: Using a polymerization initiator having a hydroxyl group (for example, 2,2'-azobis(2-methyl-N-(2-hydroxyethyl)propionamide), etc.), a monomer containing a specific group is A method of polymerizing a raw material monomer comprising.

Method [4b]: Using a chain transfer agent containing a hydroxyl group (for example, monoethanolamine thioglycolic acid, 2,3-dihydroxy-1,4-butanedithiol, etc.), a monomer containing a specific group is included A method of polymerizing raw material monomers.

In addition, the description of the said method [2a] applies about the specific example of the epoxy group containing monomer and carboxy group containing compound used in method [2b]. The polymer (B1-1) is preferably a polymer having a hydroxyl group in at least a side chain from the viewpoint of facilitating adjustment of the amount of the hydroxyl group in the polymer, and that the hydroxyl group-containing polymer can be obtained relatively easily.

As the unsaturated monomer (b2) used in the synthesis of the polymer (B1), in addition to the above, for example, N-alkylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide N-substituted maleimides such as; Aromatic vinyl compounds, such as styrene, (alpha)-methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxy Ethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane- 8-yl (meth)acrylate, dicyclopentenyl (meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acrylo (meth)acrylic acid esters such as yloxymethyl]oxetane and 3-[(meth)acryloyloxymethyl]-3-ethyloxetane;

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane vinyl ethers such as;

and macromonomers having a mono(meth)acryloyl group at the terminal of the polymer molecular chain, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane. (B) The polymer may have only 1 type of structural unit derived from an unsaturated monomer (b2), and may have it in combination of 2 or more type.

(About hydroxyl-containing compounds)

One aspect of the coloring composition of this indication WHEREIN: (B) polymer contains a hydroxyl-containing compound. (B) When using the polymer which has a hydroxyl group as a polymer, as this polymer, it has a hydroxyl group other than the said polymer (B1-1), and the polymer which does not have the partial structure represented by said Formula (1) (hereinafter, "hydroxyl group") containing polymer (B2)"). The hydroxyl group-containing polymer (B2) may have a hydroxyl group in the side chain, may have it in the main chain terminal, and may have it in both the side chain and the main chain terminal. Of these, the hydroxyl group-containing polymer (B2) is preferably a polymer having a hydroxyl group in at least a side chain from the viewpoint of facilitating adjustment of the amount of hydroxyl groups and comparatively easily obtaining the hydroxyl group-containing polymer. Examples of the method for obtaining the hydroxyl group-containing polymer (B2) include a method of polymerization without using a specific group-containing monomer in the methods [1b] to [4b] described for the polymer (B1-1). For the examples and preferred examples of the hydroxyl group-containing monomer used in the synthesis of the polymer (B2), the description of the (A) colorant applies. In addition, when manufacturing a hydroxyl-containing polymer (B2), only 1 type of methods [1b] - [4b] may be used, or 2 or more types may be combined.

In each of a polymer (B1-1) and a polymer (B2), the content rate of the structural unit which has a hydroxyl group has a polymer (B1-1) or a polymer (B2) from a viewpoint of obtaining a colored cured film with high solvent resistance It is preferable that it is 2 mass % or more with respect to all structural units, It is more preferable that it is 5 mass % or more, It is still more preferable that it is 10 mass % or more. Moreover, it is preferable that the content rate of the structural unit which has a hydroxyl group is 70 mass % or less with respect to all the structural units which a polymer (B1-1) or a polymer (B2) has from a viewpoint of making storage stability favorable, and 65 mass % or less is more preferable, and it is still more preferable that it is 60 mass % or less.

(other polymers)

The coloring composition may contain only one of a specific compound and a hydroxyl group-containing compound as the (B) polymer, but a polymer having neither of the partial structure and hydroxyl group represented by the formula (1) (hereinafter also referred to as "other polymer") ) may be used together. Further, when at least one selected from the group consisting of (A) a coloring agent and (C) a polymerizable compound, and a specific compound and a hydroxyl group-containing compound are included, the coloring composition may contain only another polymer as the (B) polymer. good.

Another polymer is not specifically limited, According to a use, it can select suitably. As a specific example of another polymer, For example, Unexamined-Japanese-Patent No. 7-140654, Unexamined-Japanese-Patent No. 8-259876, Unexamined-Japanese-Patent No. 10-31308, Unexamined-Japanese-Patent No. 10-300922, and copolymers disclosed in JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP 2004-101728 , and the like. Moreover, as (B) a polymer, Unexamined-Japanese-Patent No. 5-19467, Unexamined-Japanese-Patent No. 6-230212, Unexamined-Japanese-Patent No. 7-207211, Unexamined-Japanese-Patent No. 9-325494, for example. , a polymerizable unsaturated bond (for example, a carbon-carbon double bond in a (meth)acryloyl group) as a side chain as disclosed in Japanese Patent Application Laid-Open No. Hei 11-140144, Japanese Patent Application Laid-Open No. 2008-181095, etc. You can also use the carboxy group containing polymer which has

(B) A polymer can be manufactured by well-known methods, such as radical polymerization, anionic polymerization, cationic polymerization, living radical polymerization, living anionic polymerization, and living cationic polymerization, for example. In addition, the structure and Mw and Mw/Mn can also be controlled by the method disclosed in Unexamined-Japanese-Patent No. 2003-222717, Unexamined-Japanese-Patent No. 2006-259680, International Publication No. 07/029871 pamphlet etc., for example. . In addition, as (B) polymer, 1 type can be used individually or in mixture of 2 or more types.

(B) It is preferable that the weight average molecular weight (Mw) of polystyrene conversion measured by gel permeation chromatography (GPC) using tetrahydrofuran as an elution solvent about a polymer is 1,000-100,000. Mw becomes like this. Preferably it is 3,000 or more. Moreover, Mw becomes like this. Preferably it is 50,000 or less. If Mw is 1,000 or more, it is preferable at the point which can make a pattern shape favorable, and if it is 100,000 or less, resolution time does not become long too much, but it is preferable from a viewpoint of ensuring fairness.

Moreover, ratio (Mw/Mn) of Mw and number average molecular weight (Mn) of (B) polymer becomes like this. Preferably it is 1.0-5.0, More preferably, it is 1.0-3.0. In addition, Mn is a polystyrene conversion value measured by GPC using tetrahydrofuran as an elution solvent.

Coloring composition WHEREIN: Content of (B) polymer is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents. (B) When content of a polymer is the said range, on a coating-film formation process, sufficient alkali developability, sufficient storage stability as a product of a coloring composition, and color density sufficient with respect to the requested|required film thickness as a color filter can be ensured. (B) To [ content of a polymer / 100 mass parts of (A) coloring agents ], Preferably it is 20 mass parts or more, More preferably, it is 30 mass parts or more. Moreover, with respect to 100 mass parts of (A) coloring agents, content of (B) polymer becomes like this. Preferably it is 500 mass parts or less, More preferably, it is 300 mass parts or less.

<(C) polymerizable compound>

(C) A polymeric compound is a compound which preferably has two or more polymeric groups, and is a low molecular compound functioning as a crosslinking agent. Moreover, (C) polymeric compound is different from (A) coloring agent at the point which does not have a pigment|dye structure, and differs from (B) polymer at the point which does not have molecular weight distribution. That is, the compound which has a polymeric group and a pigment|dye structure is classified as (A) coloring agent. Polymers having a polymerizable group and not having a dye structure are classified as (B) polymers. (C) The molecular weight of a polymeric compound becomes like this. Preferably it is 1,000 or less, More preferably, it is 800 or less.

Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. Among these, it is preferable that (C) a polymeric compound is a compound which has two or more (meth)acryloyl groups, or a compound which has two or more N-alkoxymethylamino groups, and it is two or more (meth)acryloyl groups. It is especially preferable that it is a compound which has. (C) The number of polymeric groups which one molecule of polymeric compound has becomes like this. Preferably it is 2-10 pieces, More preferably, it is 2-8 pieces.

(About hydroxyl-containing compounds)

One aspect of the coloring composition of this indication WHEREIN: (C) A polymeric compound contains a hydroxyl-containing compound (henceforth "hydroxyl group-containing crosslinking agent (C1)"). By using the hydroxyl group-containing crosslinking agent (C1), the reaction ^{point with the group "-OR 1} " and the group "-OR ² " in the formula (1) can be introduced relatively easily, and to adjust the content of the hydroxyl group in the coloring composition It is preferable from an easy point.

From the viewpoint of making the hydroxyl group-containing crosslinking agent (C1) compatible with solvent resistance and storage stability, the number of hydroxyl groups in one molecule is preferably 1 to 8, more preferably 1 to 6, still more preferably 1 to 4 Do. Further, the hydroxyl group-containing crosslinking agent (C1) is particularly preferably a compound having two or more (meth)acryloyl groups from the viewpoint of high reactivity to heat and light.

When the coloring composition of this indication contains only a hydroxyl-containing crosslinking agent (C1) as a hydroxyl-containing compound, it is preferable that a hydroxyl-containing crosslinking agent (C1) is 10-500 mgKOH/g of hydroxyl values. By setting the hydroxyl value of the hydroxyl group-containing crosslinking agent (C1) to a value within the above range, the effect of increasing the solvent resistance of the colored cured film obtained using the colored composition of the present disclosure and the effect of the storage stability of the colored composition are well balanced. It is preferable that it is possible. From the viewpoint of solvent resistance, the hydroxyl value of the hydroxyl group-containing crosslinking agent (C1) is more preferably 25 mgKOH/g or more, still more preferably 50 mgKOH/g or more. Moreover, from a viewpoint of storage stability, the hydroxyl value of a hydroxyl-containing crosslinking agent (C1) becomes like this. More preferably, it is 400 mgKOH/g or less, More preferably, it is 300 mgKOH/g or less. In addition, in this specification, "hydroxyl value" represents the mg number of KOH required for neutralizing 1 g of solid content of a hydroxyl-containing crosslinking agent (C1).

The hydroxyl group-containing crosslinking agent (C1) is preferably a polyfunctional (meth)acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, and as a specific example thereof, for example, pentaerythritol tri(meth) ) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, trimethylol Propaned di(meth)acrylate, dipentaerythritol polyacrylate, etc. are mentioned. Among these, intermolecular or intramolecular crosslinking density becomes high, and since sclerosis|hardenability of a film|membrane can be improved more also by low-temperature baking, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol poly Acrylates are particularly preferred. In addition, as a hydroxyl-containing crosslinking agent (C1), you may use individually by 1 type, and may use it in combination of 2 or more type.

(Other polymerizable compounds)

The coloring composition may contain only a hydroxyl-containing compound as (C) a polymeric compound, but a polymeric compound which does not have any of the partial structure and hydroxyl group represented by said Formula (1) (hereafter also referred to as "other polymeric compound") ) may be used together. Moreover, when the coloring composition of this indication contains a specific compound and a hydroxyl-containing compound as at least 1 sort(s) selected from the group which consists of (A) a coloring agent and (B) a polymer, a coloring composition is (C) a polymeric compound You may contain only another polymeric compound.

As a specific example of another polymeric compound, it is a compound which has two or more (meth)acryloyl groups, It is polyfunctional (meth)acrylate obtained by making a trivalent or more aliphatic polyhydroxy compound react with (meth)acrylic acid, caprolactone modified. Polyfunctional (meth) acrylate obtained by reacting polyfunctional (meth) acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, (meth) acrylate having a hydroxyl group and polyfunctional isocyanate, polyfunctional urethane (meth) acrylate having a hydroxyl group The polyfunctional (meth)acrylate etc. which have a carboxy group obtained by making (meth)acrylate and an acid anhydride react are mentioned.

As a compound which has two or more N-alkoxy methylamino groups, the compound etc. which have a melamine structure, a benzoguanamine structure, and a urea structure are mentioned, for example. In addition, a melamine structure and a benzoguanamine structure mean the chemical structure which has one or more triazine rings or a phenyl-substituted triazine ring as basic skeleton, It is a concept including melamine, benzoguanamine, or those condensates. Specific examples of the compound having two or more N-alkoxymethylamino groups include N,N,N',N',N'',N''-hexa(alkoxymethyl)melamine, N,N,N',N'- tetra(alkoxymethyl)benzoguanamine, N,N,N',N'-tetra(alkoxymethyl)glycoluril, etc. are mentioned.

Among other polymerizable compounds, polyfunctional (meth)acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylate, polyfunctional urethane ( meth) acrylate, polyfunctional (meth) acrylate having a carboxy group, N, N, N', N', N'', N''-hexa (alkoxymethyl) melamine, N, N, N', N' -Tetra (alkoxymethyl) benzoguanamine is preferable, and having a polyfunctional (meth)acrylate obtained by reacting a trivalent or more aliphatic polyhydroxy compound with (meth)acrylic acid, a polyfunctional urethane (meth)acrylate, and a carboxy group Polyfunctional (meth)acrylate is more preferable. As another polymeric compound, 1 type can be used individually or in mixture of 2 or more types.

It is preferable that it is 10 mass parts or more with respect to 100 mass parts of (A) coloring agents, and, as for content of the (C) polymeric compound in a coloring composition, it is more preferable that it is 20 mass parts or more. Moreover, it is preferable that it is 1,000 mass parts or less with respect to 100 mass parts of (A) coloring agents, and, as for content of (C) polymeric compound, it is more preferable that it is 500 mass parts or less. (C) When the content rate of a polymeric compound exists in the said range, while sclerosis|hardenability sufficient as a colored cured film and sufficient alkali developability can be ensured, the scumming on the board|substrate of an unexposed part or the light-shielding layer, a film|membrane It is preferable at the point which can fully suppress generation|occurrence|production of a residue etc.

The coloring composition of this indication may contain various components other than (A) coloring agent, (B) polymer, and (C) polymeric compound as needed. Other components which may be contained in the coloring composition of this indication are demonstrated below.

<(D) Photoinitiator>

(D) The photoinitiator is a compound which generates active species capable of initiating polymerization of the (C) polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray. Examples of the photopolymerization initiator include a thioxanthone-based compound, an acetophenone-based compound, a biimidazole-based compound, a triazine-based compound, an O-acyloxime-based initiator, an onium salt-based compound, a benzoin-based compound, a benzophenone-based compound, and an α-diketone-based compound. compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, and the like. Among these, it is preferable that the (D) photoinitiator contains an oxime type initiator at the point which can fully generate|generate a radical and can fully advance film|membrane hardening. As the oxime-based initiator, an O-acyloxime-based initiator can be preferably used.

Specific examples of the O-acyloxime-based initiator include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6 -(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), ethanone,1-[9-ethyl-6-(2-methyl-4-tetrahydrofura) Nylmethoxybenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), ethanone,1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl) -1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-,1-(O-acetyloxime), 1,2-propanedione, 3-cyclohexyl-1-[4 -(phenylthio)phenyl]-,1-(O-acetyloxime) (compound represented by the following formula (D-1)), a compound represented by the following formula (D-2)

and the like. Examples of the O-acyloxime-based initiator include NCI-831, NCI-930 (above, manufactured by ADEKA Corporation), PBG-3057 (above, manufactured by Changzhou Strong Electronic New Materials), Irgacure OXE03 (above, BASF) You may use commercial items, such as Japan Corporation make).

As an O-acyl oxime type|system|group initiator, it can use preferably also about the compound represented by each of following formula (d-10), a formula (d-11), and a formula (d-12).

(In formula (d-10), X ¹ and X ² each independently represent a single bond or -CO-. However, at least one of ^{X 1} and X ^{2 is -CO-. R 1} represents 2 to 6 carbon atoms. and R ² is an alkyl group having 4 to 10 carbon atoms. R ⁴ is a monovalent organic group having a hydrocarbon ring or a heterocyclic ring. R ³ and R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms or It is a phenyl group.)

(In formulas (d-11) and (d-12), X ³ is a single bond or an alkanediyl group having 1 to 5 carbon atoms, and X ⁴ is -O-, -S- or -NR ¹⁰ -( provided that R ¹⁰ is a hydrogen atom and a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms.) X ⁵ and X ⁶ are each independently a single bond or -CO-, and R ⁶ and R ⁷ are each independently , a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R ⁸ and R ⁹ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or a substituted or unsubstituted monovalent hydrocarbon group having 3 carbon atoms to 20. R ¹¹ and R ¹² are each independently a hydrogen atom or a monovalent substituent.)

In the formula (d-10), R ¹ is preferably an ethyl group or a propyl group. Although linear or branched form may be sufficient as R<^2> , it is preferable that it is linear. It is preferable that R<^4> is the group which the hydrocarbon ring or heterocyclic ring couple|bonded with the carbon atom of the oxime ester group through the divalent coupling group. The divalent linking group is preferably at least one selected from the group consisting of an alkanediyl group having 1 to 4 carbon atoms, -S-, -O- and -CO-, and a methylene group, ethylene group, -S- or -O - is more preferable. As for a hydrocarbon ring, a cyclopentane ring or a cyclohexane ring is preferable, and, as for a heterocyclic ring, a dioxolane ring or a pyrimidine ring is preferable.

In the formulas (d-11) and (d-12), when R ⁶ , R ⁷ , R ⁸ or R ⁹ has a substituent, the substituent includes a halogen atom, a nitro group, a hydroxyl group, a carboxy group, and a sulfonic acid. group, an amino group, a cyano group, and the like. As ^{a substituent of R 11} and R ¹² , at least one hydrogen atom of a halogen atom, a nitro group, a hydroxyl group, a carboxy group, a sulfonic acid group, an amino group and a cyano group, and an alkyl group, a cycloalkyl group, a cycloalkylalkyl group or an alkylcycloalkyl group is halogen and groups substituted with an atom, a nitro group, a hydroxyl group, a carboxy group, a sulfonic acid group, an amino group, or a cyano group.

As an O-acyl oxime system initiator, from the point which can make the contrast ratio of a cured film more favorable, the acyl oxime compound which has a diphenyl sulfide skeleton, the acyl oxime compound which has a carbazole skeleton, and the acyl oxime which has a fluorene skeleton At least one selected from the group consisting of compounds can be preferably used. The O-acyl oxime-based initiator is more preferably at least one selected from the group consisting of an acyl oxime compound having a diphenyl sulfide skeleton and an acyl oxime compound having a fluorene skeleton.

(D) 0.01 mass part or more is preferable with respect to 100 mass parts of (C) polymeric compounds, and, as for the content rate of a photoinitiator, 1 mass part or more is more preferable. Moreover, 120 mass parts or less are preferable with respect to 100 mass parts of (C) polymeric compounds, and, as for the content rate of (D) photoinitiator, 100 mass parts or less are more preferable. (D) When content of a photoinitiator is the said range, while being able to ensure sufficient hardening of the coating film by an appropriate exposure amount, and sufficient alkali developability as a coloring composition, the smearing of the board|substrate or light shielding layer of an unexposed part, Generation|occurrence|production of a film|membrane residue can fully be suppressed. Moreover, the luminance fall of the coating film by yellowing of the polymerization initiator at the time of a post-baking can fully be suppressed. (D) A photoinitiator can be used individually by 1 type or in mixture of 2 or more types.

<(E) Solvent>

The coloring composition of this indication mix|blends the (E) solvent, and is prepared as a liquid composition. (E) As the solvent, each component (A), (B), (C) or other components constituting the coloring composition is dispersed or dissolved, and does not react with these components and has appropriate volatility. have.

(E) Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, (poly)alkylene glycol monoalkyl ethers such as tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether;

lactic acid alkyl esters such as methyl lactate and ethyl lactate; alkyl alcohols which may have a straight-chain, branched or cyclic structure such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol and cyclohexanol; Keto alcohols, such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether (poly)alkylene glycol monoalkyl ether acetates such as acetate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate; ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;

diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;

Alkoxycarboxylic acids such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, and 3-methyl-3-methoxybutylpropionate esters;

Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate , other esters such as n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene;

and amides or lactams such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

Among these, as (E) solvent, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol from a viewpoint of solubility, pigment dispersibility, applicability, etc. Monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1 ,6-Hexanediol diacetate, ethyl lactate, 3-methoxyethyl propionate, 3-ethoxypropionate methyl, 3-ethoxypropionate ethyl, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, At least one selected from the group consisting of i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, and ethyl pyruvate is preferable. In addition, (E) solvent can be used individually by 1 type or in mixture of 2 or more types.

The coloring composition of this indication contains at least 1 sort(s) of solvent (henceforth "specific alcohols") selected from the group which consists of a primary alcohol and a secondary alcohol in the range of predetermined amount or less, A coloring composition It is preferable at the point which can make storage stability favorable. In order for specific alcohols to implement|achieve low-temperature baking, the solvent whose boiling point is 150 degrees C or less is preferable. Preferred examples of specific alcohols include methanol, ethanol, propan-1-ol, butan-1-ol, and pentan-1-ol as primary alcohols; Examples of the secondary alcohol include propan-2-ol, butan-2-ol, pentan-2-ol, and hexan-2-ol. Among these, primary alcohol is preferable at the point which can obtain the coloring composition excellent in storage stability.

In addition, in the coloring composition of the present disclosure, crosslinking formation at the time of film formation is by transesterification reaction, and since the transesterification reaction is a reversible reaction, the equilibrium is maintained by presenting specific alcohols in the coloring composition, and the transesterification reaction It is thought that the storage stability of a coloring composition was improved by being suppressed.

The coloring composition of this indication WHEREIN: The content rate of specific alcohol is 10 mass % or less with respect to the total amount of (E) solvent contained in the coloring composition from a viewpoint of preserving the dispersibility of (A) coloring agent. It is preferable, 8 mass % or less is more preferable, and 7 mass % or less is still more preferable. Moreover, in order to acquire the improvement effect of storage stability, as for the content rate of specific alcohol, it is preferable that it is more than 0 mass %, 0.01 mass % or more is more preferable, 0.5 mass % or more is still more preferable, 1 mass % or more It is more preferable than this. In addition, as specific alcohols, 1 type can be used individually or in combination of 2 or more type.

<(F) Additives>

The coloring composition may contain various additives other than the above as needed. As an additive, For example, fillers, such as glass and alumina; high molecular compounds such as polyvinyl alcohol and poly(fluoroalkyl acrylate); surfactants such as fluorine-based surfactants and silicone-based surfactants; adhesion promoter; antioxidants; UV absorbers; polyfunctional thiols; Metal chelate compounds, such as a zirconium compound, a titanium compound, and an aluminum compound, etc. are mentioned. These compounding ratios are a range which does not impair the effect of this indication. WHEREIN: According to the kind of each additive, it can set suitably.

In the coloring composition of the present disclosure, the content ratio of the specific compound and the hydroxyl group-containing compound is within a range suitable for the content of the partial structure represented by the formula (1) and the content of the hydroxyl group, respectively, depending on the blending form of the specific compound and the hydroxyl group-containing compound. It can be set appropriately so that

<Preparation of a coloring composition>

The coloring composition of this indication can be prepared by an appropriate method. As the preparation method, the method disclosed by Unexamined-Japanese-Patent No. 2008-58642, Unexamined-Japanese-Patent No. 2010-132874, etc. is mentioned, for example. (A) When using both a dye and a pigment as a colorant, as disclosed in Japanese Patent Application Laid-Open No. 2010-132874, after passing the dye solution through the first filter, the dye solution passed through the first filter, The method of preparing by mixing with the separately prepared pigment dispersion liquid etc. and making the obtained coloring composition pass through a 2nd filter is employable. Further, a solution obtained by dissolving the dye, the polymer (B), the polymerizable compound (C), and other components used as necessary in a solvent, passing the resulting solution through the first filter, and then passing through the first filter You may employ|adopt the method of preparing by mixing with the pigment dispersion liquid prepared separately, and passing the obtained coloring composition through a 2nd filter. Further, after passing the dye solution through the first filter, the dye solution passed through the first filter, the (B) polymer and (C) the polymerizable compound, and other components used as needed are mixed and dissolved, You may employ|adopt the method of making the obtained solution pass through a 2nd filter, mixing the solution which passed through the 2nd filter with the separately prepared pigment dispersion, and making the obtained coloring composition pass through a 3rd filter.

[Color filter and manufacturing method thereof]

The color filter of this indication is equipped with the colored layer formed using said coloring composition.

As a method of manufacturing a color filter, first, a light shielding layer (black matrix) is formed on the surface of a board|substrate so that the part which forms a pixel may be partitioned as needed. Next, on this board|substrate, after apply|coating a green coloring composition (liquid composition), for example, vacuum drying or prebaking is performed, the solvent is evaporated, and a coating film is formed (film formation process). Next, after exposing this coating film through a photomask (exposure process), it develops using alkali developer (development process). At this time, in the case of a positive type, the exposed part of a coating film is dissolved and removed, and in the case of a negative type, the unexposed part of a coating film is dissolved and removed. Thereafter, by performing post-baking (heating step), a pixel array in which green pixel patterns are arranged in a predetermined arrangement is formed.

Next, using each red or blue coloring composition, application, drying, exposure, development and post-baking of each coloring composition are performed in the same manner as above, and the red pixel array and the blue pixel array are sequentially formed on the same substrate. to form Thereby, a color filter in which a pixel array of three primary colors of green, red, and blue is disposed on a substrate is obtained. However, the order of forming the pixels of each color is not limited to the above. A black matrix can be formed by making metal thin films, such as chromium, formed into a film by sputtering or vapor deposition into a desired pattern using the photolithographic method. Moreover, it can carry out similarly to the case of formation of the said pixel, and can also form using the coloring composition in which the black coloring agent was disperse|distributed.

As a board|substrate used when forming a color filter, glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. are mentioned, for example. If desired, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction method, vacuum deposition, or the like.

When apply|coating a coloring composition to a board|substrate, appropriate application|coating methods, such as a spray method, the roll coating method, the spin coating method (spin coating method), the slit die coating method (slit coating method), the bar coating method, are employable. Among these, it is preferable to employ a spin coating method or a slit die coating method from the viewpoint of obtaining a coating film having a uniform film thickness. A coating film is formed on a board|substrate by performing reduced pressure drying after application|coating. Drying under reduced pressure is usually 1 to 15 minutes at room temperature, preferably 1 to 10 minutes, and is usually performed at a pressure reaching 50 to 200 Pa. Formation of a coating film may be performed by the heat processing (pre-baking) lower than the post-baking temperature. Application thickness is a film thickness after drying, and is 0.6-8 micrometers normally, Preferably it is 1.2-5 micrometers.

Examples of the light source of radiation used for exposure include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, argon ion lasers, YAG lasers, XeCl Laser light sources, such as an excimer laser and a nitrogen laser, etc. are mentioned. As the exposure light source, an ultraviolet LED may be used. The radiation in the range of 190-450 nm is preferable, and, as for a wavelength, the radiation in the range of 300-450 nm is more preferable. As for the exposure amount of a radiation, generally 10-10,000 J/m<2> is preferable. The amount of radiation exposure is more preferably 100 J/m 2 or more, and still more preferably 200 J/m 2 or more. Moreover, the exposure amount of radiation becomes like this. More preferably, it is 5,000 J/m<2> or less, More preferably, it is 2,000 J/m<2> or less.

Examples of the alkali developer include sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1, Aqueous solutions, such as 5-diazabicyclo-[4.3.0]-5-nonene, are preferable. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the alkaline developer, for example. In addition, after alkali development, it washes with water normally. As a developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (drilling) developing method, etc. are applicable. As for image development conditions, 5-300 second is preferable at normal temperature.

Post-baking is performed by heating the patterned coating film at 70-230 degreeC. The post-baking temperature is, for example, 70 to 120° C., or 120° C. to 180° C., 180° C. to 240° C., etc., in consideration of the improvement of curing properties, solvent resistance, adhesion to the substrate, suppression of color transfer, and substrate protection The heating temperature can be set accordingly. At that time, group "OR ^1" or the group "OR ^2," at least one of the hydroxyl group-containing alcohol compound to sufficiently proceed the transesterification between the OH groups, the coloring composition containing with acids having a particular compound What is necessary is just to set the temperature higher than the boiling point of , as the heating temperature at the time of post-baking. Although the heating time at the time of a post-baking can be set suitably by heating temperature, In the low temperature of 70-120 degreeC, for example, it is 5-120 minutes normally, Preferably it is 30-100 minutes. The film thickness of the colored cured film (namely, pixel) formed on the board|substrate is 0.5-5 micrometers normally, Preferably it is 1.0-3 micrometers.

On the pixel pattern obtained in this way, after forming a protective film as needed, a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer may be further formed to obtain a color filter. A spacer is normally formed using a transparent photosensitive resin composition, but it can also be set as the spacer (black spacer) which has light-shielding property. In this case, the photosensitive coloring composition in which the black coloring agent was disperse|distributed is used. The coloring composition of this indication can be used suitably also formation of such a black spacer.

The coloring composition of this indication can be used suitably also for formation of any colored cured film, such as each color pixel used for a color filter, a black matrix, and a black spacer. The color filter thus formed has high luminance and color purity, and is particularly useful for a color liquid crystal display element, a solid-state image sensor, a color sensor, an organic EL display element, electronic paper, and the like.

[display element]

The display element of this indication is equipped with the color filter of this indication. As a display element, a color liquid crystal display element, an organic electroluminescent display element, electronic paper, etc. are mentioned.

The color liquid crystal display element provided with the color filter of this indication may be equipped with the backlight unit which uses a white LED as a light source other than a cold cathode fluorescent tube (CCFL:Cold Cathode Fluorescent Lamp). As the white LED, for example, a white LED that obtains white light by mixing a red LED, a green LED, and a blue LED, a white LED that obtains white light by mixing a blue LED, a red LED, and a green phosphor, and a blue LED A white LED that obtains white light by mixing a red light-emitting phosphor and a green light-emitting phosphor, a white LED that obtains white light by mixing a blue LED and a YAG-based phosphor, and a blue LED, an orange light-emitting phosphor and a green light-emitting phosphor and a white LED which obtains white light by a combination of an ultraviolet LED, a red light-emitting fluorescent substance, a green light-emitting fluorescent substance, and a blue light-emitting fluorescent substance, and obtains white light by color mixing, and the like.

The organic EL display element provided with the color filter of this indication can take an appropriate structure, for example, the structure currently disclosed by Unexamined-Japanese-Patent No. 11-307242 is mentioned. Moreover, the structure disclosed by Unexamined-Japanese-Patent No. 2007-41169 is mentioned, for example of the electronic paper provided with the color filter of this indication.

[Light-receiving element]

The light receiving element of this indication is equipped with the colored cured film formed using the above-mentioned coloring composition. The light-receiving element of the present disclosure may have an appropriate structure. For example, the above colored cured film is used as a color filter constituting a solid-state image-capturing element, and is combined with a photodiode to constitute an image-capturing element such as a solid-state image sensor. can Moreover, the pixel for infrared light detection can be comprised by using the cured film of this indication as an infrared light transmission filter, and combining with a photodiode.

[Curable composition]

The curable composition of this indication contains the above-mentioned (B) polymer and (C) a polymeric compound. In particular, in the curable composition of the present disclosure, at least one selected from the group consisting of (B) polymer and (C) polymerizable compound has a partial structure represented by Formula (1), (B) polymer and (C) polymerization At least 1 sort(s) selected from the group which consists of a sexual compound has a hydroxyl group. In addition, the partial structure and hydroxyl group represented by said Formula (1) may exist in the same molecule|numerator, and may exist in a different molecule|numerator.

The curable composition of this indication is a composition used in order to form a cured film. Examples of the cured film include a bank (partition rib) defining a region for forming each color pixel, an interlayer insulating film, a planarization film, and a light emitting layer used for a display element or a light receiving element, a black matrix, a spacer, a protective film, and the like. As a display element, a color liquid crystal display element, organic electroluminescent element, electronic paper etc. are mentioned, for example, As a light receiving element, a CCD image sensor, a CMOS image sensor, etc. are mentioned, for example.

[Example]

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In addition, unless otherwise indicated, "part" and "%" in an Example and a comparative example are based on mass. In this Example, the weight average molecular weight (Mw) of the polymer was measured by GPC. The compound used in the present Example and its abbreviation are shown below.

(crosslinkable monomer)

(Other monomers)

(dye monomer)

Dye monomer I is a compound of the structural formula in which the anion moiety of the raw material monomer of the dye polymer XIV described in Paragraph 0434 of Japanese Patent No. 5377595, which has a known structure, is exchanged with a bis(trifluoromethanesulfonyl)imide anion. Dye monomers II to XI are compounds represented by the structural formulas shown below.

(dyes)

(Hydroxy group-containing dye)

(Photoinitiator)

(Polymerizable compound)

C-2A: A compound represented by the above formula (C-2) and having a hydroxyl value of 60 to 100 mgKOH/g

C-2B: A compound represented by the above formula (C-2) and having a hydroxyl value of 100 to 140 mgKOH/g

1. Synthesis of dye resin

[Synthesis Example 1-1]

In a reaction vessel equipped with a cooling tube, dye monomer I 8.70 g, methacrylic acid (MA) 1.41 g, malonic acid-2-[[[[[2-methyl-1-oxo-2-propenyl] oxy] ethyl ]amino]carbonyl]-1,3 diethyl ester (manufactured by Showa Denko, trade name "Karenz MOI-DEM", hereinafter referred to as "compound (M-1)") 2.25 g, 2-hydroxyethyl 1.97 g of methacrylate (HEMA) and 0.42 g of 2-ethylhexyl-3-mercaptopropionate (EHMP) were added, and dissolved in 25.4 g of propylene glycol monomethyl ether acetate (PGMEA) and 59.2 g of n-butanol. This solution was heated to 75 degreeC with stirring under nitrogen stream. While stirring at the same temperature, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., trade name "V-70", hereinafter simply "V-70") ') was added, and stirring was continued for 3 hours. Then, 0.42g of V-70 was further added, and stirring was continued for 3 hours. Next, after cooling the reaction solution to room temperature, 60 g of PGMEA was added to make a uniform solution, and this solution was dripped at 1.1 L of hexane. The produced precipitate was filtered off and washed with hexane. The obtained solid was dried under reduced pressure at 50 degreeC, and 15.30g of polymers (this is called "polymer (A-1)") were obtained. GPC confirmed that the obtained polymer (A-1) had Mw of 19,000 and Mn of 9,800.

[Synthesis Examples 1-2 to 1-10, 1-12 to 1-22 and Comparative Synthesis Examples 1-1 to 1-4]

Polymers (A-2) to (A-10), (A-12) to polymers (A-2) to (A-10), (A-12) to (A-22) and polymers (AR-1) to (AR-4) were synthesized, respectively. In addition, in Table 1, "-" shows that the applicable component is not mix|blended (the same also about the following table|surface).

[Synthesis Example 1-11]

In a reaction vessel equipped with a cooling tube, dye monomer I 8.70 g, MA 1.41 g, compound (M-1) 2.25 g, glycerol monomethacrylate (GLM) 1.97 g, thioglycolic acid monoethanolamine (TG-MEA) 0.42 g was added and dissolved in 25.4 g PGMEA and 59.2 g n-butanol. This solution was heated to 75 degreeC with stirring under nitrogen stream. While stirring at the same temperature, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] (manufactured by Wako Pure Chemical Industries, Ltd., water-soluble radical initiator, trade name "VA-086", hereinafter simply " VA-086") was added, and stirring was continued for 3 hours. Then, 0.42g of VA-086 was further added, and stirring was continued for 3 hours. Next, after cooling the reaction solution to room temperature, 60 g of PGMEA was added to make a uniform solution, and this solution was dripped at 1.1 L of hexane. The produced precipitate was filtered off and washed with hexane. The obtained solid was dried under reduced pressure at 50°C to obtain 15.30 g of a polymer (this is referred to as “polymer (A-11)”). The obtained polymer (A-11) confirmed by GPC that Mw was 19,300 and Mn was 10,000.

[Synthesis Example 1-23]

In a reaction vessel equipped with a cooling tube, p-(vinylphenyl)trifluoromethanesulfonylimidic acid triethylamine salt (this is referred to as “acidic monomer I”) 8.45 g, MA 1.41 g, compound (M-1) ) 2.25 g, HEMA 1.97 g, pentaerythritol tetrakis (3-mercaptopropionate) (PEMP) 0.42 g were added, and dissolved in cyclohexanone (CHN) 25.40 g and n-butanol 59.20 g. This solution was heated to 75 degreeC with stirring under nitrogen stream. While stirring at the same temperature, 0.84 g of V-70 was added, and stirring was continued for 4 hours. Next, after cooling the reaction solution to room temperature, 60 g of acetone was added to make a uniform solution, and this solution was dripped at 1.1 L of hexane. The produced precipitate was filtered off and washed with hexane. The obtained solid was dried under reduced pressure at 50° C. to obtain 15.01 g of an anionic group-containing polymer represented by the following structural formula (this is referred to as “polymer (A-23-1)”). The obtained polymer (A-23-1) confirmed by GPC that Mw was 11,100 and Mn was 6,900.

2.0 g of the polymer (A-23-1) synthesized above was dissolved in 40 mL of acetone. Next, as shown in the following scheme, the number of moles of structural units derived from p-(vinylphenyl)trifluoromethanesulfonylimid acid triethylamine salt calculated from the copolymerization ratio of the polymer (A-23-1) An equivalent molar amount of CIBasic Red 12 (basic dye I) was added thereto, and the mixture was stirred at room temperature for 1 hour. Then, 200 mL of ion-exchanged water was added to the residue obtained by concentrating the reaction solution under reduced pressure, and the precipitate formed was filtered out, and water washing was carried out. The obtained solid was dried under reduced pressure at 50°C to obtain 2.61 g of a polymer represented by the following structural formula (this is referred to as "polymer (A-23)").

[Synthesis Examples 1-24, 1-25]

Polymers (A-24) and (A-25) were synthesized in the same manner as in Synthesis Example 1-23, except that the kind of basic dye to be used was changed as shown in Table 2 below.

[Synthesis Example 1-26]

In a reaction vessel with a cooling tube, 8.45 g of methacryloylpropyltrimethylammonium chloride (basic monomer I), 1.41 g of MA, 2.25 g of compound (M-1), 1.97 g of HEMA, 0.42 g of PEMP were mixed with 25.0 g of CHN and It was dissolved in 60.0 g of n-butanol. This solution was heated to 75 degreeC with stirring under nitrogen stream. While stirring at the same temperature, 0.80 g of V-70 was added, and stirring was continued for 4 hours. Next, after cooling the reaction solution to room temperature, 60.0 g of acetone was added to make a uniform solution, and this solution was dripped at 1.10 L of hexane. The produced precipitate was filtered off and washed with hexane. The obtained solid was dried under reduced pressure at 50° C. to obtain 15.11 g of a cationic group-containing polymer represented by the following structural formula (this is referred to as “polymer (A-26-1)”). The obtained polymer (A-26-1) confirmed by GPC that Mw was 10,500 and Mn was 7,000.

2.00 g of the polymer (A-26-1) synthesized above was dissolved in 40.0 mL of acetone. Next, as shown in the following reaction formula, an equivalent molar amount of CIAcid Blue 93 (acid dye I) is added to the number of moles of ammonium salt-derived structural units calculated from the copolymerization ratio of the polymer (A-26-1), and then at room temperature was stirred for 1 hour. Then, 200 mL of ion-exchanged water was added to the residue obtained by concentrating the reaction solution under reduced pressure, and the precipitate formed was filtered out, and water washing was carried out. The obtained solid was dried under reduced pressure at 50°C to obtain 2.62 g of a dye multimer represented by the following structural formula (this is referred to as "polymer (A-26)"). The obtained polymer (A-26) confirmed by GPC that Mw was 12,600 and Mn was 7,500.

[Synthesis Example 1-27]

A cationic group-containing polymer represented by the following structural formula by performing the same operation as in Synthesis Example 1-26 above except that the cationic monomer was changed to dimethylaminoethyl methacrylate (this is referred to as "basic monomer II") 15.02 g of this was called "polymer (A-27-1)"). The obtained polymer (A-27-1) confirmed by GPC that Mw was 11,400 and Mn was 6,800. Then, a dye of the polymer (A-27-1) and CIAcid Blue 93 (acid dye I) by performing the same operation as in Synthesis Example 1-26 above using the polymer (A-27-1) A multimer (this is referred to as "polymer (A-27)") was obtained.

[Synthesis Example 1-28]

Except for changing the cationic monomer to N,N-dimethylaminomethylstyrene (this is referred to as "basic monomer III"), by performing the same operation as in Synthesis Example 1-26, the cationic group represented by the following structural formula 15.07 g of polymer (this is called "polymer (A-28-1)") was obtained. The obtained polymer (A-28-1) confirmed by GPC that Mw was 11,300 and Mn was 7,100. Then, the dye of the polymer (A-28-1) and CIAcid Blue 93 (acid dye I) by performing the same operation as in Synthesis Example 1-26 above using the polymer (A-28-1). A multimer (this is referred to as "polymer (A-28)") was obtained.

[Synthesis Example 1-29]

Except for changing the cationic monomer to N-vinylpyrrolidone (this is referred to as "basic monomer IV"), by performing the same operation as in Synthesis Example 1-26, a cationic group-containing polymer represented by the following structural formula ( 15.03 g of this was called "polymer (A-29-1)"). The obtained polymer (A-29-1) confirmed by GPC that Mw was 12,100 and Mn was 7,400. Then, the dye of the polymer (A-29-1) and CIAcid Blue 93 (acid dye I) by performing the same operation as in Synthesis Example 1-26 above using the polymer (A-29-1). A multimer (this is referred to as "polymer (A-29)") was obtained.

[Synthesis Example 1-30]

Polymer (A-26-1) and CIAcid Red 289 (acid dye II) were mixed with the polymer (A-26-1) by performing the same operation as in Synthesis Example 1-26 except that CIAcid Red 289 (acid dye II) was used as the acid dye. A dye multimer (this is called "polymer (A-30)") was obtained.

In Table 2, the abbreviation of the compound is as follows.

Acidic monomer I: p-(vinylphenyl)trifluoromethanesulfonylimidic acid triethylamine salt

Basic monomer I: methacryloylpropyltrimethylammonium chloride

Basic monomer II: dimethylaminoethyl methacrylate

Basic monomer III: N,N-dimethylaminomethylstyrene

Basic monomer IV: N-vinylpyrrolidone

2. Synthesis of binder resin

[Synthesis Example 2-1]

In a reaction vessel, 28.0 g of compound (M-1), 24.5 g of 2-hydroxyethyl methacrylate (HEMA), 7.0 g of N-cyclohexylmaleimide (CHMI), 3.5 g of styrene (ST), and methacrylic acid ( MA) 7.0 g, 2,2'-azobis (2,4-dimethylvaleronitrile) 4.92 g was weighed, and dissolved in propylene glycol monomethyl ether acetate 40 g and n-butanol 90 g. The temperature of the reaction solution was raised to 75°C while stirring under a nitrogen stream, and stirring was continued for 5 hours. After cooling the reaction solution to room temperature, 200 g of the polymer solution whose solid content concentration is 35 mass % was collect|recovered. The obtained polymer (this is called "polymer (B-1)") confirmed that Mw was 16,000 and Mn was 7,000 by GPC measurement.

[Synthesis Examples 2-2 to 2-7, 2-9 to 2-17 and Comparative Synthesis Examples 2-1 to 2-5]

Polymers (B-2) to (B-7), (B-9) to polymers (B-2) to (B-7), (B-9) to (B-17) and polymers (BR-1) to (BR-5) were synthesized, respectively.

[Synthesis Example 2-8]

In a reaction vessel, 28.0 g of compound (M-1), 24.5 g of glycerin monomethacrylate (GLM), 7.0 g of N-cyclohexylmaleimide (CHMI), 3.5 g of styrene (ST), 7.0 g of methacrylic acid (MA) g, 4.60 g of 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] (manufactured by Wako Pure Chemical Industries, Ltd., water-soluble radical initiator, trade name "VA-086") was weighed and put , It was dissolved in 40 g of propylene glycol monomethyl ether acetate and 90 g of n-butanol. The temperature of the reaction solution was raised to 75°C while stirring under a nitrogen stream, and stirring was continued for 5 hours. After cooling the reaction solution to room temperature, 200 g of the polymer solution whose solid content concentration is 35 mass % was collect|recovered. The obtained polymer (this is called "polymer (B-8)") confirmed that Mw was 15,200 and Mn was 6,800 by GPC measurement.

[Synthesis Example 2-18]

In a reaction vessel, glycidyl methacrylate (GMA) 32.0 g, styrene (ST) 10.9 g, butyl methacrylate (BMA) 27.1 g, 2,2'-azobis (2,4-dimethylvaleronitrile) 7.0 g was weighed and dissolved in 130 g of propylene glycol monomethyl ether acetate. The temperature of the reaction solution was raised to 75°C while stirring under a nitrogen stream, stirring was continued for 3 hours, and then, the temperature of the reaction solution was raised to 100°C and polymerization was further performed for 1 hour to obtain 200 g of a polymer solution. After cooling the polymer solution to room temperature, it was switched under an air stream, acrylic acid (AA) 16.5g and tetrabutylammonium bromide (TBAB) 2.2g were added there, and the heating reaction was performed at 105 degreeC for 10 hours. Then, 22.6 g of tetrahydrophthalic anhydride and 33 g of propylene glycol monomethyl ether acetate were added, and it was made to react at 105 degreeC for 3 hours. After cooling the reaction solution to room temperature, 270 g of polymer solutions whose solid content concentration is 40 mass % were collect|recovered. The obtained polymer (this is called "polymer (B-18)") had Mw of 11,700 and Mn of 6,700.

[Synthesis Example 2-19]

In a reaction vessel, 19.4 g of compound (M-1), 26.4 g of methacrylic acid (MA), 24.2 g of butyl methacrylate (BMA), and 2,2'-azobis(2,4-dimethylvaleronitrile) 7.0 g was weighed and dissolved in 100 g of propylene glycol monomethyl ether acetate and 30 g of n-butanol. The reaction solution was heated to 75°C while stirring under a nitrogen stream, stirring was continued for 3 hours, and then the temperature of the reaction solution was raised to 90°C and polymerization was further performed for 1 hour to obtain 200 g of a polymer solution. After cooling to room temperature, it was switched under an air stream, 27.0 g of methacrylic acid [(3,4-epoxycyclohexane)-1-yl] methyl and 1.9 g of tetrabutylammonium bromide (TBAB) were added thereto, and 105 ° C. Heating reaction was performed for 10 hours. After cooling the reaction solution to room temperature, 240 g of the polymer solution whose solid content concentration is 40 mass % was collect|recovered. The obtained polymer (referred to as "polymer (B-19)") had Mw of 11,900 and Mn of 6,600.

[Synthesis Example 2-20]

3 parts by mass of 2,2'-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer. To this flask, 12 parts by mass of N-cyclohexylmaleimide (CHMI), 10 parts by mass of styrene, 20 parts by mass of methacrylic acid (MA), 15 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 2-ethyl 29 parts by mass of hexyl methacrylate (EHMA), 14 parts by mass of benzyl methacrylate (BzMA), and 5 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Sakai Chemical Co., Ltd.) added, and nitrogen was substituted. Thereafter, by stirring slowly, the temperature of the reaction solution was raised to 80°C, and polymerization was carried out by preserving this temperature for 3 hours. Then, the temperature of the reaction solution was heated up to 100 degreeC, and the binder resin solution containing 33.3 mass % of binder resins (this is called "polymer (BA-1)") was obtained by superposing|polymerizing for 1 hour further. The polymer (BA-1) had Mw of 9,700 and Mn of 5,700.

[Synthesis Example 2-21]

A polymer (B-20) having Mw of 16,000 and Mn of 7,000 was synthesized in the same manner as in Synthesis Example 2-1 except that ethanol was used instead of n-butanol.

3. Synthesis of hydroxyl-containing dyes

[Synthesis Example 3-1]

Using dye A1, 1 equivalent of succinic anhydride was stirred in a pyridine solvent in the presence of a catalytic amount of dimethylaminopyridine at room temperature, followed by solvent distillation after solvent distillation, washing with water and dehydration to obtain a terminal carbonic acid compound. Then, 1 equivalent of tris(hydroxymethyl)aminomethane was stirred at room temperature using 1.2 equivalents of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride in a dichloromethane solvent, followed by washing with water. After dehydration, solvent distillation was performed to obtain dye A3.

[Synthesis Example 3-2]

It replaced with the dye A1 and obtained the dye A4 which is a target object by the method similar to the said synthesis example 3-1 except using the dye which changed the anion of dye A2 into the iodine anion.

[Synthesis Example 3-3]

It replaced with the dye A1, and the dye C which is a target object was obtained by the method similar to the said synthesis example 3-1 except using the pigment|dye of Paragraph 0003 of Unexamined-Japanese-Patent No. 2004-506775.

[Synthesis Example 3-4]

It replaced with the dye A1, except for using the compound [2] described in Chinese patent CN102786459, the method similar to the said synthesis example 3-1 was followed, and the target dye E was obtained.

In addition, dye A1 was synthesize|combined by a well-known method, and dye D was synthesize|combined by a well-known method with reference to Unexamined-Japanese-Patent No. 2812624.

4. Preparation of Colorant Dispersion

[Preparation Example 4-1]

As a colorant, C.I. 13 parts by mass of Pigment Green 58, BYK-LPN21116 (manufactured by Bikchemi Co., Ltd., solid content concentration of 40.0 mass%) as a solution as a solution and a polymer (BA-1) as a binder resin in 13 mass parts (solid content concentration of 33.3 mass%) as a solution (33.3 mass%) as a binder resin. ) as 13.0 parts by mass, and a mixture consisting of 55.0 parts by mass of propylene glycol methyl ether acetate and 8 parts by mass of propylene glycol monomethyl ether as a solvent, mixed and dispersed for 12 hours by a bead mill, and a colorant dispersion (MB-G-1 ) was prepared.

[Preparation Example 4-2]

The type of colorant is C.I. Except having changed into Pigment Green 59, it prepared similarly to the said Preparation Example 4-1, and obtained the coloring agent dispersion liquid (MB-G-2).

[Preparation Example 4-3]

The type of colorant is C.I. Except having changed into Pigment Green 7, it prepared similarly to the said Preparation Example 4-1, and obtained the coloring agent dispersion liquid (MB-G-3).

[Preparation Example 4-4]

The type of colorant is C.I. Except having changed into Pigment Yellow 138, it prepared similarly to the said Preparation Example 4-1, and obtained the coloring agent dispersion liquid (MB-Y-1).

[Preparation Example 4-5]

The type of colorant is C.I. Except having changed into Pigment Yellow 139, it prepared similarly to the said Preparation Example 4-1, and obtained the coloring agent dispersion liquid (MB-Y-2).

[Preparation Example 4-6]

The type of colorant is C.I. Except having changed into Pigment Yellow 185, it prepared similarly to the said Preparation Example 4-1, and obtained the coloring agent dispersion liquid (MB-Y-3).

[Preparation Example 4-7]

The type of colorant is C.I. Except having changed into Pigment Red 177, it prepared similarly to the said Preparation Example 4-1, and obtained the coloring agent dispersion liquid (MB-R-1).

[Preparation Example 4-8]

The type of colorant is C.I. Except having changed to Pigment Blue 15:6, it prepared similarly to the said Preparation Example 4-1, and obtained the coloring agent dispersion liquid (MB-B-1).

[Preparation Example 4-9]

As a colorant, C.I. Pigment Blue 60 7 parts by mass, C.I. Except using 6 mass parts of pigment violet 29, it prepared similarly to the said preparation example 4-1, and prepared the coloring agent dispersion liquid (MB-Bk-1).

[Preparation Example 4-10]

Except having changed the kind of coloring agent into the lactam pigment (Irgaphor Black S0100 CF by BASF), it prepared similarly to the said preparation example 4-1, and obtained the coloring agent dispersion liquid (MB-Bk-2).

[Preparation Example 4-11]

Except having changed the kind of coloring agent into the perylene pigment (Lumogen Black FK4280 by BASF), it prepared similarly to the said Preparation Example 4-1, and obtained the coloring agent dispersion liquid (MB-Bk-3).

[Preparation Example 4-12]

Except having changed the kind of coloring agent into carbon black (TPX1227R by Cabot Corporation), it prepared similarly to the said preparation example 4-1, and obtained the coloring agent dispersion liquid (MB-Bk-4).

5. Preparation and evaluation of coloring composition [1]

[Example 1-1]

(1) Preparation of coloring composition

5.7 parts by mass of the polymer (A-1) obtained in Synthesis Example 1-1, 0.7 parts by mass of Valifast Orange32 (manufactured by Orient Chemical Co., Ltd.), 11.7 parts by mass of a colorant dispersion (MB-Y-2), and a polymer (BA) as a binder resin -1) as a polymer solution (solid content concentration of 33.3 mass%) 5.6 parts by mass, (C) 3.2 parts by mass of dipentaerythritol penta/hexaacrylate as a polymerizable compound, (D) an oxime-based initiator as a photopolymerization initiator ( D-1) 1.0 parts by mass, 0.03 parts by mass of Megapack F-554 (manufactured by DIC Corporation) as a fluorine-based surfactant is mixed, and the solid content concentration of the final composition is 15.0 mass%, to 10% by mass of the total solvent. A corresponding amount of methoxybutyl acetate is added, n-butanol in an amount equivalent to 5 mass % of the total solvent amount is added, diacetone alcohol in an amount equivalent to 20 mass % of the total solvent amount is added, and the remainder The propylene glycol monomethyl ether acetate of the quantity corresponded to the amount of solvent was added, and the coloring composition (G1-1) was prepared.

(2) evaluation

About the coloring composition (G1-1), it evaluated according to following (i) and (ii).

(i) Evaluation of solvent resistance

The coloring composition (G1-1) was _{applied using a spin coater on a soda glass substrate on which a SiO 2} film for preventing sodium ion elution was formed on the surface, and then dried under reduced pressure at room temperature to form a coating film having a thickness of 2.5 µm. did.

Next, using a high-pressure mercury lamp, through a photomask, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 600 J/m 2 . Then, shower development was performed for 60 second by discharging the developing solution which consists of 0.04 mass % potassium hydroxide aqueous solution at 23 degreeC with respect to this board|substrate at a developing pressure of 1 kgf/cm<2> (nozzle diameter 1mm). Then, after wash|cleaning this board|substrate with ultrapure water and air-drying, the rectangular-shaped pattern was formed on the board|substrate by further performing post-baking in 150 degreeC clean oven for 30 minutes. For this rectangular pattern, using a color analyzer (MCPD2000 manufactured by Otsuka Denshi Co., Ltd.), the chromaticity coordinate values (x, y) and stimulus values (Y) in the CIE color space under a C light source and a 2 degree field of view was measured.

Next, for the rectangular pattern after being immersed in a mixed solvent of diethylene glycol methyl ethyl ether / ethylene glycol monobutyl ether = 50/50 (mass ratio) for 5 minutes, a color analyzer (MCPD2000 manufactured by Otsuka Denshi Co., Ltd.) The chromaticity coordinate values (x, y) and the stimulus values (Y) in the CIE color space were measured using a C light source and a 2 degree field of view. The color change before and after immersion, ie, ΔE*ab, was calculated. The evaluation criteria are as follows.

(Evaluation standard)

(double-circle): The value of ΔE*ab is 3.0 or less

○: The value of ΔE*ab is greater than 3.0 and less than or equal to 7.0

Δ: The value of ΔE*ab is greater than 7.0 and less than or equal to 15.0

×: the value of ΔE*ab is greater than 15.0

As a result of evaluation, in Example 1-1, solvent resistance was "double-circle".

(ii) Evaluation of storage stability

The viscosity Vo immediately after preparing the coloring composition (G1-1) was measured using the E-type viscometer (made by Tokyo Keiki). Next, the coloring composition (G1-1) was filled in a light-shielding glass container, and after leaving still at 25 degreeC in a sealed state for 14 days, the viscosity was measured again using the E-type viscometer (made by Tokyo Keiki). The increase rate ΔV[%] (=((Va-Vo)/Vo)×100) of the viscosity Va after storage for 14 days with respect to the viscosity Vo immediately after preparation was calculated, and storage stability was evaluated by the increase rate ΔV. The evaluation criteria are as follows.

(Evaluation standard)

○: increase rate ΔV less than 5%

Δ: increase rate ΔV of 5% or more and less than 10%

x: increase rate ΔV of 10% or more

As a result of evaluation, in Example 1-1, storage stability was "(circle)".

[Examples 1-2 to 1-30 and Comparative Examples 1-1 to 1-4]

Example 1 except that in Example 1-1, the types of the colorant and other components were changed as the chromaticity coordinate values (x, y) in the CIE color space at the C light source show the values in Table 4 below. It carried out similarly to -1, and prepared the coloring compositions (G1-2) - (G1-30) and (G1-1R) - (G1-4R), respectively. About the obtained coloring composition (G1-2) - (G1-30), and (G1-1R) - (G1-4R), it carried out similarly to Example 1-1, and evaluated solvent resistance and storage stability. Those results are shown in Table 4 below.

In Table 4, the abbreviation of a compound is as follows (it is also the same about the following Tables 5-9).

Q-1: Valifast Orange3209

C-1: dipentaerythritol penta/hexaacrylate (manufactured by Toagosei Co., Ltd., trade name Aronix M-402)

D-1: oxime-based initiator (compound represented by the above formula (D-1))

E1: methoxybutyl acetate

E2: propylene glycol monomethyl ether acetate

E3: n-butanol

E4: diacetone alcohol

E5: cyclohexanone

F-1: Megapack F-554 (manufactured by DIC Corporation)

6. Preparation and evaluation of coloring composition [2]

[Example 2-1]

(1) Preparation of coloring composition

28.5 parts by mass of colorant dispersion (MB-G-1), 29.1 parts by mass of colorant dispersion (MB-Y-1), 2.7 parts by mass of polymer (B-3) as binder resin (solid content concentration of 35% by mass), (C) 4.2 parts by mass of dipentaerythritol penta/hexaacrylate as a polymerizable compound, (D) 0.5 parts by mass of an oxime-based initiator (D-1) as a photopolymerization initiator, Megapack F-554 as a fluorine-based surfactant ( DIC Corporation make) 0.03 parts by mass), methoxybutyl acetate in an amount corresponding to 10 mass % of the total solvent amount is added so that the solid content concentration of the final composition becomes 15.0 mass %, and 5 mass % of the total solvent amount The n-butanol of the quantity corresponded to was added, the propylene glycol monomethyl ether acetate of the quantity corresponded further to the remaining solvent amount was added, and the coloring composition (G2-1) was prepared.

(2) evaluation

About the coloring composition (G2-1), it carried out similarly to Example 1-1, and evaluated solvent resistance and storage stability. Those results are shown in Table 5 below.

[Examples 2-2 to 2-27 and Comparative Examples 2-1 to 2-5]

Example 2, except that in Example 2-1, the types of the colorant and other components were changed as the chromaticity coordinate values (x, y) in the CIE color space in the C light source show the values in Table 5 below. It carried out similarly to -1, and prepared the coloring compositions (G2-2) - (G2-27) and (G2-1R) - (G2-5R), respectively. About the obtained coloring composition, it carried out similarly to Example 1-1, and evaluated solvent resistance and storage stability. Those results are shown in Table 5 below.

[Examples 2-28 to 2-31 and Comparative Examples 2-6 to 2-9]

About the coloring composition (G2-4) and the coloring composition (G2-3R), it carried out similarly to Example 1-1, except having changed the temperature in the clean oven at the time of post-baking as shown in Table 6 below, Contents The consistency was evaluated. Their results are shown in Table 6 below.

[Example 2-32]

Example 2, except that in Example 2-1, the types of the colorant and other components were changed as the chromaticity coordinate values (x, y) in the CIE color space in the C light source show the values in Table 6 below. It carried out similarly to -1, and prepared the coloring composition (G2-4A). About the obtained coloring composition (G2-4A), it carried out similarly to Example 1-1, and evaluated solvent resistance except the point which changed the temperature in the clean oven at the time of a post-baking to 85 degreeC. The results are shown in Table 6 below.

7. Preparation and evaluation of coloring composition [3]

[Example 3-1]

(1) Preparation of coloring composition

3.4 parts by mass of dye A1, 0.7 parts by mass of Valifast Orange3209 (manufactured by Orient Chemical Co., Ltd.), 11.7 parts by mass of colorant dispersion (MB-Y-2), and polymer (B-13) as binder resin in a polymer solution (solid content concentration) 35% by mass) as 7.9 parts by mass, (C) as a polymerizable compound, 3.2 parts by mass of dipentaerythritol penta/hexaacrylate, (D) as a photopolymerization initiator, 1.0 parts by mass of an oxime-based initiator (D-1); 0.03 parts by mass of Megapack F-554 (manufactured by DIC Corporation) was mixed as a fluorine-based surfactant, and methoxybutyl acetate in an amount equivalent to 10% by mass of the total solvent so that the solid content concentration of the final composition was 15.0% by mass. , add n-butanol in an amount equivalent to 5 mass % of the total solvent amount, add diacetone alcohol in an amount equivalent to 20 mass % of the total solvent amount, and further add an amount equivalent to the remaining solvent amount Propylene glycol monomethyl ether acetate was added to prepare a coloring composition (G3-1).

(2) evaluation

About the coloring composition (G3-1), it carried out similarly to Example 1-1, and evaluated solvent resistance and storage stability. Their results are shown in Table 7 below.

[Examples 3-2 to 3-13 and Comparative Examples 3-1 to 3-5]

Example 3-1 in Example 3-1, except that the colorant and other components were changed as shown in Table 7 below for the chromaticity coordinate values (x, y) in the CIE color space from the C light source In the same manner as described above, coloring compositions (G3-2) to (G3-13) and (G3-1R) to (G3-5R) were prepared, respectively. About the obtained coloring composition (G3-2) - (G3-13) and (G3-1R) - (G3-5R), it carried out similarly to Example 1-1, and evaluated solvent resistance and storage stability. Their results are shown in Table 7 below.

8. Preparation and evaluation of coloring composition [4]

[Example 4-1]

(1) Preparation of coloring composition

30.9 parts by mass of dye IX, 24.2 parts by mass of colorant dispersion (MB-Y-1), 6.5 parts by mass of polymer (B-12) as binder resin (solid content concentration of 35 mass %), (C) polymerizable compound 3.9 parts by mass of dipentaerythritol penta/hexaacrylate having a hydroxyl value of 100 to 140 mgKOH/g, (D) 0.8 parts by mass of an oxime-based initiator (D-1) as a photopolymerization initiator, and a fluorine-based surfactant 0.03 parts by mass of Pack F-554 (manufactured by DIC Corporation) is mixed, and methoxybutyl acetate is added in an amount corresponding to 10 mass% of the total solvent so that the solid content concentration of the final composition is 15.0 mass%, and the total solvent n-butanol in an amount corresponding to 5% by mass of the total amount of the solvent is added, cyclohexanone in an amount corresponding to 40% by mass of the total amount of solvent is added, and propylene glycol monomethyl ether in an amount corresponding to the remaining amount of solvent. Acetate was added to prepare a coloring composition (G4-1).

(2) evaluation

About the coloring composition (G4-1), it carried out similarly to Example 1-1, and evaluated solvent resistance and storage stability. Their results are shown in Table 8 below.

[Examples 4-2 to 4-11]

Example 4-1 in Example 4-1, except that the colorant and other components were changed as shown in Table 8 below for the chromaticity coordinate values (x, y) in the CIE color space at the C light source It carried out similarly to the coloring composition (G4-2) - (G4-11), respectively, and was prepared. About the obtained coloring composition (G4-2) - (G4-11), it carried out similarly to Example 1-1, and evaluated solvent resistance and storage stability. Their results are shown in Table 8 below.

In Table 8, the abbreviation of the compound is as follows.

C-2A: dipentaerythritol penta/hexaacrylate (hydroxyl value: 60-100 mgKOH/g)

C-2B: dipentaerythritol penta/hexaacrylate (hydroxyl value: 100 to 140 mgKOH/g)

9. Preparation and evaluation of coloring composition [5]

[Example 5-1]

(1) Preparation of coloring composition

16 parts by mass of colorant dispersion (MB-Bk-1), 1.4 parts by mass of colorant dispersion (MB-Bk-4), 25.2 parts by mass of polymer (B-1) as binder resin (solid content concentration of 35% by mass), (C) 3.9 parts by mass of dipentaerythritol penta/hexaacrylate as a polymerizable compound, (D) 1.9 parts by mass of an oxime-based initiator (D-1) as a photopolymerization initiator, Megapack RS-72- as a fluorine-based surfactant 0.2 mass parts of K (manufactured by DIC Corporation) is mixed, and methoxybutyl acetate in an amount corresponding to 10 mass % of the total solvent is added so that the solid content concentration of the final composition is 30.0 mass %, 5 of the total solvent amount The n-butanol of the quantity corresponded to mass % was added, the propylene glycol monomethyl ether acetate of the quantity corresponded further to the remaining solvent amount was added, and the coloring composition (Bk5-1) was prepared.

(2) evaluation

About the coloring composition (Bk5-1), solvent resistance was evaluated according to following (i). Moreover, it carried out similarly to Example 1-1, and evaluated storage stability. Their results are shown in Table 9 below.

(i) Evaluation of solvent resistance

The coloring composition (Bk5-1) was _{applied using a spin coater on a soda glass substrate on which a SiO 2} film for preventing sodium ion elution was formed on the surface, followed by drying under reduced pressure at room temperature to form a coating film having a thickness of 10 µm. did.

Next, using a high-pressure mercury lamp, through a photomask, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 600 J/m 2 . Then, shower development was performed for 60 second by discharging the developing solution which consists of 0.04 mass % potassium hydroxide aqueous solution at 23 degreeC with respect to this board|substrate at a developing pressure of 1 kgf/cm<2> (nozzle diameter 1mm). Then, after washing this board|substrate with ultrapure water, air-drying, and also post-baking in 85 degreeC clean oven for 60 minutes, 3-50 micrometers in width (every 1 micrometer) on a board|substrate, and 1 mm in length formed a line pattern.

Next, the formed line pattern was immersed in a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 50/50 (mass ratio) for 5 minutes, and the line pattern after immersion was observed with an optical microscope. . Solvent resistance was evaluated by the line width which becomes the minimum among the residual patterns after immersion.

(Evaluation standard)

◎: Minimum line width 5㎛ or less

○: Minimum line width 6㎛ or more and 10㎛ or less

△: Minimum line width of 11 µm or more and 30 µm or less

×: Minimum line width of 31 μm or more

As a result of evaluation, in Example 5-1, solvent resistance was "(circle)".

[Examples 5-2 to 5-6 and Comparative Examples 5-1 to 5-6]

In Example 5-1, the coloring composition (Bk5-Bk5- 2) to (Bk5-6) and (Bk5-1R) to (Bk5-6R) were prepared, respectively. About the obtained coloring composition (Bk5-2) - (Bk5-4), (Bk5-6), (Bk5-2R) - (Bk5-4R), and (Bk5-6R), the film|membrane of the coating film in solvent resistance evaluation Except having changed the thickness to 1 micrometer, it carried out similarly to Example 5-1, and evaluated solvent resistance and storage stability. Their results are shown in Table 9 below.

In Table 9, the abbreviation of the compound is as follows.

E6: ethanol

F-2: Megapack RS-72-K (manufactured by DIC Corporation)

From the above results, (A) coloring agent, (B) polymer, and (C) polymerizable compound WHEREIN: The curable composition containing the partial structure and hydroxyl group represented by said Formula (1) in the same molecule or in different molecules has a viscosity It became clear that the cured film excellent in solvent resistance could be manufactured even when post-baking temperature was made low while it was excellent in storage stability with few time-dependent changes of.

Claims (25)

(A) a colorant, (B) a polymer (with the proviso that the (A) colorant is excluded), and (C) a polymerizable compound (with the proviso that the (A) colorant and the (B) polymer are excluded). As a coloring composition to
At least one selected from the group consisting of the (A) colorant, the (B) polymer, and the (C) polymerizable compound has a partial structure represented by the following formula (1),
The coloring composition in which at least 1 sort(s) chosen from the group which consists of said (A) coloring agent, said (B) polymer, and said (C) polymeric compound has a hydroxyl group.

(in formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms; L ¹ is a divalent organic ^{group; X 1} is a divalent linking group having electron withdrawing property; n1 and n2 are each independently an integer of 0 to 2; "*" represents a bond) According to claim 1,
The coloring composition in which at least one of the said (A) coloring agent and the said (B) polymer contains the polymer containing the structural unit (a) which has a partial structure represented by said Formula (1). 3. The method of claim 2,
The said structural unit (a) is a structural unit derived from at least 1 sort(s) chosen from the group which consists of a (meth)acrylic-type monomer, a styrene-type monomer, and a maleimide-type monomer, The coloring composition. 3. The method of claim 2,
The said structural unit (a) is a structural unit represented by following formula (1-2), The coloring composition.

(In Formula (1-2), R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ¹ , R ² , L ¹ , X ¹ , n1 and n2 each have the same meaning as in Formula (1) above. being) 3. The method of claim 2,
The coloring composition containing the said structural unit (a) and the polymer (A1) containing the structural unit (b) which has a pigment|dye structure as said (A) coloring agent. 6. The method of claim 5,
The said structural unit (b) has a structure which consists of a cationic chromophore and a counter anion as said pigment|dye structure, or a structure which consists of an anionic chromophore and a counter cation, The coloring composition. 6. The method of claim 5,
The said polymer (A1) has a structural unit which has a hydroxyl group further, The coloring composition. 8. The method of claim 7,
The structural unit which has the said hydroxyl group is a structural unit derived from the monomer which has an ethylenically unsaturated group, The coloring composition. 3. The method of claim 2,
The coloring composition containing the alkali-soluble polymer which has the said structural unit (a) as said (B) polymer. 10. The method of claim 9,
The said alkali-soluble polymer has a structural unit which has a hydroxyl group further, The coloring composition. 11. The method of claim 10,
The structural unit which has the said hydroxyl group is a structural unit derived from the monomer which has an ethylenically unsaturated group, The coloring composition. 10. The method of claim 9,
The coloring composition containing the coloring agent which has a hydroxyl group as said (A) coloring agent. According to claim 1,
The coloring composition containing the polymer containing the structural unit which has a hydroxyl group as said (B) polymer. 14. The method of claim 13,
The structural unit which has the said hydroxyl group is a structural unit derived from the monomer which has an ethylenically unsaturated group, The coloring composition. According to claim 1,
The coloring composition containing the compound which has a hydroxyl group and two or more polymeric groups as said (C) polymeric compound. According to claim 1,
X ¹ is a group having at least one electron withdrawing group selected from the group consisting of a carbonyl group, an amide group, an imide group, an ester group, a sulfonyl group, a sulfinyl group, a thiocarbonyl group, and a carbonimidyl group, colored, composition. According to claim 1,
The coloring composition whose content of alcohol is more than 0 mass % and 10 mass % or less with respect to the whole quantity of the solvent contained in the said coloring composition. According to claim 1,
The (A) colorant contains a dye,
The coloring composition whose content rate of the said dye is 5 mass % or more with respect to the whole quantity of the said (A) coloring agent. The colored cured film formed using the coloring composition in any one of Claims 1-18. The color filter formed using the coloring composition in any one of Claims 1-18. A display element provided with the colored cured film of Claim 19. The light receiving element provided with the colored cured film of Claim 19. The process of apply|coating the coloring composition in any one of Claims 1-18 on a board|substrate to form a coating film,
A process of removing the solvent contained in the coating film
The manufacturing method of the colored cured film containing. 24. The method of claim 23,
exposing the coating film;
Process of developing the exposed coating film
Further comprising, a method for producing a colored cured film. A curable composition comprising (B) a polymer (with the proviso that the colorant is excluded) and (C) a polymerizable compound (with the proviso that the colorant and the (B) polymer are excluded),
At least one selected from the group consisting of the (B) polymer and the (C) polymerizable compound has a partial structure represented by the following formula (1),
The curable composition in which at least 1 sort(s) chosen from the group which consists of said (B) polymer and said (C) polymeric compound has a hydroxyl group.

(in formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms; L ¹ is a divalent organic ^{group; X 1} is a divalent linking group having electron withdrawing property; n1 and n2 are each independently an integer of 0 to 2; "*" represents a bond)