CN113759660A - Coloring composition and coating film forming composition containing the same - Google Patents

Abstract

The invention provides a coloring composition and a coating film forming composition which can form a cured film which can inhibit the reduction of contrast even being repeatedly exposed to a high-temperature environment and has good brightness and contrast. The coloring composition of the present invention is a coloring composition containing a coloring agent, a dispersant, a (meth) acrylic polymer and a solvent, wherein the coloring agent contains a phthalocyanine compound represented by a specific general formula, the (meth) acrylic polymer comprises a tertiary carbon-containing (meth) acrylate monomer unit, a hydroxyl group-containing monomer unit and a (meth) acrylic acid unit, and the content of the tertiary carbon-containing (meth) acrylate monomer unit is 15 to 90% by mass relative to 100% by mass of the total amount of monomer component units.

Description

Coloring composition and coating film forming composition containing the same

Technical Field

The present invention relates to a coloring composition and a coating film-forming composition containing the same.

Background

In printing inks and paints, for example, in inks for inkjet printers and inks for color filters, a pigment having excellent heat resistance, light resistance and the like is dispersed in a fine state, so that a high coloring power can be exerted, and a spread or a coated product such as a printed matter can be provided with a clear hue, gloss and the like, or a coating film such as a color filter can be provided with suitability for brightness, contrast and the like, and such treatments are widely used. In recent years, higher clarity, gloss, brightness, contrast, and the like have been demanded for these applications. In particular, color filters are used in liquid crystal display devices and organic EL display devices for television applications, and there is an increasing demand for high image quality. However, although a pigment mainly used as a colorant is superior to a dye in heat resistance, light resistance, and the like, it is increasingly difficult to stably disperse the pigment in a fine state, and thus, improvement of brightness and the like is increasingly difficult. Therefore, a proposal of replacing the pigment with the dye has been studied (for example, see patent document 1).

Patent document 1 discloses a colored resin composition containing a colorant, a solvent, a binder resin and a photopolymerization initiator, wherein the colorant contains a phthalocyanine compound having a specific chemical structure, and the binder resin contains an epoxy (meth) acrylate resin. The colored resin composition is considered to have practically sufficient luminance of a color filter and good pattern formability.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2019-144543

Disclosure of Invention

Problems to be solved by the invention

However, the present inventors have found that when a cured film is formed by using the phthalocyanine compound described in patent document 1 and changing various conditions such as a binder resin, the brightness may be improved as compared with the conventional one, but the contrast may be lowered when the cured film is repeatedly exposed to a high-temperature environment of about 100 to 250 ℃.

Accordingly, an object of the present invention is to provide a coloring composition and a coating film forming composition which can form a cured film having good brightness and contrast while suppressing a decrease in contrast even when repeatedly exposed to a high-temperature environment.

Means for solving the problems

The present inventors have made extensive studies to solve the above problems. As a result, they have found that the above-mentioned problems can be solved by using a specific phthalocyanine compound in combination with a specific (meth) acrylic polymer.

A first embodiment of the present invention relates to a coloring composition, wherein:

the coloring composition contains a coloring agent, a dispersing agent, (meth) acrylic acid polymer and a solvent,

the colorant contains a phthalocyanine compound represented by the following formula (1),

the (meth) acrylic polymer comprises a tertiary carbon-containing (meth) acrylate monomer unit, a hydroxyl group-containing monomer unit, and a (meth) acrylic acid unit, and the content of the tertiary carbon-containing (meth) acrylate monomer unit is 15 to 90 mass% relative to 100 mass% of the total amount of monomer component units,

(in the formula (1), A¹～A¹⁶Each independently represents a hydrogen atom, a halogen atom or a group represented by the following general formula (2). Wherein A is¹～A¹⁶Wherein 1 or more of the groups are represented by the following general formula (2). )

(in the formula (2), X represents a linking group having a valence of 2. the benzene ring in the formula (2) may have an optional substituent. ﹡ represents a valence bond.)

In an embodiment of the present invention, the colorant may contain a in the formula (1)²、A³、A⁶、A⁷、A¹⁰、A¹¹、A¹⁴、A¹⁵Independently is a group of formula (2) and A¹、A⁴、A⁵、A⁸、A⁹、A¹²、A¹³、A¹⁶Phthalocyanine compounds which are halogen atoms.

In an embodiment of the present invention, the colorant may contain a in the formula (1)²、A³、A⁶、A⁷、A¹⁰、A¹¹、A¹⁴、A¹⁵And (b) a phthalocyanine compound which is independently a group represented by the formula (2) and in which the benzene ring in the formula (2) has a substituent selected from the group consisting of-COOR and-OR (R independently represents an alkyl group having 1 to 4 carbon atoms which may have a substituent).

In an embodiment of the present invention, the content of the tertiary carbon-containing (meth) acrylate monomer unit may be 20 to 60 mass%, the content of the hydroxyl group-containing monomer unit may be 15 to 50 mass%, and the content of the (meth) acrylic acid unit may be 13 to 30 mass% with respect to 100 mass% of the total amount of the monomer component units in the (meth) acrylic polymer.

In an embodiment of the present invention, the weight average molecular weight of the (meth) acrylic polymer may be 10000 to 50000.

In an embodiment of the present invention, the acid value of the (meth) acrylic polymer may be 80 to 200 mgKOH/g.

In an embodiment of the present invention, the dispersant may be a block copolymer having a tertiary amine.

In an embodiment of the present invention, the amine value of the dispersant may be 50 to 200 mgKOH/g.

The second embodiment of the present invention relates to a coating film-forming composition containing the coloring composition and a coating film-forming component.

Effects of the invention

According to the present invention, it is possible to provide a coloring composition and a coating film forming composition which can form a cured film having good brightness and contrast while suppressing a decrease in contrast even when repeatedly exposed to a high-temperature environment.

Detailed Description

(coloring composition)

The coloring composition according to the embodiment of the present invention is a coloring composition containing a colorant, a dispersant, (meth) acrylic polymer, and a solvent. The colorant contains a phthalocyanine compound represented by the following formula (1). The (meth) acrylic polymer includes a tertiary carbon-containing (meth) acrylate monomer unit, a hydroxyl group-containing monomer unit, and a (meth) acrylic acid unit, and the content of the tertiary carbon-containing (meth) acrylate monomer unit is 15 to 90 mass% relative to 100 mass% of the total amount of monomer component units.

(in the formula (1), A¹～A¹⁶Each independently represents a hydrogen atom, a halogen atom or a group represented by the following general formula (2). Wherein A is¹～A¹⁶Wherein 1 or more of the groups are represented by the following general formula (2). )

(in the formula (2), X represents a linking group having a valence of 2. the benzene ring in the formula (2) may have an optional substituent. ﹡ represents a valence bond.)

By using a specific phthalocyanine compound in combination with a specific (meth) acrylic copolymer in this manner, heat resistance can be improved, and even when the cured film is repeatedly exposed to a high-temperature environment, a decrease in contrast of the obtained cured film can be suppressed, and a cured film having good brightness and contrast can be formed. The main reason for this is not clear, but it is presumed that the aggregation of the phthalocyanine compound in the film is suppressed by the interaction between the (meth) acrylic copolymer and the phthalocyanine compound after the film formation.

< coloring agent >

The phthalocyanine compound represented by the formula (1) (hereinafter, may be simply referred to as "phthalocyanine compound") may be any phthalocyanine compound represented by the formula (1), and the phthalocyanine compound described in patent document 1 may be used. Referring to the description of patent document 1, the details of formulae (1) and (2) are as follows.

As A in formula (1)¹～A¹⁶Examples of the halogen atom in (2) include a fluorine atom, a chlorine atom, and a bromine atom. Fluorine atoms are preferred from the viewpoint of adjusting the hue to the best hue as a green pigment used for a color filter and from the viewpoint of improving the luminance.

The linking group having a valence of 2 represented by X in the formula (2) is not particularly limited, but may be an oxygen atom, a sulfur atom or-N (R)¹) -radical (R)¹Represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. ). Among these, from the viewpoint of stability under a high-temperature environment, an oxygen atom or a sulfur atom is preferable, and an oxygen atom is more preferable.

The substituent that the benzene ring in the formula (2) may have is not particularly limited. Examples thereof include a halogen atom, an alkyl group and an alkoxy group (-OR)²Radical (wherein R²Represents an alkyl group. ) - (COOR), alkoxycarbonyl (-COOR)²Radical (wherein R²Represents an alkyl group. ) Aryl, aryloxy (-OR)³Radical (wherein R³Represents an aryl group. ) - (COOR), aryloxycarbonyl (-COOR)³Radical (wherein R³Represents an aryl group. ) Alkyl groups (-R) contained in these groups (-R)²Yl), aryl (-R)³These substituents may be further contained in the group). Among these, alkoxy groups and alkoxycarbonyl groups are preferable, and alkoxycarbonyl groups are more preferable, from the viewpoint of solubility in a solvent and brightness.

The alkyl group contained in these groups may be linear, branched or cyclic, but is preferably linear from the viewpoint of solubility in a solvent. The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 6 or less, more preferably 5 or less, and still more preferably 4 or less. When the amount is equal to or more than the lower limit, the solubility of the phthalocyanine compound in the solvent tends to be improved, and when the amount is equal to or less than the upper limit, the phthalocyanine compound tends to exhibit hydrophobic interaction with a hydrophobic portion in the (meth) acrylic polymer. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and the like, and from the viewpoint of effectively exhibiting hydrophobic interaction together with a hydrophobic moiety in the (meth) acrylic polymer while maintaining solubility in an organic solvent, the alkyl group is preferably a methyl group or an ethyl group, and more preferably an ethyl group.

The aryl group contained in these groups may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. The number of carbon atoms of the aryl group is not particularly limited, but is usually 4 or more, preferably 6 or more, and further preferably 12 or less, more preferably 10 or less, and still more preferably 8 or less. When the amount is equal to or more than the lower limit, the solubility of the phthalocyanine compound in a solvent tends to be improved, and when the amount is equal to or less than the upper limit, the hue change due to an aryl group tends to be suppressed.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring and the like having a free valence of 1.

The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include groups having a valence of 1 free atom such as a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, a 4H-thiopyran ring, a pyridine ring, a1, 3-oxazole ring, an isoxazole ring, a1, 3-thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furazan ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a1, 3, 5-triazine ring, a benzofuran ring, a 2-benzofuran ring, a benzothiophene ring, a 2-benzothiophene ring, a 1H-pyrrolidine ring, an indole ring, an isoindole ring, an indolizine ring, a 2H-1-benzopyran ring, a 1H-2-benzopyran ring, a quinoline ring, an isoquinoline ring, a 4H-quinazoline ring, a benzimidazole ring, a 1H-indazole ring, a quinoxaline ring, a quinazoline ring, a cinnoline ring, a phthalazine ring, a1, 8-naphthyridine ring, a purine ring, and a pteridine ring.

When the benzene ring in the formula (2) has an arbitrary substituent, the number of substitution is not particularly limited, but from the viewpoint of improving heat resistance by pi-pi stacking of phthalocyanine compound molecules and suppressing decrease in luminance due to decomposition of the phthalocyanine compound, the number of substitution for 1 benzene ring is preferably 1. When the benzene ring in formula (2) has an optional substituent, the substitution position may be either ortho, meta or para, but para is preferred from the viewpoint of promoting pi-pi stacking between phthalocyanine compound molecules, improving heat resistance, and suppressing decrease in luminance due to decomposition of the phthalocyanine compound.

A¹～A¹⁶Of these, 1 or more represents a group represented by the above general formula (2), but A is preferably A from the viewpoint of solubility in a solvent and brightness¹～A⁴Wherein 1 or more are a group represented by the above general formula (2), A⁵～A⁸Wherein 1 or more are a group represented by the above general formula (2), A⁹～A¹²Wherein 1 or more are groups represented by the above general formula (2) and A¹³～A¹⁶Wherein 1 or more are groups represented by the above general formula (2), more preferably A¹～A⁴Wherein 2 or more are a group represented by the above general formula (2), A⁵～A⁸Wherein 2 or more are a group represented by the above general formula (2), A⁹～A¹²Wherein 2 or more are groups represented by the general formula (2) and A¹³～A¹⁶Wherein 2 or more are groups represented by the above general formula (2). From the viewpoint of color tone required for color filters, solubility in solvents, and suppression of contrast reduction, a is more preferable²、A³、A⁶、A⁷、A¹⁰、A¹¹、A¹⁴And A¹⁵Is a group represented by the above general formula (2) and A¹、A⁴、A⁵、A⁸、A⁹、A¹²、A¹³And A¹⁶Is a halogen atom. Of these, more preferably, the benzene ring in the general formula (2) has a structure selected from the group consisting of-COOR and-OR (R independently represents a group which may haveThe substituent is an alkyl group having 1 to 4 carbon atoms. ) The substituent (1) in (1). The substituents which may be contained in R are as described above.

The phthalocyanine compound can be obtained by, for example, the method described in Japanese patent application laid-open No. H05-345861.

The colorant may contain other colorants in addition to the phthalocyanine compound. Examples of such a colorant include pigments and dyes. When the color filter is a green pixel, a yellow pigment or dye can be used as a complementary color. In addition, other green pigments and dyes can be used for adjusting the color tone.

Examples of yellow pigments, indicated by color index numbers, include c.i. pigment yellow 1, 1: 1, 2,3, 4,5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35: 1, 36: 1, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62: 1, 63, 65, 73, 74, 75, 81, 83, 86, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127: 1, 128, 129, 133, 134, 136, 137, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 167, 168, 166, 183, 168, 166, 183, 175, 188, 165, 188, 165, 180, 175, 185, 189, 183, 180, 168, 183, 168, 189, 180, 168, 166, 180, 166, 180, 166, 168, 150, 166, and 168, 190, 70, c, b, c, b, c, b, c, b, c, b, c, b, c, b, c, b, c, b, c, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, etc. Among them, c.i. pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 are preferable, and 83, 138, 139, 180, 185 are more preferable from the viewpoint of high luminance and high color gamut.

Examples of the yellow dye include barbituric acid azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes, and cerinnine dyes. Specific examples thereof include the specific compounds described in jp 2010-168531 a.

Examples of the green pigment include c.i. pigment green 7, 36, 58, 59, 62, and 63 when indicated by a color index. As the green dye, among the substances classified as dyes in the color index, the c.i. solvent dyes include, for example, c.i. solvent green 1,3, 4,5, 7, 28, 29, 32, 33, 34, 35, and the like. Examples of the c.i. acid dye include c.i. acid-green 1,3,5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, and c.i. mordant-green 1,3, 4,5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, and 53.

When the pigment is contained, the average primary particle diameter can be appropriately adjusted within a range not affecting contrast or the like. The average primary particle diameter is preferably 10 to 100nm, more preferably 10 to 50nm, and particularly preferably 10 to 30 nm. The primary particle diameter can be measured from an image obtained by imaging the pigment with a transmission electron microscope at a magnification of 10 ten thousand, for example. The average primary particle diameter can be determined by, for example, measuring 100 particles and defining the average value as the average primary particle diameter.

Depending on the type of pigment, the pigment may be subjected to a grinding treatment in advance from the viewpoint of adjusting the average primary particle diameter. The grinding treatment can be carried out by a conventional method in accordance with the kind of pigment or the like. Examples of such a polishing treatment include a solvent salt polishing method.

The content of the colorant is preferably 3 to 20% by mass of the coloring composition. The content of the phthalocyanine compound in the colorant is preferably 30 to 100% by mass based on the solid content.

< pigment derivative >

When the pigment is contained, the pigment derivative may be used as a dispersion aid for more stable dispersion of the pigment in the coloring composition. When a pigment derivative is used, a portion having affinity with a dispersant, which will be described later, or a pigment derivative having a polar group introduced thereto is adsorbed on the surface of each pigment, and may serve as an adsorption site of the dispersant. In this case, since the dispersant can be present on the pigment surface via the pigment derivative, each pigment can be dispersed in the pigment dispersion in the form of fine particles more stably. In addition, re-aggregation can be more effectively prevented.

Specifically, the pigment derivative is a compound obtained by introducing an acidic group, a basic group or an aromatic group into a side chain of a pigment as a matrix skeleton. Specific examples of the pigment to be a matrix skeleton include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, pyrrolopyrroledione pigments, benzimidazolone pigments, dioxazine pigments, and the like. Further, the matrix skeleton includes a pale yellow aromatic polycyclic compound such as a naphthalene-based, anthraquinone-based, triazine-based, or quinoline-based compound which is not generally called a coloring matter.

As the pigment derivative, there can be used those described in Japanese patent application laid-open Nos. 11-49974, 11-189732, 10-245501, 2006-265528, 8-295810, 11-199796, 2005-234478, 2003-240938, 2001-356210 and the like.

The content (solid content) of the pigment derivative in the coloring composition is preferably 2 to 15 parts by mass, and more preferably 5 to 10 parts by mass, based on 100 parts by mass of the pigment, from the viewpoint of dispersion stability. The optimum amount of the pigment derivative to be added may be appropriately adjusted depending on the combination with the type of the pigment and dispersant to be used, and the like.

(meth) acrylic polymer

The (meth) acrylic polymer comprises a tertiary carbon-containing (meth) acrylate monomer unit, a hydroxyl group-containing monomer unit, and a (meth) acrylic acid unit, and the content of the tertiary carbon-containing (meth) acrylate monomer unit is 15 to 90% by mass relative to 100% by mass of the total amount of monomer component units. As such a (meth) acrylic polymer, for example, a (meth) acrylic polymer described in Japanese patent laid-open publication No. 2018-16807 can be used. The details of the (meth) acrylic polymer will be described below with reference to the description of this patent document.

The (meth) acrylate monomer unit containing a tertiary carbon is a structural unit in which a polymerizable carbon-carbon double bond (C ═ C) in the monomer is a single bond (C — C), but the monomer is preferably a monomer having a structure in which an oxygen atom adjacent to a (meth) acryloyl group is bonded to a tertiary carbon atom. That is, the (meth) acrylate monomer having a tertiary carbon preferably has a structure in which an oxygen atom adjacent to a (meth) acryloyl group is bonded to a tertiary carbon atom. The tertiary carbon atom means a carbon atom having 3 carbon atoms as other carbon atoms bonded to the carbon atom.

The tertiary carbon-containing (meth) acrylate monomer is preferably a compound having 1 polymerizable carbon-carbon double bond in the molecule, that is, 1 (meth) acryloyl group (H) in the molecule₂The compound represented by C (b) -C (═ O) -) is preferably a compound represented by the following general formula (3):

H₂C＝C(B)－C(＝O)－O－Y (3)

(B represents a hydrogen atom or a methyl group and Y represents a monovalent organic group having a structure having a tertiary carbon atom on the oxygen atom side).

In the above general formula (3), the organic group represented by Y may be represented by, for example, -C (Q)¹)(Q²)(Q³) And (4) showing. In this case, Q is preferably Q¹、Q²And Q³The same or different is a hydrocarbon group having 1 to 30 carbon atoms, and the hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The hydrocarbon group may have a cyclic structure or may have a substituent. In addition, Q¹、Q²And Q³Or may be linked at the terminal portions to form a ring structure.

As will be described later, the new compound produced by cleaving the O — C bond between the oxygen atom adjacent to the (meth) acryloyl group and the tertiary carbon atom in Y adjacent thereto is easily volatilized, and from this viewpoint, the number of carbon atoms of the organic group represented by Y is preferably 12 or less. Among them, the organic group represented by Y is preferably a group derived from t-butyl (meth) acrylate and/or t-amyl (meth) acrylate. In addition, the organic group represented by Y may have a branched structure.

In the tertiary-carbon-containing (meth) acrylate monomer, at least 1 of the tertiary carbon atoms bonded to the oxygen atom adjacent to the (meth) acryloyl group, preferably the adjacent carbon atoms, is bonded to a hydrogen atom. For example, the (meth) acrylate monomer having a tertiary carbon is a compound represented by the general formula (3) wherein Y is-C (Q)¹)(Q²)(Q³) In the case of the groups shown, Q¹、Q²And Q³At least 1 of them is a carbon atom containing 1 or more hydrogen atoms, and the carbon atom is preferably bonded to a tertiary carbon atom. In such an embodiment, the heating cuts off the O — C bond between the oxygen atom adjacent to the (meth) acryloyl group and the tertiary carbon atom adjacent thereto, thereby forming (meth) acrylic acid and, at the same time, a double bond (C ═ C) between the tertiary carbon atom and the carbon atom adjacent thereto, thereby more stably producing a new compound.

The novel compounds are preferably capable of volatilization. In this case, the new compound volatilizes from the cured product, and the film thickness of the cured product (cured film) decreases, and the concentration of the colorant increases after heating. Therefore, the color purity can be further enhanced while further thinning is achieved. In view of this, Q is preferably selected¹、Q²And Q³The same or different are saturated hydrocarbon groups having 1 to 15 carbon atoms. More preferably a saturated hydrocarbon group having 1 to 10 carbon atoms, still more preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, and particularly preferably a saturated hydrocarbon group having 1 to 3 carbon atoms.

The content of the (meth) acrylate monomer unit containing a tertiary carbon is preferably 15% by mass or more with respect to 100% by mass of the total amount of the monomer components. This can exhibit the aforementioned effects due to the structural unit derived from the (meth) acrylate monomer having a tertiary carbon. More preferably 20% by mass or more. The upper limit of the content may be appropriately set in consideration of the content of other monomers, but is preferably 90 mass% or less in view of further improving pattern characteristics and developability when used for color filters, for example. Preferably 75% by mass or less, and more preferably 60% by mass or less.

The monomer unit having a hydroxyl group is, for example, a unit derived from a monomer having an alcoholic hydroxyl group bonded to a compound having a polymerizable double bond. By having such a monomer unit, a cured film having improved curability and excellent solvent resistance and transparency can be formed. Examples of the monomer having a hydroxyl group in the molecule include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2, 3-hydroxypropyl (meth) acrylate.

The content ratio of the monomer unit having a hydroxyl group is not particularly limited, but is preferably 5 to 50% by mass, more preferably 10 to 50% by mass, even more preferably 15 to 40% by mass, and most preferably 15 to 35% by mass, relative to 100% by mass of the total amount of the monomer components, from the viewpoint of solvent resistance and developability.

The (meth) acrylic acid unit can impart alkali-solubility and has a function of imparting good developability. This unit refers to a structural unit derived from (meth) acrylic acid in the case where (meth) acrylic acid is copolymerized or graft-polymerized. The acid value of the (meth) acrylic polymer can be adjusted by adjusting the content ratio of the (meth) acrylic unit.

The content ratio of the (meth) acrylic acid monomer is preferably set so that the acid value of the (meth) acrylic acid polymer falls within a desired range. For example, the content is preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more, and particularly preferably 13% by mass or more, based on 100% by mass of the total amount of the monomer components. Further, it is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less. The preferable range of the content ratio is, for example, 13 to 30% by mass relative to 100% by mass of the total amount of the monomer components.

The (meth) acrylate polymer preferably has a ring structure in the main chain. For example, a polymer obtained by copolymerizing a monomer capable of forming a ring structure in the main chain is more preferable. Examples of the ring structure include an imide ring, a tetrahydropyran ring, a tetrahydrofuran ring, and a lactone ring. Examples of the monomer capable of forming a ring structure in the main chain include an N-substituted maleimide monomer, a dialkyl-2, 2' - (oxydimethylene) diacrylate monomer, and an α - (unsaturated alkoxyalkyl) acrylate monomer (preferably an alkyl- (α -allyloxymethyl) acrylate monomer). In this way, the (meth) acrylate polymer preferably further contains at least 1 monomer unit selected from the group consisting of an N-substituted maleimide monomer unit, a dialkyl-2, 2' - (oxydimethylene) diacrylate monomer unit, and an α - (unsaturated alkoxyalkyl) acrylate monomer. Further, 1 or 2 or more of (meth) acrylate monomers, aromatic vinyl monomers, and the like may be suitably used in accordance with the required physical properties.

For example, when an N-substituted maleimide monomer and/or a dialkyl-2, 2' - (oxydimethylene) diacrylate monomer and/or an alkyl- (. alpha. -allyloxymethyl) acrylate monomer is used, a cured film having improved heat resistance, hardness, color material dispersibility, and the like can be further provided. In particular, when a dialkyl-2, 2' - (oxydimethylene) diacrylate monomer and/or an alkyl- (α -allyloxymethyl) acrylate monomer is used, a cured film having more excellent heat-resistant coloring properties can be obtained.

The content of the monomer capable of forming a ring structure in the main chain is preferably 60% by mass or less, and more preferably 50% by mass or less, based on 100% by mass of the total amount of the monomer components. In particular, when the N-substituted maleimide monomer, dialkyl-2, 2' - (oxydimethylene) diacrylate monomer and/or α - (unsaturated alkoxyalkyl) acrylate monomer are contained, the content thereof is preferably 2 to 60% by mass, more preferably 2 to 50% by mass, and still more preferably 3 to 40% by mass, from the viewpoints of heat resistance, hardness, color material dispersibility, development speed, transparency, and the like.

Examples of the N-substituted maleimide monomer include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-t-butylmaleimide, N-dodecylmaleimide, N-benzylmaleimide, and N-naphthylmaleimide, and 1 or 2 or more of these monomers can be used. Among them, from the viewpoint of transparency, N-phenylmaleimide and N-benzylmaleimide are preferable, and N-benzylmaleimide is particularly preferable.

As N-benzylmaleimide, there may be mentioned, for example, benzylmaleimide; alkyl-substituted benzylmaleimides such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl-substituted benzylmaleimides such as p-hydroxybenzylmaleimide; halogen-substituted benzylmaleimides such as o-chlorobenzylmaleimide, o-dichlorobenzylmaleimide and p-dichlorobenzylmaleimide; and the like.

Examples of the dialkyl-2, 2 '- (oxydimethylene) diacrylate monomers include compounds having at least 1 tertiary carbon in the ester site such as 2, 2' - [ oxybis (methylene) ] bisacrylic acid, dialkyl-2, 2 '- [ oxybis (methylene) ] bis-2-acrylate, and dialkyl-2, 2' - [ oxybis (methylene) ] bis-2-acrylate. Among these, from the viewpoint of transparency, dispersibility, industrial availability and the like, for example, dimethyl-2, 2' - [ oxybis (methylene) ] bis-2-acrylate and the like are preferably used.

Examples of the α - (unsaturated alkoxyalkyl) acrylate monomer include α -allyloxymethylacrylic acid, α -allyloxymethylmethacrylate, ethyl α -allyloxymethylacrylate, n-propyl α -allyloxymethylmethacrylate, isopropyl α -allyloxymethylacrylate, n-butyl α -allyloxymethylacrylate, sec-butyl α -allyloxymethylmethacrylate, tert-butyl α -allyloxymethylacrylate, n-pentyl α -allyloxymethylmethacrylate, sec-pentyl α -allyloxymethylmethacrylate, tert-pentyl α -allyloxymethylacrylate and neopentyl α -allyloxymethylmethacrylate. In addition, alkyl- (. alpha. -methallyloxymethyl) acrylate monomers and the like are also preferred. Among them, alkyl- (. alpha. -allyloxymethyl) acrylate monomers are preferred. As the alkyl- (. alpha. -allyloxymethyl) acrylate monomer, for example, methyl- (. alpha. -allyloxymethyl) acrylate or the like is preferably used from the viewpoints of transparency, dispersibility, industrial availability, and the like.

The α - (unsaturated alkoxyalkyl) acrylate can be produced by, for example, the production method disclosed in international publication No. 2010/114077.

The (meth) acrylic polymer may contain a (meth) acrylate monomer, an aromatic vinyl monomer, and other copolymerizable monomer units for the purpose of controlling developability, solvent solubility, and the like.

The (meth) acrylate monomer is preferably a monomer containing an alicyclic skeleton, for example, in view of the surface hardness of the cured product. Specific examples thereof include cyclohexyl (meth) acrylate, cyclohexyl methyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, methyl (3, 4-epoxycyclohexyl) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecenyl (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, pentacyclopentadecane dimethanol di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate, norbornandimethanol di (meth) acrylate, p-xylylene glycol di (meth) acrylate, and mixtures thereof

Alkane-1, 8-diol di (meth) acrylate, p-xylene glycol

Alkane-2, 8-diol di (meth) acrylate, p-xylene glycol

Alkane-3, 8-diol di (meth) acrylate, bicyclo [2.2.2]-octane-1-methyl-4-isopropyl-5, 6-dimethylol di (meth) acrylate, and the like. Among these, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclodecenyl (meth) acrylate are preferable from the viewpoints of versatility, availability, and the like. In addition, alicyclic epoxy compounds such as glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, and ethylglycidyl (meth) acrylate are also preferably used.

Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, n-pentyl (meth) acrylate, sec-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, and mixtures thereof, Tetrahydrofurfuryl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, methyl α -hydroxymethylacrylate, ethyl α -hydroxymethylacrylate, t-butyl α -hydroxymethylacrylate, t-amyl α -hydroxymethylacrylate, and the like, further examples of the solvent include 1, 4-dioxaspiro [4,5] decan-2-yl methacrylic acid, (meth) acryloylmorpholine, tetrahydrofurfuryl acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1, 3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1, 3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-cyclohexyl-1, 3-dioxolane, 4- (meth) acryloyloxymethyl-2, 2-dimethyl-1, 3-dioxolane and the like. Among them, alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and benzyl (meth) acrylate are preferable because a balance among heat resistance, color material dispersibility, and solvent re-solubility is easily obtained.

Examples of the aromatic vinyl monomer include styrene, vinyltoluene, α -methylstyrene, and methoxystyrene. Among them, styrene and/or vinyltoluene are preferable particularly in view of the resistance to thermal coloration and thermal decomposition of the copolymer.

The other copolymerizable monomers may be 1 or 2 or more of the following compounds, for example.

(meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; macromonomers having a (meth) acryloyl group at one end of a polymer molecular chain of polystyrene, poly (methyl (meth) acrylate), polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, polycaprolactam, or the like; conjugated dienes such as 1, 3-butadiene, isoprene and chloroprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, and 4-hydroxybutyl vinyl ether; n-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine and N-vinylacetamide; unsaturated isocyanates such as isocyanatoethyl (meth) acrylate and allylisocyanate; and the like.

As a method for polymerizing the monomer component, a commonly used method such as bulk polymerization, solution polymerization, emulsion polymerization, etc. can be used, and it may be appropriately selected depending on the purpose and use. Among them, solution polymerization is preferable because it is industrially advantageous and the structure such as molecular weight can be easily adjusted. In addition, as the polymerization mechanism of the monomer component, a polymerization method based on a mechanism such as radical polymerization, anion polymerization, cation polymerization, coordination polymerization, etc. can be used, but a polymerization method based on a radical polymerization mechanism is industrially advantageous and is preferable.

When monomer components including a monomer capable of forming a ring structure in the main chain, a (meth) acrylate monomer containing a tertiary carbon, acrylic acid, and other (meth) acrylate monomers are polymerized, the compounding ratio (mass%) of the monomer capable of forming a ring structure in the main chain (5 to 20 mass%), the (meth) acrylate monomer containing a tertiary carbon (15 to 40 mass%), the monomer having a hydroxyl group (10 to 30 mass%), acrylic acid (5 to 30 mass%), and the (meth) acrylate monomer (10 to 40 mass%) are preferable.

When the monomer component is polymerized by a solution polymerization method, the polymerization solvent used for the polymerization is not particularly limited as long as it is inactive in the polymerization reaction. For example, polymerization conditions may be appropriately set according to the polymerization mechanism, the kind and amount of the monomer used, the polymerization temperature, the polymerization concentration, and the like, but when a solvent is used as a diluent or the like in the subsequent production of the curable resin composition, it is preferable to use a solvent containing the solvent for the solution polymerization of the monomer component from the viewpoint of efficiency.

The polymerization solvent includes, for example, the following compounds, and 1 or 2 or more of these can be used.

Monoalcohols such as methanol, ethanol, isopropanol, n-butanol, and sec-butanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; glycol monoethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and 3-methoxybutanol; glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, and propylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, and the like; alkyl esters such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl acetoacetate, and ethyl acetoacetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; aliphatic hydrocarbons such as hexane, cyclohexane, and octane; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; and the like.

The amount of the polymerization solvent used is preferably 50 to 1000 parts by mass, more preferably 100 to 500 parts by mass, based on 100 parts by mass of the monomer component.

As other polymerization conditions, for example, the kinds and amounts of the polymerization initiator and the chain transfer agent, the polymerization temperature, the polymerization time, etc., the conditions described in Japanese patent laid-open publication No. 2018-16807 can be employed.

The acid value of the (meth) acrylic polymer is preferably 80 to 200mgKOH/g, more preferably 100 to 180mgKOH/g, from the viewpoint of solvent resistance and developability. The acid value (acid value in terms of solid content) can be determined, for example, by a method in DIN EN ISO 2114.

The weight average molecular weight of the (meth) acrylic polymer is preferably 10000 to 50000, more preferably 12000 to 40000, and still more preferably 15000 to 30000, from the viewpoint of solvent resistance and developability. The weight average molecular weight can be determined, for example, in the manner of examples described later.

The content of the (meth) acrylic polymer (based on solid content) is preferably 5 to 35 parts by mass based on 100 parts by mass of the total of the colorant or the colorant and the pigment derivative.

< dispersant >

Examples of the dispersant include a resin type dispersant and a surfactant type dispersant. The dispersant has a function of stabilizing and allowing the colorant and the (meth) acrylic polymer to coexist in a solvent. The case where the colorant contains a pigment is more preferable.

Examples of the resin type dispersant include polyurethane; a polyester; an unsaturated polyamide; a phosphate ester; polycarboxylic acids and their amine, ammonium, alkylamine salts; a polycarboxylate; a polycarboxylate containing hydroxyl groups; a polysiloxane; a modified polyacrylate; water-soluble high molecular compounds such as alginic acid, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, polyvinylpyrrolidone, and gum arabic; resins containing ethylenic double bonds such as styrene-acrylic resins, styrene-methacrylic resins, styrene-acrylic acid-acrylate resins, styrene-maleic acid ester resins, methacrylic acid-methacrylate resins, acrylic acid-acrylate resins, isobutylene-maleic acid resins, vinyl-ester resins, rosin-modified maleic acid resins, and the like; amine resins such as polyallylamine, polyvinylamine, and polyethyleneimine; and the like.

The resin-type dispersant is preferably a block copolymer having a tertiary amine from the viewpoint of further exerting an effect of suppressing a decrease in contrast of a cured film. In addition, the amine value is preferably 50 to 200mgKOH/g, more preferably 60 to 160mgKOH/g, and still more preferably 70 to 150mgKOH/g, from the viewpoint of further exhibiting the effect of improving the brightness of the cured film and the effect of suppressing the decrease in contrast.

The amine value of the resin type dispersant can be determined by the functional group contained in the resin constituting the resin type dispersant and the content thereof. The amine value (amine value in terms of solid content) can be determined, for example, by the method in DIN 16945.

As the resin type dispersant, a commercially available resin type dispersant can be used. Specific examples of commercially available products are as follows, but are not limited thereto.

Manufactured by LUBRIZOL corporation of japan: SOLSPERSE 3000, 9000, 13240, 17000, 20000, 24000, 26000, 27000, 28000, 32000, 32500, 36000, 38500, 39000, 55000, 41000;

BYK CHEMIE-JAPAN: disperbyk 108, 110, 112, 140, 142, 145, 161, 162, 163, 164, 166, 167, 171, 174, 182, 190, 2000, 2001, 2050, 2070, 2150, LPN6919, LPN22101, LPN21116, LPN 22956;

manufactured by BASF corporation: EFKA 4401, 4403, 4406, 4330, 4340, 4010, 4015, 4046, 4047, 4050, 4055, 4060, 4080, 5064, 5207, 5244;

ajinomoto Fine-Techno, manufactured by Ajinomoto corporation: AJISPER-PB 821(F), PB822, PB 880;

chuanchuan fine chemical company, made by: HINACT T-8000;

manufactured by Nanben Kabushiki Kaisha: DISPARON PW-36, DISPARON DA-325, 375, 7301; and the like.

The molecular weight of the resin type dispersant is not particularly limited, but the weight average molecular weight is preferably 1000 to 100000.

The surfactant-type dispersant includes, in accordance with its ionic nature, anionic surfactants (anionic) such as naphthalene sulfonic acid formaldehyde condensate salts, aromatic sulfonic acid formaldehyde condensates, polyoxyethylene alkyl phosphate esters, etc., nonionic surfactants (nonionic) such as polyoxyethylene alkyl ethers, etc., cationic surfactants (cationic) such as alkylamine salts, quaternary ammonium salts, etc., and the like. Various surface-active dispersants are also commercially available, and specific examples thereof include, but are not limited to, the following.

Manufactured by kao corporation: demo N, RN, MS, SN-B, EMULGEN 120, 430, ACETAMIN 24, 86, QUARTAMIN 24P;

manufactured by heliochemical corporation: NIKKOL BPS-20, BPS-30, DHC-30, BPSH-25;

first industrial pharmaceutical co: plursf AL, a 208F;

manufactured by lion king corporation: ARQUAD C-50, T-28, T-50; and the like.

The number of the above-mentioned dispersants may be 1 or a combination of 2 or more. The content of the dispersant (solid content or active ingredient) is preferably 10 to 40 parts by mass relative to 100 parts by mass of the total of the colorant or the colorant and the pigment derivative, from the viewpoint of allowing the colorant and the (meth) acrylic polymer to coexist satisfactorily and stably. However, the optimum amount of the dispersant to be added may be appropriately adjusted depending on the kind and combination of the pigment to be used.

< solvent >

The solvent can be appropriately selected according to the kind of the coating film forming component described later, and examples thereof include various organic solvents such as aromatic solvents, ketone solvents, ester solvents, glycol ether solvents, alcohol solvents, and aliphatic solvents. Among these, from the viewpoint of film formability, organic solvents selected from aromatic, ketone, ester, and glycol ether are preferable. The organic solvent may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Examples of the aromatic organic solvent include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene.

Examples of the ketone-based organic solvent include methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, acetylacetone, isophorone, acetophenone, and cyclohexanone.

Examples of the ester-based organic solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, isopropyl acetate, methyl propionate, 3-methoxybutyl acetate, ethylene glycol acetate, propylene glycol monomethyl ether acetate (PMA), propylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, methyl monochloroacetate, ethyl monochloroacetate, butyl monochloroacetate, methyl acetoacetate, ethyl acetoacetate, butyl carbitol acetate, butyl lactate, ethyl-3-ethoxy propionate, ethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, propyl acetate, and 1, 3-butanediol diacetate.

Examples of the glycol ether-based organic solvent include water-soluble glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-isopropyl ether, diethylene glycol mono-isopropyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-isopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-isopropyl ether, propylene glycol mono-n-butyl ether, and dipropylene glycol mono-n-butyl ether; and water-insoluble glycol ethers such as ethylene glycol monohexyl ether, ethylene glycol-2-ethylhexyl ether, ethylene glycol phenyl ether, diethylene glycol n-hexyl ether, diethylene glycol-2-ethylhexyl ether, propylene glycol monobutyl ether, dipropylene glycol propyl ether, and propylene glycol methyl ether propionate.

Examples of the alcohol-based organic solvent include alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol, and isopropanol; ethylene glycol, propylene glycol, diethylene glycol, pentamethylene glycol, trimethylene glycol, 2-butene-1, 4-diol, 2-ethyl-1, 3-hexanediol, 2-methyl-2, 4-pentanediol, tripropylene glycol, polyethylene glycol having a molecular weight of 2000 or less, 1, 3-propanediol, isopropylene glycol, isobutylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, glycerol, meso-erythritol (meso-erythritol), pentaerythritol, and the like.

Examples of the aliphatic organic solvent include aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane.

The amount of the solvent to be added may be such that the solid content concentration is 10 to 30 mass% in the coloring composition from the viewpoint of workability.

< other ingredients >

The coloring composition may contain other additives in addition to the above components. Examples of the other additives include an antioxidant, an anti-coagulation agent, and a surface conditioner (leveling agent).

< production of coloring composition >

When the coloring composition contains a pigment in the colorant, the above-mentioned components can be added to a known dispersing machine such as a bead mill, a sand mill, a dispersing machine, a paint mixer, or the like, and dispersed to obtain a dispersion. In the case of performing the dispersion treatment using a medium such as beads, the dispersion treatment may be performed 1 time using a medium having a predetermined particle diameter, or the dispersion treatment may be performed after appropriately changing the particle diameter of the medium, for example, by successively reducing the particle diameter. The method of adding the components is not particularly limited, and a substance obtained by mixing the components at the same time may be dispersed, or for example, in the case of using a plurality of pigments as a colorant, a dispersion of each pigment is prepared in advance, and then the dispersion is mixed and then the dispersion is performed again. When the colorant does not contain a pigment, a uniform liquid can be obtained by mixing the above components.

The dispersion or homogeneous liquid obtained in the above manner may also be subjected to a filtration treatment as required.

(composition for Forming coating film)

The coating film-forming composition according to an embodiment of the present invention contains the above-described coloring composition and a coating film-forming component. Thus, since the above-mentioned specific coloring composition is contained, a cured film obtained using the composition for forming a coating film has good brightness even under a high-temperature environment, and the decrease in contrast is suppressed.

< coating film-forming component >

Examples of the coating film-forming component include a polymerizable component, a polymer, and a mixture thereof.

Examples of the polymer include thermoplastic polyurethane resins, (meth) acrylic resins, polyamide resins, polyimide resins, styrene-maleic acid resins, polyester resins, silicone resins, and Cardo resins.

The content of the polymer in the composition for forming a coating film is preferably 10 to 40% by mass, more preferably 20 to 30% by mass, based on the total solid content of the composition for forming a coating film. The content of the polymer in the coating film-forming composition is the total amount of the polymer and the (meth) acrylic polymer contained in the coloring composition. The molecular weight of the polymer can be appropriately determined.

Among the polymers as the coating film forming component, an alkali-soluble resin showing solubility in a solution in an alkaline region is preferable.

When the alkali-soluble resin is contained, for example, in a photolithography step in the production of a color filter, when the pigment composition is used for pattern formation, the pattern formability can be further improved.

Examples of such an alkali-soluble resin include the aforementioned (meth) acrylic polymers. Examples of other alkali-soluble resins include alkali-soluble resins described in jp 2009-179789 a.

The weight average molecular weight of the alkali-soluble resin is preferably 5000 to 50000 from the viewpoint of developability.

There are many alkali-soluble resins available on the market, and specific examples thereof are as follows, but not limited thereto.

Showa Polymer K.K.: ripoxy SPC-2000;

manufactured by mitsubishi yang corporation: dianal NR series;

diamond hamrock co.ltd., system: photomer6173 (COOH-containing urethane acrylic oligomer);

osaka organic chemical industry, manufactured by Osaka: viscoat R-264, KS RESIST 106, SOP-005;

manufactured by Daiiol chemical industries, Ltd.: cyclomer P series, PLACCEL CF200 series;

manufactured by masson cellulose UCB corporation: ebecryl 3800;

japanese catalyst of japan: ACRYCURE (registered trademark) RD-Y-503, RD-Y-702-A, BX-Y-10; and the like.

Since a pattern is easily applied by development (negative development), a photopolymerizable component is preferable as the polymerizable component.

The photopolymerizable component that can be used includes a photopolymerizable compound and a photopolymerization initiator. As such a photopolymerizable compound and a photopolymerization initiator, for example, those described in japanese patent laid-open publication No. 2009-179789 can be used. More specifically, such photopolymerizable compounds are addition polymerizable compounds having at least one ethylenically unsaturated double bond, and are selected from compounds having at least 1, preferably 2 or more terminal ethylenically unsaturated bonds. Such a compound group is a compound widely known in the art, and these compounds can be used without particular limitation. The photopolymerizable compound has a chemical form such as a monomer, a prepolymer, a 2-mer, a 3-mer, and an oligomer, or a mixture thereof and a copolymer thereof.

Examples of the monomer and its copolymer include an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or an ester or amide thereof, and preferably an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound or an amide of an unsaturated carboxylic acid and an aliphatic polyhydric amine compound. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, mercapto groups, etc. with monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. are also preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituent groups such as isocyanate group and epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituent groups such as halogen group and p-toluenesulfonyloxy group with monofunctional or polyfunctional alcohols, amines and thiols are also preferable. In addition, as another example, instead of the above-mentioned unsaturated carboxylic acid, a group of compounds such as unsaturated phosphonic acid, styrene, and vinyl ether can be used.

The photopolymerizable compound is preferably contained in an amount of 5 to 70% by mass, more preferably 10 to 60% by mass, based on the total solid content (nonvolatile content) in the coating film forming composition. These may be used alone or in combination of 2 or more. In addition, the photopolymerizable compound can be used in any suitable configuration, formulation, and amount of addition, from the viewpoint of the degree of inhibition of polymerization with respect to oxygen, resolution, overlapping properties, refractive index change, surface adhesiveness, and the like.

As the photopolymerization initiator, the photopolymerization initiator described in Japanese patent laid-open No. 2009-179789 can be used.

Examples thereof include acetophenone type, ketal type, benzophenone type, benzoin type, benzoyl type, xanthone type, active halogen compounds (triazine type, oxadiazole type, coumarin type), acridine type, binadiazole type, and oxime ester type.

Specific examples of these include benzophenone, 4 ' -bis (dimethylamino) benzophenone, 4 ' -bis (diethylamino) benzophenone, 4 ' -dichlorobenzophenone, and the like.

The content of the photopolymerization initiator in the coating film-forming composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total solid content of the coating film-forming composition. When the content of the photopolymerization initiator is within this range, the polymerization reaction can be favorably advanced, and a film having a favorable strength can be formed.

When the composition for forming a coating film contains a photopolymerizable component as a coating film-forming component, the composition may contain the alkali-soluble resin.

Various additives such as a sensitizer (sensitizing dye), a chain transfer agent, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a filler, a surfactant, an adhesion promoter, an antioxidant, an anti-agglomerating agent, and a surface conditioner (leveling agent) may be added to the composition for forming a coating film as needed.

The composition for forming a coating film can be obtained by, for example, mixing and stirring the above-described components by a dispersing machine, a vibration stirrer, or the like. The resulting mixed solution may be subjected to filtration treatment as needed.

The cured film obtained by using the composition for forming a coating film according to the conventional method can have good brightness and contrast even under a high-temperature environment of about 100 to 250 ℃. Therefore, the composition for forming a coating film can be suitably used as a color filter which is widely used as a component of a display (LCD) of a liquid crystal display device, a display of an organic Electroluminescence (EL) display device, or the like.

[ example 1]

The following describes embodiments of the present invention in detail based on examples. Various physical properties of the production examples described below were measured in the following manner.

< weight average molecular weight >

Polystyrene was used as a standard substance, tetrahydrofuran was used as an eluent, and the molecular weight distribution of the polystyrene was measured by using HLC-8220 GPC (manufactured by Tosoh corporation), column chromatography: TSKgel SuperHZM-M (manufactured by Tosoh corporation) was measured for the weight average molecular weight by GPC (gel permeation chromatography).

< acid number >

Determined according to DIN EN ISO 2114.

< amine number >

Determined according to DIN 16945.

< solid component >

About 1g of the polymer solution (also referred to as a polymer solution) was weighed into an aluminum bowl, dissolved by adding about 3g of acetone, and then naturally dried at room temperature. Then, the resultant was dried at 140 ℃ for 1.5 hours under vacuum using a hot air dryer (product name: PHH-101, manufactured by ESPEC Co., Ltd.), and then cooled in a desiccator, and the mass was measured. The solid content (% by mass) of the polymer solution was calculated from the mass reduction amount.

Production example 1 production of Phthalocyanine Compound

A green cake was obtained in accordance with example 30 of Japanese patent application laid-open No. H05-345861, and then dried in a hot air dryer to prepare a phthalocyanine compound represented by the following formula (4) (solid content 100%). In formula (4), Et represents an ethyl group.

Production example 2 production of pigment derivative

20 parts by mass of C.I. pigment Yellow 138 (manufactured by BASF Co., Ltd., Paliotol gel K0961HD) and 300 parts by mass of 98% sulfuric acid were put in a 500ml separable flask and reacted at 120 ℃ for 5 hours to obtain a sulfonated phthalimide quinophthalone compound. The reaction mixture was poured into 3000 parts of water while stirring to precipitate the sulfonated phthalimide quinophthalone compound, and after stirring for 30 minutes, the filtration and washing were repeated 3 times. The obtained wet cake was washed with 300 parts by mass of 1% dilute sulfuric acid, filtered, and washed with water. After drying in a hot air dryer, 54 parts by mass (solid content 100%) of a pigment derivative represented by the following formula (5) was obtained.

The obtained pigment derivative was subjected to mass analysis using a liquid chromatograph-mass spectrometer "LC/MS" (Electro Spray Ionization) manufactured by Hewlett packard company, and as a result, M/z 733 [ M-H ] -was detected. Elemental analysis and mass analysis of the pigment derivative were performed, and it was found that, in formula (5), p is 0.8.

Production example 3 production of (meth) acrylic Polymer 1 (Polymer 1)

290 parts by mass of propylene glycol monomethyl ether acetate (PMA) was charged into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping vessel inlet, and after nitrogen substitution, the temperature was raised to 90 ℃. On the other hand, as the dropping tank (a), a mixture of 10 parts by mass of N-benzylmaleimide (BzMI), 35 parts by mass of t-butyl methacrylate (t-BMA), 20 parts by mass of Methyl Methacrylate (MMA), 20 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 15 parts by mass of Acrylic Acid (AA), and 2 parts by mass of t-butyl peroxy (2-ethylhexanoate) (manufactured by nippon oil co., ltd., Perbutyl (registered trademark) O) was prepared in a beaker, and a mixture of 1.5 parts by mass of N-dodecylmercaptan and 10 parts by mass of PMA was prepared in a dropping tank (B) by stirring and mixing. After the temperature of the reaction vessel reached 90 ℃, the polymerization was carried out by starting dropping from the dropping vessel over 3 hours while maintaining the temperature. After dropping, the mixture was kept at 90 ℃ for 30 minutes, and then heated to 115 ℃ to cure the mixture for 90 minutes. Analysis of the obtained solution containing polymer 1 revealed that the weight average molecular weight was 11300, the acid value was 121mgKOH/g, and the solid content was 35% by mass.

Production example 4 production of (meth) acrylic Polymer 2 (Polymer 2)

The same operation as in production example 3 was carried out, except that methacrylic acid (MAA) was used instead of Acrylic Acid (AA). Analysis of the resulting solution containing polymer 2 revealed that the weight-average molecular weight was 11100, the acid value was 101mgKOH/g, and the solid content was 35% by mass.

Production example 5 production of (meth) acrylic Polymer 3 (Polymer 3)

The same operation as in production example 3 was carried out, except that the charged amount of n-dodecylmercaptan was changed to 0.6 parts by mass. Analysis of the obtained solution containing polymer 3 revealed that the weight-average molecular weight was 19900, the acid value was 121mgKOH/g, and the solid content was 35% by mass.

The compounding ratios of the monomers in production examples 3 to 5 (corresponding to the ratio of the structural units of the polymers 1 to 3 in total of 100 parts by mass), the weight average molecular weights and acid values of the obtained polymers 1 to 3, and the solid contents of the obtained polymer solutions are shown in Table 1.

[ Table 1]

Production example 6 production of resin type dispersant 1

Into a flask equipped with a nitrogen inlet tube, a cooling tube and a stirrer, 34.0 parts by mass of methyl methacrylate, 22.7 parts by mass of Propylene Glycol Monomethyl Ether Acetate (PGMEA), and 5.0 parts by mass of a living radical polymerization initiator were charged, and after nitrogen substitution, the temperature was raised to 70 ℃ to carry out living radical polymerization for 5 hours. Further, 33.0 parts by mass of n-butyl methacrylate and 22.0 parts by mass of PGMEA were added to the reaction solution, and living radical polymerization was carried out at 70 ℃ for 5 hours. To the reaction solution were further added 33.0 parts by mass of dimethylaminoethyl methacrylate and 55.3 parts by mass of PGMEA, and living radical polymerization was carried out at 70 ℃ for 6 hours. The reaction mixture was dropped into 1.00L of n-heptane with stirring to precipitate a polymer, which was recovered by suction filtration and dried under reduced pressure at 60 ℃. The obtained polymer was dissolved in PGMEA to obtain a solution of a triblock copolymer having a tertiary amine (resin type dispersant 1). Analysis of the solution containing the obtained polymer revealed that the weight average molecular weight was 10000, the amine value was 110mgKOH/g, and the solid content was 40% by mass.

Production example 7 production of resin type dispersant 2

A flask equipped with a nitrogen inlet tube, a cooling tube and a stirrer was charged with 40.5 parts by mass of methyl methacrylate, 27.0 parts by mass of PGMEA, and 5.5 parts by mass of a living radical polymerization initiator, and after nitrogen substitution, the temperature was raised to 70 ℃ to carry out living radical polymerization for 5 hours. Further, 40.5 parts by mass of n-butyl methacrylate and 27.0 parts by mass of PEGMA were added to the reaction solution, and living radical polymerization was carried out at 70 ℃ for 5 hours. To the reaction solution were further added 19.0 parts by mass of dimethylaminoethyl methacrylate and 46.0 parts by mass of PGMEA, and living radical polymerization was carried out at 70 ℃ for 5 hours. The reaction mixture was dropped into 1.00L of n-heptane with stirring to precipitate a polymer, which was recovered by suction filtration and dried under reduced pressure at 60 ℃. The obtained polymer was dissolved in PGMEA to obtain a solution of a triblock copolymer having a tertiary amine (resin type dispersant 2). Analysis of the solution containing the obtained polymer revealed that the weight-average molecular weight was 8500, the amine value was 60mgKOH/g, and the solid content was 40% by mass.

The components used in the following examples and comparative examples, except for production examples 1 to 7, are shown in tables 2 and 3.

(1) Yellow pigment

·Y138

Pigment Yellow 138 (manufactured by BASF Co., Ltd., Paliotol Gelb K0961HD), solid content 100 mass%

(2) Polymer and method of making same

·CF－F－115

Fuji film and Wako pure chemical industries, CF-F-115,

a photocurable resin having no (meth) acrylate monomer unit containing a tertiary carbon, weight average molecular weight: 12300, acid number: 146mgKOH/g, solid content 32% by mass

·RD－Y－221

RD-Y-221, manufactured by Nippon catalyst K.K.,

acrylic resin having no (meth) acrylate-based monomer unit containing a tertiary carbon, weight average molecular weight: 12000, acid value: 114mgKOH/g, 35% by mass of solid content

(3) Dispersing agent

·LPN6919

BYK-CHEMIE-JAPAN, Disperbyk-LPN 6919,

block copolymer with tertiary amine, amine number: 120mgKOH/g, acid value: 1g KOH/g, solid content 60% by mass

·LPN22956

BYK-CHEMIE-JAPAN, Disperbyk-LPN 22956,

block copolymer with tertiary amine, amine number: 160mgKOH/g, acid value: 41mgKOH/g, 39% by mass of solid content

(4) Solvent(s)

·PMA

Propylene glycol monomethyl ether acetate (examples 1 to 7, comparative examples 1 and 2): preparation of coloring composition

Each component was charged into a sand mill so as to have a composition shown in table 2. 100 parts by mass of each mixed solution were charged with 400 parts by mass of zirconia beads having a diameter of 0.8mm, and the dispersion treatment was carried out at 2000 revolutions for 30 minutes. Thereafter, the zirconia beads having a diameter of 0.8mm were removed, 400 parts by mass of the zirconia beads having a diameter of 0.05mm were put in, and the dispersion treatment was carried out at 2000 revolutions for 30 minutes. Thereafter, the zirconia beads were removed to obtain a coloring composition.

[ Table 2]

Unit: mass portion of

Examples 8 to 14 and comparative examples 3 and 4): production of composition for Forming coating film

Using the colored compositions obtained in examples 1 to 7 and comparative examples 1 and 2, the respective colored compositions and coating film-forming components were mixed in the blending amounts shown in table 3 and stirred by a dispersing machine to obtain coating film-forming compositions.

(evaluation)

< formation of coating film >

The coating film-forming compositions obtained in examples 8 to 14 and comparative examples 3 and 4 were coated with a spin coater (spin coater MS-150A, manufactured by sanko corporation) by adjusting the rotation speed so as to obtain (x, y) ═ 0.2760, 0.5820 when measured using a colorimeter (MCPD-6800, manufactured by MCPD), and coating plates were prepared, respectively. The resulting coated plate was dried at room temperature for 5 minutes, and then preliminarily dried at 100 ℃ for 2 minutes (Prebake). Next, it was dried at 230 ℃ for 30 minutes (Postbake 1). Subsequently, it was dried at 230 ℃ for 2 hours (Postbake 2).

< measurement of luminance Y and Contrast Ratio (CR) >

Each cured film after Postbake1 was subjected to tristimulus value measurement by the xyz color method using a colorimeter (MCPD-6800, manufactured by tsukamur electronics corporation). The Contrast Ratio (CR) was determined using a color luminance meter (TOPCON TECHNOROUSE CORPORATION, BM-5 AS). Subsequently, the mixture was heated at 230 ℃ for 2 hours (Postbake2), and the tristimulus value was obtained by the xyz color method using a colorimeter (MCPD-6800, manufactured by tsukamur electronic corporation). The measurement results are shown in table 3.

[ Table 3]

As is apparent from tables 1 to 3, by using a specific phthalocyanine compound and a specific (meth) acrylic polymer, the brightness (Y value) and the Contrast (CR) are better than those in the case where the specific phthalocyanine compound and the specific (meth) acrylic polymer are not used even after repeated heating to a high temperature.

Claims (9)

1. A coloring composition characterized by:

the coloring composition contains a coloring agent, a dispersant, a (meth) acrylic polymer and a solvent,

the colorant contains a phthalocyanine compound represented by the following formula (1),

the (meth) acrylic polymer comprises a tertiary carbon-containing (meth) acrylate monomer unit, a hydroxyl group-containing monomer unit, and a (meth) acrylic acid unit, and the content of the tertiary carbon-containing (meth) acrylate monomer unit is 15 to 90 mass% relative to 100 mass% of the total amount of monomer component units,

in the formula (1), A¹～A¹⁶Each independently represents a hydrogen atom, a halogen atom or a group represented by the following general formula (2) wherein A¹～A¹⁶Wherein 1 or more of the above-mentioned groups represent a group represented by the following general formula (2),

in formula (2), X represents a linking group having a valence of 2, the benzene ring in formula (2) may have an optional substituent, and ﹡ represents a bond.

2. A coloring composition according to claim 1, wherein:

the colorant contains A in the formula (1)²、A³、A⁶、A⁷、A¹⁰、A¹¹、A¹⁴、A¹⁵Independently is a group of formula (2) and A¹、A⁴、A⁵、A⁸、A⁹、A¹²、A¹³、A¹⁶Phthalocyanine compounds which are halogen atoms.

3. A coloring composition according to claim 1 or 2, wherein:

the colorant contains A in the formula (1)²、A³、A⁶、A⁷、A¹⁰、A¹¹、A¹⁴、A¹⁵And (b) a phthalocyanine compound which is independently a group represented by the formula (2) wherein the benzene ring in the formula (2) has a substituent selected from the group consisting of-COOR and-OR, wherein R independently represents an alkyl group having 1 to 4 carbon atoms which may have a substituent.

4. A coloring composition according to any one of claims 1 to 3, wherein:

the (meth) acrylic polymer contains 20 to 60 mass% of the tertiary carbon-containing (meth) acrylate monomer unit, 15 to 50 mass% of the hydroxyl group-containing monomer unit, and 13 to 30 mass% of the (meth) acrylic unit, based on 100 mass% of the total amount of monomer component units.

5. A coloring composition according to any one of claims 1 to 4, wherein:

the weight average molecular weight of the (meth) acrylic polymer is 10000 to 50000.

6. A coloring composition according to any one of claims 1 to 5, wherein:

the acid value of the (meth) acrylic polymer is 80 to 200 mgKOH/g.

7. A coloring composition according to any one of claims 1 to 6, wherein:

the dispersant is a block copolymer with a tertiary amine.

8. A coloring composition according to any one of claims 1 to 7, wherein:

the amine value of the dispersant is 50-200 mgKOH/g.

9. A composition for forming a coating film, characterized in that: comprising the coloring composition according to any one of claims 1 to 8 and a coating film-forming component.