JP5867331B2 - Coloring composition for color filter, color filter and display element - Google Patents

Description

  The present invention relates to a coloring composition for a color filter, a color filter, and a display element, and more specifically, a color used for a transmissive or reflective color liquid crystal display element, a solid-state imaging element, an organic EL display element, electronic paper, and the like. The present invention relates to a color filter coloring composition used for forming a color layer useful for a filter, a color filter including a color layer formed using the color composition, and a display element including the color filter.

  In producing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape. There are known methods (for example, Patent Documents 1 and 2) for obtaining pixels of each color by irradiation (hereinafter referred to as “exposure”) and development. A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (for example, Patent Document 3) is also known. Furthermore, a method for obtaining pixels of each color by an inkjet method using a pigment-dispersed colored resin composition is also known (for example, Patent Document 4).

  By the way, in the field of color filters used for liquid crystal display elements and solid-state image sensors, pigments used tend to be increasingly atomized with the demand for higher brightness and higher contrast. It is known that the use of a dispersant is effective for realizing such stable and good dispersion of the atomized pigment. Various methods (for example, patent documents 5-6) which improve the dispersibility of a pigment using such a dispersant and improve not only contrast and dispersion stability but also developability have been proposed.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP 2003-26949 A JP 2009-25813 A

However, even with the methods described in Patent Documents 5 to 6, it is difficult to realize the recent demands for high contrast, high color purity, and high brightness of color liquid crystal display elements. In particular, C.I. I. In the case of using a quinophthalone pigment typified by CI Pigment Yellow 138, a pigment dispersion solution prepared by a conventionally proposed dispersion method and a known dispersant not only has a high viscosity but also deteriorates storage stability. However, the color filter produced using the pigment dispersion solution has a problem that the contrast is insufficient. Therefore, there is a strong demand for the development of a coloring composition for a color filter that realizes the recent demands for high contrast, high color purity, and high brightness, and is excellent in dispersibility and storage stability.
Therefore, the subject of this invention is C.I. I. An object of the present invention is to provide a coloring composition for a color filter using a quinophthalone pigment typified by CI Pigment Yellow 138, having excellent chromaticity characteristics, good dispersibility and storage stability. Furthermore, the subject of this invention is providing the display element which comprises the color filter provided with the colored layer formed from the said coloring composition, and the said color filter.

  In view of this situation, the present inventors have conducted extensive research and found that the above problems can be solved by using a copolymer having a specific repeating unit, and thus completed the present invention.

That is, the present invention comprises the following components (A), (B) and (C);
(A) a colorant containing a quinophthalone pigment,
(B) A repeating unit represented by the following formula (1) [hereinafter also referred to as “repeating unit (1)”] and a repeating unit represented by the following formula (2) [hereinafter referred to as “repeating unit (2)”. And a copolymer having an amine value of 80 to 250 mgKOH / g (hereinafter also referred to as “(B) copolymer”), and (C) a crosslinking agent. A coloring composition for a filter is provided.

[In Formula (1),
R ¹ represents a hydrogen atom or a methyl group,
Z represents —NR ² R ³ (wherein R ² and R ³ each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group) or a substituted or unsubstituted nitrogen-containing heterocyclic group. Show
X ¹ represents a divalent linking group. ]

[In Formula (2),
R ⁴ represents a hydrogen atom or a methyl group,
R ⁵ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group. ]

  The present invention also provides a color filter comprising a colored layer formed using the colored composition, and a display element comprising the color filter. Here, the “colored layer” means each color pixel, black matrix, black spacer, etc. used in the color filter.

Furthermore, the present invention provides the following components (a1), (B) and (F);
(A1) a quinophthalone pigment,
(B) A pigment dispersion for a color filter comprising: a repeating unit (1); a copolymer containing the repeating unit (2) and an amine value of 80 to 250 mgKOH / g; and (F) a solvent. A liquid is provided.

The coloring composition for a color filter of the present invention is excellent in chromaticity characteristics, and is excellent in dispersibility and storage stability. If the coloring composition of this invention is used, the color filter which has each color pixel with a high contrast can be obtained.
Accordingly, the color composition for color filters of the present invention is a color filter for color liquid crystal display elements, a color filter for color separation of solid-state image sensors, a color filter for organic EL display elements, and a color filter for electronic paper. It can be used very suitably for the production of a color filter.

Hereinafter, the present invention will be described in detail.
Color Filter Color Composition Hereinafter, the components of the color filter color composition of the present invention (hereinafter also simply referred to as “color composition”) will be described.

-(A) Colorant-
The coloring composition of the present invention is characterized by containing (a1) a quinophthalone pigment as (A) a coloring agent.

  Examples of the quinophthalone pigment include C.I. I. Pigment Yellow 138 is preferable from the viewpoint of availability of raw materials and absorption spectrum.

  In the present invention, (a1) quinophthalone pigments can be used alone or in admixture of two or more. Moreover, the coloring composition of this invention can contain (a2) another coloring agent further as a coloring agent with (a1) quinophthalone pigment. (A2) Other colorants are not particularly limited. For example, (a1) a quinophthalone pigment is used together with a green colorant to form a color composition for forming a green pixel. Can do. Moreover, it can be set as the coloring composition for forming a red pixel or a yellow pixel by using (a1) quinophthalone pigment with a red colorant.

  (A2) As the other colorant, any of pigments other than quinophthalone pigments, dyes, and natural pigments can be used, but in terms of obtaining pixels with high luminance and color purity, organic pigments, organic Dyes are preferred. As organic pigments, compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), that is, the following color index (CI) names are given. Things can be mentioned.

C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 211;

C. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 71, C.I. I. Pigment orange 72, C.I. I. Pigment orange 73, C.I. I. Pigment orange 74;

C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment red 272;

C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment blue 1, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment blue 80;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58;
C. I. Pigment brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment black 7;
Xanthene-based lake pigments described in JP 2010-26334 A;
Rhodamine lake pigments described in JP 2010-191304 A and JP 2011-22502 A;
Triarylmethane-based lake pigments described in JP2011-138094A and JP2011-22502A;
Various lake pigments described in JP 2010-237569 A, JP 2011-6602 A, and JP 2011-150195 A.

  Moreover, as an organic dye, what has the following color index (CI) name can be mentioned, for example.

C. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Azo dyes such as Moldant Black 7;

C. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Anthraquinone dyes such as Disperse Blue 60;

C. I. Phthalocyanine dyes such as Pad Blue 5;
C. I. Basic Blue 3, C.I. I. Quinone imine dyes such as Basic Blue 9;
C. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Quinoline dyes such as Disperse Yellow 64;
C. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Nitro dyes such as Disperse Yellow 42;
Methine dyes such as Disperse Yellow 201.

  In the present invention, (a2) other colorants can be used alone or in admixture of two or more.

  In the present invention, the pigment can be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Moreover, the pigment surface may be used by modifying the particle surface with a resin if desired. Examples of the resin that modifies the particle surface of the pigment include vehicle resins described in JP-A No. 2001-108817, and various commercially available resins for dispersing pigments. As a resin coating method on the carbon black surface, for example, methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969 and the like can be employed. The organic pigment may be used after the primary particles are refined by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be employed.

  When the coloring composition of the present invention is used for forming a green pixel, (A) the colorant includes (a1) a quinophthalone pigment and C.I. I. Pigment green 7, C.I. I. Pigment green 36 and C.I. I. It is preferable to contain at least one selected from the group consisting of CI Pigment Green 58. In this case, the content ratio of the (a1) quinophthalone pigment is preferably 1 to 80% by mass, more preferably 2 to 70% by mass in the total colorant. I. Pigment green 7, C.I. I. Pigment green 36 and C.I. I. The total content of at least one selected from the group consisting of CI Pigment Green 58 is preferably 20 to 99% by mass, more preferably 30 to 98% by mass, based on the total colorant.

  (A) The content ratio of the colorant is usually 5 to 70% by mass in the solid content of the coloring composition, preferably from the point of forming a pixel having high luminance and excellent color purity, or a black matrix having excellent light shielding properties. 5 to 60% by mass. Here, solid content is components other than the solvent mentioned later.

-(B) Copolymer-
The copolymer (B) in the present invention is a copolymer containing the repeating unit (1) and the repeating unit (2) and having an amine value of 80 to 250 mgKOH / g, and (A) a dispersant for a colorant. Function as.

The repeating unit (1) is represented by the above formula (1).
In the above formula (1), R ¹ is preferably a methyl group among a hydrogen atom and a methyl group.

In the above formula (1), Z represents —NR ² R ³ or a substituted or unsubstituted nitrogen-containing heterocyclic group, and R ² and R ³ are each independently a hydrogen atom or a substituted or unsubstituted hydrocarbon. In the present invention, the “hydrocarbon group” is a concept including an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and includes linear, branched and cyclic groups. Any form may be sufficient and a saturated hydrocarbon group or an unsaturated hydrocarbon group may be sufficient. The position of the unsaturated bond of the unsaturated hydrocarbon group may be in the molecular chain or at the molecular chain end.

  The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms and more preferably 1 to 12 carbon atoms, and more specifically, an alkyl group having 1 to 20 carbon atoms and further 1 to 12 carbon atoms. Examples thereof include an alkenyl group having 2 to 20, further 2 to 12, an alkynyl group having 2 to 20 carbon atoms, and further 2 to 12 carbon atoms. Specifically, as the alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group Octyl group, decyl group, dodecyl group and the like. Examples of the alkenyl group include ethenyl, 1-propenyl, 1-butenyl, 1,3-butadienyl, 1-pentenyl, 2-pentenyl, 1-hexenyl, 2-ethyl-2- A butenyl group, a 2-octenyl group, a (4-ethenyl) -5-hexenyl group, a 2-decenyl group, and the like can be mentioned. Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a 1-butynyl group, and the like. A pentynyl group, 3-pentynyl group, 1-hexynyl group, 2-ethyl-2-butynyl group, 2-octynyl group, (4-ethynyl) -5-hexynyl group, 2-decynyl group and the like can be mentioned.

The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms and more preferably 3 to 12 carbon atoms, specifically, a cycloalkyl having 3 to 20 carbon atoms and further 3 to 12 carbon atoms. More specifically, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group, and the like can be given. Here, in the present invention, the “alicyclic hydrocarbon group” is a general term for carbocyclic compounds having a structure in which carbon atoms are bonded in a cyclic manner, excluding aromatic compounds, and the above-mentioned aliphatic carbonization. Those having a hydrogen group as a substituent or a linking group to —COO— are also included.
Further, the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, further 6 to 14 carbon atoms, and further 6 to 10 carbon atoms, and more specifically, 6 to 20 carbon atoms, and further 6 to 6 carbon atoms. 14 and 6 to 10 aryl groups. Here, in the present invention, the “aryl group” refers to a monocyclic to tricyclic aromatic hydrocarbon group, and specifically includes a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an azulenyl group, and the like. Can do.
In addition, as a substituent of a hydrocarbon group, a halogen atom, a hydroxyl group, a C1-C6 alkoxy group etc. can be mentioned, for example. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, A pentyloxy group, a phenoxy group, etc. can be mentioned.

  In the present invention, the “nitrogen-containing heterocyclic group” refers to a heterocyclic group having at least one nitrogen atom as a ring component, and a heterocyclic monocyclic group or a condensed heterocyclic group formed by condensing two of these. A cyclic group is preferred. These heterocyclic groups may be an unsaturated ring or a saturated ring, and may have a hetero atom (for example, an oxygen atom or a sulfur atom) other than a nitrogen atom in the ring.

  Examples of the unsaturated heterocyclic ring include a pyridine ring, an imidazole ring, a thiazole ring, an oxazole ring, a triazole ring, an imidazoline ring, and a piperazine ring. Examples of the saturated heterocyclic ring include a morpholine ring, a piperidine ring, and a tetrahydropyrimidine ring. Examples of the substituent in the nitrogen-containing heterocyclic group include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a carboxyl group, an alkoxycarbonyl group, an alkoxy group, a hydroxyl group, an amino group, an amide group, a thiol group, and a thioether group. Etc. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, and the halogen atom includes a fluorine atom. , Chlorine atom, bromine atom and iodine atom. As the alkoxycarbonyl group, for example, an alkoxycarbonyl group having 2 to 7 carbon atoms is preferable, and specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, a formyloxy group, an acetoxy group, and a benzoyloxy group. As an alkoxy group, a C1-C6 alkoxy group is preferable, and a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a phenoxy group etc. can be mentioned specifically ,. Examples of the amino group include an amino group, a methylamino group, a diethylamino group, and a diphenylamino group. Examples of the amide group include a formamide group, an acetamido group, and a propioamide group. The thioether group is preferably a thioether group having 1 to 6 carbon atoms, and specific examples include a methylthioether group, an ethylthioether group, and a butylthioether group.

  The heteromonocyclic group is preferably a 5- to 7-membered ring, and specifically includes a group having a basic skeleton represented by the following formula (1-1), and these heteromonocyclic groups have a substituent. You may do it.

  In the formula (1-1), “*” indicates a bond.

  Specific examples of the fused heterocyclic group include groups having a basic skeleton represented by the following formulas (1-2) to (1-4). These fused heterocyclic groups have a substituent. You may do it.

  In formulas (1-2) to (1-4), “*” indicates a bond.

In the above formula (1), examples of the divalent linking group (X ¹ ) include an alkanediyl group having 1 to 10 carbon atoms and 1 to 6 carbon atoms; an arylene group having 6 to 20 carbon atoms and further 6 to 14 carbon atoms; A —CONH—R ¹⁰ — group; a —COO—R ¹¹ — group, and the like. Here, R ¹⁰ and R ¹¹ are each independently a single bond, an alkanediyl group having 1 to 10 carbon atoms, and further 1 to 6 carbon atoms, or an alkyleneoxyalkylene group having 2 to 10 carbon atoms. Examples of the alkanediyl group include a methylene group, an ethylene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, Propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,4-diyl group, pentane-1,5 -Diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group, etc. can be mentioned. Examples of the arylene group include a phenylene group, a naphthylene group, a biphenylene group, and an anthrylene group. Examples of the alkyleneoxyalkylene group having 2 to 10 carbon atoms include an ethyleneoxyethylene group, an ethyleneoxypropylene group, a propyleneoxypropylene group, and an ethyleneoxybutylene group.
Among these, X ¹ is preferably a —COO—R ¹¹ — group, and R ¹¹ is preferably an alkanediyl group having 2 to 6 carbon atoms.

The repeating unit (2) is represented by the above formula (2).
In the above formula (2), R ⁴ is preferably a methyl group among a hydrogen atom and a methyl group.
Examples of the aliphatic hydrocarbon group for R ⁵ include an alkyl group, an alkenyl group, and an alkynyl group. The aliphatic hydrocarbon group may be either linear or branched, and when the aliphatic hydrocarbon group is an alkenyl group or an alkynyl group, the position of the unsaturated bond is within the molecular chain and the molecule. Any of the chain ends may be used.
Examples of the alicyclic hydrocarbon group in R ⁵ include a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridged ring hydrocarbon group, a spiro hydrocarbon group, and a cyclic terpene hydrocarbon group. Can be mentioned. The alicyclic hydrocarbon group may further have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group having 1 to 6 carbon atoms. Specific examples of these substituents are the same as those described above.
Among them, R ⁵ is preferably an alkyl group having 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, and an alicyclic hydrocarbon group having 3 to 20 carbon atoms and further 4 to 15 carbon atoms. Group, propyl group, butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, isodecyl group, dodecyl group, cyclohexyl group, t-butylcyclohexyl group, decahydro-2-naphthyl group, tricyclo [5.2.1 .0 ^2,6] decan-8-yl group, an adamantyl group, a dicyclopentenyl group, penta cyclopentadiene deca group, tri cyclopentenyl group, isobornyl group particularly preferred.

  The copolymer (B) may have a repeating unit other than those described above. Examples of such a repeating unit include a repeating unit represented by the following formula (3) [hereinafter referred to as “repeating unit”. (Also referred to as “(3)”]; repeating unit having an acidic group [hereinafter also referred to as “repeating unit (4)”]; styrene monomer such as styrene and α-methylstyrene; Quaternary ammonium salts such as (meth) acrylic acid aralkyl ester; (meth) acryloyloxyethyl (4-benzoylbenzyl) dimethylammonium bromide, (meth) acryloyloxyethylbenzyldimethylammonium chloride, (meth) acryloyloxyethylbenzyl diethylammonium chloride (Meth) acrylic acid ester having a structure; (Meth) acrylic acid halide monomers such as (meth) acrylic acid chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether; glycidyl crotonic acid Ether; repeating units derived from monomers such as N-methacryloylmorpholine. Especially, it is preferable to have at least one of a repeating unit (3) and a repeating unit (4) from a dispersible viewpoint, and it is more preferable to have a repeating unit (3). Here, in the present invention, “(meth) acrylate” means “acrylate or methacrylate”.

[In Formula (3),
R ⁶ represents a hydrogen atom or a methyl group,
R ⁷ , independently of each other, represents an alkanediyl group having 2 to 4 carbon atoms,
R ⁸ represents an alkyl group having 1 to 6 carbon atoms,
n shows the integer of 1-150. ]

In formula (3), R ⁶ is preferably a methyl group among hydrogen atoms or methyl groups.
Examples of the alkanediyl group in R ⁷ include an ethylene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, and a propane-1,3-diyl group. Group, propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group and the like.
Examples of the alkyl group for R ⁸ include the same as those described above.
Although n shows the integer of 1-150, the integer of 1-20 is preferable, the integer of 1-10 is more preferable, and the integer of 1-5 is especially preferable.

Although the repeating unit (4) has an acidic group, the acidic group is not particularly limited, and examples thereof include a phenolic hydroxyl group, a carboxyl group, a sulfo group, —SO ₂ NH ₂ , —C (CF ₃ ) _2. -OH etc. are mentioned. In the present invention, the acidic group is preferably a phenolic hydroxyl group or a carboxyl group, and particularly preferably a carboxyl group, from the viewpoint of dispersibility and alkali developability of the resulting colored composition.

  Examples of the repeating unit (4) include a repeating unit represented by the following formula (4).

[In Formula (4),
R ⁹ represents a hydrogen atom or a methyl group,
A represents an acidic group,
X ² represents a single bond or a divalent linking group. ]

In the above formula (4), R ⁹ is preferably a methyl group among a hydrogen atom and a methyl group.
Examples of the divalent linking group (X ² ) include, for example, an alkanediyl group having 1 to 10 carbon atoms and further 1 to 6 carbon atoms, an arylene group, a —CONH—R ¹² — group, a —COO—R ¹³ — group, and —OCOR. ¹⁴ - ^{group, -R 15 -OCO-R 16 -} , - COO- (C m H 2m COO) l -C m H 2m - ^{group, -COO-R 17 -OCO-R} 18 - , and the like. Here, R ^{12 to} R ¹⁶ are each independently a single bond, an alkanediyl group having 1 to 10 carbon atoms, or 1 to 6 carbon atoms, or an alkyleneoxyalkylene group having 2 to 10 carbon atoms, and m is 1 Represents an integer of 1 to 10, 1 represents an integer of 1 to 4, R ¹⁷ represents an alkanediyl group having 1 to 10 carbon atoms and 1 to 6 carbon atoms, R ¹⁸ represents a single bond, 1 to 10 carbon atoms, 1 to 6 alkanediyl group, cyclohexane-1,2-diyl group or phenylene group (for example, 1,2-phenylene group, 1,4-phenylene group). Specific examples of the alkanediyl group, the arylene group, and the alkyleneoxyalkylene group include the same ones as described above.
Among them, as X ² , a single bond, a phenylene group, a —COO—R ¹³ — group, a —COO— (C _m H _2m COO) ₁ —C _m H _2m — group or a —COO—R ¹⁷ —OCO—R ¹⁸ -Is preferred.

  (B) In the copolymer, the copolymerization ratio of each repeating unit is not particularly limited as long as the amine value of the copolymer is in the range of 80 to 250 mgKOH / g, but from the viewpoint of dispersibility. Any one of the following aspects (i) to (iii) is preferable, and any one of (ii) and (iii) is more preferable.

When (i) (B) copolymer consists only of the repeating structure (1) and the repeating structure (2), the copolymerization ratio of the repeating structure (1) is preferably 20 to 80% by mass in all repeating units, More preferably, it is 30-70 mass%, More preferably, it is 40-60 mass%, and the copolymerization ratio of a repeating structure (2) is a remainder.
(Ii) When the copolymer (B) has a repeating unit (3) other than the repeating structure (1) and the repeating structure (2), the copolymerization ratio of the repeating structure (1) is preferably among all the repeating units. 20 to 70% by mass, more preferably 30 to 65% by mass, still more preferably 40 to 60% by mass, and the copolymerization ratio of the repeating structure (2) is preferably 5 to 50% by mass in all repeating units. More preferably, it is 10-45 mass%, More preferably, it is 15-40 mass%, The copolymerization ratio of a repeating unit (3) is preferably 5-40 mass% in all the repeating units, More preferably, it is 10-30. % By mass.
(Iii) When the copolymer (B) has a repeating unit (3) and a repeating unit (4) other than the repeating structure (1) and the repeating structure (2), the copolymerization ratio of the repeating structure (1) is In the repeating unit, preferably 20 to 70% by mass, further 30 to 65% by mass, and further 40 to 60% by mass. The copolymerization ratio of the repeating structure (2) is preferably 5 to 50% by mass in all repeating units. %, More preferably 10 to 45% by mass, still more preferably 15 to 40% by mass, and the copolymerization ratio of the repeating unit (3) is preferably 5 to 40% by mass, more preferably 10% in all repeating units. The copolymerization ratio of the repeating unit (4) is preferably 1 to 10% by mass and more preferably 1 to 5% by mass in all repeating units.

  (B) The amine value of the copolymer is 80 mgKOH / g or more and 250 mgKOH / g or less, but from the viewpoint of further improving the contrast, it is preferably 100 to 250 mgKOH / g, more preferably 150 to 250 mgKOH / g, and further Preferably it is 150-200 mgKOH / g, Most preferably, it is 155-190 mgKOH / g. Here, in the present invention, the “amine value” is the number of mg of KOH equivalent to the acid required to neutralize 1 g of the non-volatile content excluding the solvent of the copolymer solution. This is measured by the method described in the examples.

  On the other hand, when the copolymer (B) has a repeating unit (4), the acid value of the copolymer (B) is preferably 30 mgKOH / g or less, more preferably 25 mgKOH / g or less, from the viewpoint of storage stability. More preferably, it is 20 mgKOH / g or less. Although a minimum is not specifically limited, 0.5 mgKOH / g or more is preferable and 1 mgKOH / g or more is more preferable. Here, in the present invention, the “acid value” is the number of mg of KOH required to neutralize 1 g of the non-volatile content excluding the solvent of the copolymer solution. It is measured by the method described in 1.

  The copolymer (B) is not particularly limited as long as it has the repeating unit (1) and the repeating unit (2). However, the repeating unit (2) and the repeating unit (3 ) And A block having no repeating unit (4) and having repeating unit (1), repeating unit (1) without repeating unit (1), and repeating unit (2) and repeating unit (3), optionally repeating unit It is preferable that it is a block copolymer containing B block which has (4). The block copolymer is preferably an AB block copolymer or a BAB block copolymer.

  In the A block, the repeating unit (1) may be contained in two or more kinds in one A block. In that case, each repeating unit is a random copolymer and a block copolymer in the A block. It may be contained in any aspect.

  A repeating unit other than the repeating unit (1) may be contained in the A block, and examples of such a repeating unit are derived from the (meth) acrylic acid ester having the quaternary ammonium salt structure. Repeating units to be mentioned.

  On the other hand, in the B block, the repeating unit (2), the repeating unit (3) and the repeating unit (4) may be contained in any form of random copolymerization and block copolymerization. (B) When the copolymer is a B-A-B block copolymer, the B1 block having the repeating unit (2) and the repeating unit (3) and not having the repeating unit (4), and the repeating unit It may be a B1-A-B2 block copolymer having (2) and a B2 block having the repeating unit (4) and not having the repeating unit (3). In addition, the repeating unit (2), the repeating unit (3) and the repeating unit (4) may be contained in one B block in two or more, and in that case, each repeating unit is represented by the B block. It may be contained in any form of random copolymerization and block copolymerization.

  (B) The copolymer can be produced by a known method. However, when the copolymer (B) is a block copolymer, for example, the monomer for introducing each of the above repeating units is subjected to living polymerization. Can be manufactured. Examples of the living polymerization method include, for example, JP-A-9-62002; JP-A-2002-31713; Lutz, P.M. Masson et al, Polym. Bull. 12, 79 (1984); C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981); Hatada, K .; Ute, et al, Polym. J. et al. 17, 977 (1985); Hatada, K .; Ute, et al, Polym. J. et al. 18, 1037 (1986); Koichi Right-hand, Koichi Hatada, Polymer Processing, 36, 366 (1987); Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Thesis, 46, 189 (1989); Kuroki, T .; Aida, J .; Am. Chem. Soc, 109, 4737 (1987); Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985); Y. Sogoh, W .; R. Hertler et al, Macromolecules, 20, 1473 (1987); Polym. Sci. Part A Polym. Chem. 47, 3773-3794 (2009); Polym. Sci. Part A Polym. Chem. 47, 3544-3557 (2009), etc., can be used.

  Examples of the monomer that gives the repeating unit (1) include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, and the like. These can be used alone or in admixture of two or more.

Examples of the monomer that gives the repeating unit (2) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate. , T-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane- 8-yl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, decahydro-2-naphthyl (meth) acrylate, pentacyclopentadecanyl (meth) acrylate , Tri cyclopentenyl (meth) acrylate. These can be used alone or in admixture of two or more.

  Examples of the monomer that gives the repeating unit (3) include 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and methoxypropylene glycol (meth). Examples include acrylate and methoxydipropylene glycol (meth) acrylate. These can be used alone or in admixture of two or more.

  Examples of the monomer that gives the repeating unit (4) include (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, (meth) acrylic acid carboxymethyl ester, and (meth) acrylic. Acid 2-carboxy-ethyl ester, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, p-vinylbenzoic acid, p-hydroxystyrene, p-hydroxy-α -Methylstyrene, 2-acryloyloxyethyl sulfonic acid, 2-methacryloxyethyl sulfonic acid, sodium 2-acryloyloxyethyl sulfonate, lithium 2-acryloyloxyethyl sulfonate, ammonium 2-acryloyloxyethyl sulfonate 2-acryloyloxyethyl sulfone Imidazolium acid, pyridinium 2-acryloyloxyethylsulfonate, sodium 2-methacryloxyethylsulfonate, lithium 2-methacryloxyethylsulfonate, ammonium 2-methacryloxyethylsulfonate, imidazolium 2-methacryloxyethylsulfonate , Pyridinium 2-methacryloxyethyl sulfonate, styrene sulfonic acid and the like. These can be used alone or in admixture of two or more.

(B) The molecular weight of the copolymer is Mw in terms of polymethyl methacrylate measured by GPC (elution solvent: DMF), preferably 1,000 to 30,000, particularly preferably 5,000 to 15,000. is there.
Further, the ratio (Mw / Mn) of Mw of the block copolymer (B) and Mn in terms of polymethyl methacrylate measured by GPC (elution solvent: DMF) is preferably 1.0 to 1.9, More preferably, it is 1.0-1.8, More preferably, it is 1.0-1.7, More preferably, it is 1.0-1.5, Most preferably, it is 1.0-1.3. (B) By making a copolymer into such an aspect, the coloring composition excellent in the dispersibility and alkali developability can be obtained.

  (B) A copolymer can be used individually or in mixture of 2 or more types. (B) Content of a copolymer is 1-100 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 5-70 mass parts, More preferably, it is 10-50 mass parts. (B) When there is too much content of a copolymer, there exists a possibility that developability may be impaired.

  In the present invention, a known dispersing agent may be further contained in order to improve dispersibility. Known dispersants include, for example, urethane dispersants, polyethylene imine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants. Examples thereof include a dispersant, a polyester-based dispersant, an acrylic dispersant, and a pigment derivative.

  Such dispersants are commercially available. For example, acrylic dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK Corporation (BYK)) Dispersbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (Lubrisol) Co., Ltd.) as a polyethylenimine-based dispersant, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.) as a polyester-based dispersant, Ajisper PB8 1, Adisper PB822, Adisper PB880, the Ajisper PB881 (Ajinomoto Fine-Techno Co., Ltd.), and the like, can be mentioned, respectively. Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivative of quinophthalone.

-(C) Crosslinking agent-
In the present invention, (C) a crosslinking agent refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, (C) the crosslinking agent is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.

  Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a caprolactone-modified polyfunctional ( (Meth) acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, hydroxyl-functional (meth) acrylate and polyfunctional isocyanate obtained by reacting with polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid The polyfunctional (meth) acrylate which has a carboxyl group obtained by making an anhydride react can be mentioned.

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of trivalent or higher aliphatic polyhydroxy compounds. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol diester. A methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. Examples of the polyfunctional (meth) acrylate modified with alkylene oxide include di (meth) acrylate modified with at least one selected from ethylene oxide of bisphenol A and propylene oxide of bisphenol A, ethylene oxide of isocyanuric acid and isocyanuric acid Tri (meth) acrylate modified with at least one selected from propylene oxide, tri (meth) acrylate modified with at least one selected from ethylene oxide of trimethylolpropane and propylene oxide of trimethylolpropane, pentaerythritol Tri (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide of pentaerythritol Modified with at least one selected from tetra (meth) acrylate modified with at least one selected from ethylene oxide of pentaerythritol and propylene oxide of pentaerythritol, ethylene oxide of dipentaerythritol and propylene oxide of dipentaerythritol Examples include hexa (meth) acrylate modified with at least one selected from penta (meth) acrylate, ethylene oxide of dipentaerythritol, and propylene oxide of dipentaerythritol.

  Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine or a condensate thereof. 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 Examples include '-tetra (alkoxymethyl) benzoguanamine, N, N, N', N'-tetra (alkoxymethyl) glycoluril and the like.

Among these crosslinking agents, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, polyfunctional (meth) acrylates modified with caprolactone, polyfunctional urethanes ( (Meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N′-tetra ( Alkoxymethyl) benzoguanamine is preferred. Among the polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Erythritol hexaacrylate is a compound obtained by reacting pentaerythritol triacrylate and succinic anhydride, among polyfunctional (meth) acrylates having a carboxyl group, obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride. The compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and background stains and film residues are hardly generated on the unexposed substrate and the light shielding layer.
In the present invention, the crosslinking agent (C) can be used alone or in admixture of two or more.

  In the present invention, the content of the (C) crosslinking agent is preferably 10 to 1,000 parts by mass, and particularly preferably 20 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. In this case, if the content of the crosslinking agent is too small, sufficient curability may not be obtained. On the other hand, if the content of the crosslinking agent is too large, when the coloring composition of the present invention is imparted with alkali developability, the alkali developability is deteriorated, and the soil or film on the unexposed portion of the substrate or on the light shielding layer is deteriorated. There is a tendency for the rest to occur easily.

-(D) Binder resin-
The coloring composition of the present invention can contain (D) a binder resin (however, excluding the component (B)). Thereby, alkali developability and the binding property to a board | substrate can be improved to a coloring composition. Such a binder resin is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). (D1) ”) and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as“ unsaturated monomer (d2) ”).

Examples of the unsaturated monomer (d1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meta ) Acrylate, p-vinylbenzoic acid and the like.
These unsaturated monomers (d1) can be used alone or in admixture of two or more.

Examples of the unsaturated monomer (d2) include:
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2 -10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) ) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate Glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[( (Meth) acrylic acid esters such as (meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as 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 ;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These unsaturated monomers (d2) can be used alone or in admixture of two or more.

  In the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2), the copolymerization ratio of the unsaturated monomer (d1) in the copolymer is preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (d1) within such a range, a colored composition having excellent alkali developability and storage stability can be obtained.

  Specific examples of the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. Copolymers disclosed in JP-A-10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, and the like. Can be mentioned.

  In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, As disclosed in Kaikai 2008-181095 and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin.

  The binder resin in the present invention has a polystyrene-reduced weight average molecular weight measured by GPC (elution solvent: tetrahydrofuran) of usually 1,000 to 100,000, preferably 3,000 to 50,000. If Mw is too small, the remaining film rate of the resulting film may be reduced, pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. On the other hand, if Mw is too large, resolution may be reduced. In addition, the pattern shape may be damaged, and dry foreign matter may be easily generated during application by the slit nozzle method.

  In addition, the ratio (Mw ′ / Mn ′) of the weight average molecular weight (Mw ′) and the number average molecular weight to (Mw ′) of the binder resin in the present invention is preferably 1.0 to 5.0, more preferably 1. 0.0-3.0. Here, Mw 'and Mn' refer to polystyrene-reduced weight average molecular weight and number average molecular weight measured by GPC (elution solvent: tetrahydrofuran).

  The binder resin in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

  In this invention, binder resin can be used individually or in mixture of 2 or more types.

  In this invention, content of binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts. If the content of the binder resin is too small, for example, the alkali developability may be decreased, or the storage stability of the resulting colored composition may be decreased. On the other hand, if the content is too large, the colorant concentration is relatively high. Therefore, it may be difficult to achieve the target color density as a thin film.

-(E) Photopolymerization initiator-
The coloring composition of the present invention can contain (E) a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The (E) photopolymerization initiator used in the present invention generates an active species capable of initiating the polymerization of the above (C) crosslinking agent upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. A compound.

  Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -A diketone type compound, a polynuclear quinone type compound, a diazo type compound, an imide sulfonate type compound etc. can be mentioned.

  In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.

  Among preferred photopolymerization initiators in the present invention, specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.

  Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′. -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4, Examples thereof include 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

  In addition, when using a biimidazole-type compound as a photoinitiator, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In the present invention, hydrogen donors can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine-based compounds having a halomethyl group such as xystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone and 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -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) and the like. As commercially available O-acyloxime compounds, NCI-831, NCI-930 (manufactured by ADEKA Corporation) and the like can also be used.

  In this invention, when using photoinitiators other than biimidazole type compounds, such as an acetophenone type compound, a sensitizer can also be used together. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

  In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) crosslinking agents, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. In this case, if the content of the photopolymerization initiator is too small, curing by exposure may be insufficient. On the other hand, if the content is too large, the formed colored layer tends to be detached from the substrate during development.

-(F) Solvent-
The coloring composition of the present invention usually comprises (a1) a colorant containing a quinophthalone pigment in (F) a solvent, (B) a copolymer and, if necessary, one of other dispersants and (D) a binder resin. Along with the part, for example, a bead mill, a roll mill or the like is used to mix and disperse while pulverizing to obtain a pigment dispersion, and then to this pigment dispersion, (C) a crosslinking agent, and (D) a binder resin, if necessary, (E) A photopolymerization initiator, an additional (F) solvent and the like are added and mixed. (F) As a solvent, as long as components (A) to (C) and other components constituting the colored composition are dispersed or dissolved and do not react with these components and have appropriate volatility. Can be appropriately selected and used. However, when preparing the pigment dispersion, from the viewpoint of dispersibility and stability, (f1) a solvent having a hydroxyl group (hereinafter also referred to as “solvent (f1)”) and (f2) having a hydroxyl group. It is preferable to use a solvent that does not (hereinafter also referred to as “solvent (f2)”).

Among such solvents, as the solvent (f1), for example,
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, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol;
Examples thereof include keto alcohols such as diacetone alcohol.

  Of these solvents (f1), (poly) alkylene glycol monoalkyl ethers are preferable, and propylene glycol monomethyl ether and propylene glycol monoethyl ether are particularly preferable. A solvent (f1) can be used individually or in mixture of 2 or more types.

Moreover, as a solvent (f2), for example,
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 acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Alkoxycarboxylic esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate ;
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-butyric acid Other esters such as -propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

  Of these solvents (f2), (poly) alkylene glycol monoalkyl ether acetates, ethers, ketones, diacetates, and alkoxycarboxylic acid esters are preferred, particularly ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. , Propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, 3 -Ethyl methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl are preferred. A solvent (f2) can be used individually or in mixture of 2 or more types.

  In the present invention, the content ratio (f1 / f2) of the solvent (f1) to the solvent (f2) in the colorant dispersion is preferably 0.5 / 99.5 to 40/60, more preferably 1/99 to 30/70, particularly preferably 5/95 to 25/75.

  Although the content of the solvent is not particularly limited, the total concentration of each component excluding the pigment dispersion or the solvent of the colored composition is the same regardless of whether it is a pigment dispersion or a colored composition. The amount of 5 to 50% by mass is preferable, and the amount of 10 to 40% by mass is particularly preferable. By setting it as such an aspect, the coloring agent dispersion liquid with favorable dispersibility and stability and the coloring composition with favorable coating property and stability can be obtained.

-Additives-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitor: malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2 -Propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanedio Residue improving agents such as succinic acid; development of succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. And the like, and the like.

Color filter and method for producing the same The color filter of the present invention includes a colored layer formed using the colored composition of the present invention.

  As a method for producing a color filter, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, on this substrate, for example, after applying a liquid composition of the radiation-sensitive composition of the present invention in which a red colorant containing a quinophthalone pigment is dispersed, pre-baking is performed to evaporate the solvent, and a coating film is formed. Form. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which red pixel patterns are arranged in a predetermined arrangement.

  Next, each colored radiation-sensitive composition of green or blue is used, and each colored radiation-sensitive composition is applied, pre-baked, exposed, developed, and post-baked in the same manner as described above, so that the green pixel array and blue Are sequentially formed on the same substrate. Thereby, a color filter in which pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

  The black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithography method. Using the radiation composition, it can be formed in the same manner as in the pixel formation.

Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, 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, gas phase reaction method, vacuum deposition, etc., if desired.

  When the colored radiation-sensitive composition is applied to the substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a bar coating method may be employed. In particular, it is preferable to employ a spin coating method or a slit die coating method.

  Pre-baking is usually performed by combining vacuum drying and heat drying. The drying under reduced pressure is usually performed until the pressure reaches 50 to 200 Pa. Moreover, the conditions of heat drying are 70-110 degreeC normally for about 1 to 10 minutes.

  The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, as the film thickness after drying.

  Examples of radiation light sources used in forming pixels and / or black matrices include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, and low pressure mercury lamps. Examples thereof include a light source, a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. An ultraviolet LED can also be used as the exposure light source. The radiation is preferably in the range of 190 to 450 nm.

Exposure of the radiation is generally preferred 10~10,000J / m ^2.
Examples of the alkali developer include sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-. An aqueous solution of undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene or the like is preferable.

An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

The post-baking conditions are usually 180 to 280 ° C. and about 10 to 60 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1 to 3 μm.

  Further, as a second method for producing a color filter, a method of obtaining pixels of each color by an ink jet method disclosed in JP-A-7-318723 and JP-A-2000-310706 can be employed. . In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, for example, after the liquid composition of the colored composition of the present invention in which a red pigment is dispersed in the formed partition wall is ejected by an ink jet apparatus, pre-baking is performed to evaporate the solvent. Next, this coating film is exposed as necessary and then cured by post-baking to form a red pixel pattern.

  Subsequently, using each coloring composition of green or blue, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as described above. Thereby, a color filter in which pixel patterns of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

In addition, the partition has not only a light shielding function but also a function for preventing the color composition of each color discharged in the section from being mixed, so that the film is a film compared to the black matrix used in the first method described above. Thick. Therefore, a partition is normally formed using a black radiation sensitive composition.
The substrate used when forming the color filter, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. Thus, the film thickness of the pixel formed by the ink jet method is approximately the same as the thickness of the black matrix.

A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer). In this case, a colored radiation-sensitive composition in which a black colorant is dispersed is used, but the colored composition of the present invention can also be suitably used for forming such a black spacer.
Since the color filter of the present invention thus obtained has extremely high luminance and color purity, it is extremely useful for color liquid crystal display elements, color image pickup tube elements, color sensors, organic EL display elements, electronic paper, and the like.

Display element The display element of the present invention comprises the color filter of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.
A color liquid crystal display device including the color filter of the present invention can have an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. In addition, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped with tin) electrode is formed are a liquid crystal layer. It is also possible to adopt a structure that is opposed to each other. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.

  The color liquid crystal display device including the color filter of the present invention may include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED that obtains white light by color mixing by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by color mixing by combining a blue LED, a red LED, and a green phosphor, and a blue LED White LED that obtains white light by mixing colors, red LED and green light emitting phosphor, white LED that obtains white light by mixing colors of blue LED and YAG phosphor, blue LED, orange light emitting phosphor and green light emitting fluorescence A white LED that obtains white light by color mixing by combining the body, a white LED that obtains white light by color mixing by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor can be exemplified.

  The color liquid crystal display device having the color filter of the present invention includes a TN (twisted nematic) type, an STN (super twisted nematic) type, an IPS (in-plane switching) type, a VA (vertical alignment) type, and an OCB (Optic Optical). An appropriate liquid crystal mode such as a birefringence type can be applied.

  Moreover, the organic EL display element provided with the color filter of the present invention can have an appropriate structure, for example, the structure disclosed in JP-A-11-307242.

  In addition, the electronic paper including the color filter of the present invention can have an appropriate structure, for example, a structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Measurement of Mw and Mw / Mn>
Mw and Mn of the (B) copolymer obtained in each of the following synthesis examples were measured by gel permeation chromatography (hereinafter abbreviated as GPC) having the following specifications. In Table 1, a measurement result is shown with the copolymerization ratio (mass%) of each monomer in (B) copolymer.
Apparatus: GPC-104 (made by Showa Denko KK).
Column: KD-G, KF-603, KF-602, KF-601 (manufactured by Showa Denko KK) were used in combination.
Mobile phase: DMF.

<Synthesis of (B) copolymer>
Hereinafter, the abbreviations of the raw materials used for “(B) copolymer synthesis” are as follows.
THF: Tetrahydrofuran EEMA: 1-Ethoxyethyl methacrylate MA: Methacrylic acid nBMA: Normal butyl methacrylate MMA: Methyl methacrylate AIBN: 2,2′-azobisisobutyronitrile DAMA: Dimethylaminoethyl methacrylate CHMA: Cyclohexyl methacrylate BzMA: Benzyl Methacrylate PME-200: Methoxypolyethylene glycol monomethacrylate (manufactured by NOF Corporation, trade name PME-200, n≈4 in the above formula (3))
PME-100: Methoxypolyethylene glycol monomethacrylate (manufactured by NOF Corporation, trade name PME-100, n = 2 in the above formula (3))

Synthesis example 1
To a 1000 mL flask equipped with a stirrer, 516.1 g of THF, 34.1 g of lithium chloride (4.1% by mass concentration THF solution), and 3.6 g of diphenylethylene were added and cooled to −60 ° C. After adding 9.2 g of n-butyllithium (15.4 mass% hexane solution) and aging for 10 minutes, a mixed solution of 18.5 g of PME-200, 34.0 g of nBMA, 6.1 g of EEMA was added dropwise, and the reaction was performed for 15 minutes. Continued.
Next, 55.4 g of DAMA was dropped, and after the dropping, the reaction was continued for 30 minutes, and then 3.2 g of methanol was added to stop the reaction. The obtained copolymer was adjusted to a 25 mass% concentration propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) solution, 114 g of water was added, and the mixture was heated to 100 ° C. and reacted for 8 hours. By this reaction, EEMA was hydrolyzed to generate a repeating unit derived from MA. The water was distilled off and adjusted to a 40 mass% PGMEA solution. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200, nBMA, and MA was obtained. The obtained copolymer is referred to as “copolymer (B-1)”.

Synthesis example 2
To a 300 mL flask equipped with a stir bar, 30 g of toluene, 4.2 g of PME-200, 5.6 g of MMA, 121 mg of AIBN and 312 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were added and dissolved, and nitrogen substitution was performed for 30 minutes. It was. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 60 ° C., and this temperature was maintained for 24 hours to perform living radical polymerization.
Next, a solution in which 983 mg of AIBN and 18.2 g of DAMA were dissolved in 20 g of toluene and then purged with nitrogen for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 60 ° C. for 24 hours. Then, it adjusted to the PGMEA solution of 40 mass% concentration by concentration under reduced pressure. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200 and MMA was obtained. Let the obtained block copolymer be a "copolymer (B-2)."

Synthesis example 3
To a 2000 mL flask equipped with a stirrer, 987.6 g of THF and 51.4 g of lithium chloride (3.9 mass% concentration in THF) were added and cooled to −60 ° C. Add 21.4 g of n-butyllithium (15.4% strength by weight hexane solution), stir for 10 minutes, then add 4.9 g of diisopropylamine, stir for 15 minutes, then add 4.7 g of methyl isobutyrate for an additional 15 minutes. Stir. A mixed solution of MMA 87.9 g and PME-200 45.3 g was added dropwise, and the reaction was continued for 15 minutes.
Next, 133.6 g of DAMA was added dropwise, and the reaction was continued for 30 minutes after the dropwise addition. Then, 7.7 g of methanol was added to stop the reaction. The obtained copolymer was adjusted to a 40% by mass PGMEA solution. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200 and MMA was obtained. The obtained copolymer is referred to as “copolymer (B-3)”.

Synthesis example 4
To a 300 mL flask equipped with a stir bar, 30 g of toluene, 7.6 g of nBMA, 9.2 g of PME-200, 174 mg of AIBN and 449 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were added and dissolved, and nitrogen substitution was performed for 30 minutes. It was. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 60 ° C., and this temperature was maintained for 24 hours to perform living radical polymerization.
Next, a solution in which 716 mg of AIBN and 11.2 g of DAMA were dissolved in 20 g of toluene and then purged with nitrogen for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 60 ° C. for 24 hours. Then, it adjusted to the PGMEA solution of 40 mass% concentration by concentration under reduced pressure. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200 and nBMA was obtained. Let the obtained block copolymer be a "copolymer (B-4)."

Synthesis example 5
To a 300 mL flask equipped with a stir bar, 20 g of toluene, 187 mg of AIBN, and 12.3 g of DAMA were added and dissolved, followed by nitrogen replacement for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 60 ° C., and this temperature was maintained for 24 hours to perform living radical polymerization.
Next, MMA 2.2 g, PME-200 7.0 g, CHMA 5.6 g, MA 0.8 g, AIBN 809 mg, and pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester 461 mg were dissolved in 30 g of toluene, followed by nitrogen substitution for 30 minutes. The resulting solution was added to the reaction solution, and living radical polymerization was performed at 60 ° C. for 24 hours. Then, it adjusted to the PGMEA solution of 40 mass% concentration by concentration under reduced pressure. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200, MMA, CHMA, and MA was obtained. Let the obtained block copolymer be a "copolymer (B-5)."

Synthesis Example 6
To a 1000 mL flask equipped with a stirrer, 503.0 g of THF and 59.5 g of lithium chloride (4.1% by mass concentration THF solution) were added and cooled to −60 ° C. Add 11.9 g of n-butyllithium (15.4% strength by weight hexane solution) and stir for 10 minutes, then add 2.8 g of diisopropylamine and stir for 15 minutes, then add 2.8 g of methyl isobutyrate for another 15 minutes. Stir. A mixed solution of MMA 74.6 g and PME-100 32.2 g was dropped, and the reaction was continued for 15 minutes.
Next, 52.1 g of DAMA was dropped, and after the dropping, the reaction was continued for 30 minutes, and then 4.5 g of methanol was added to stop the reaction. The obtained copolymer was adjusted to a 40% by mass PGMEA solution. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200 and MMA was obtained. The obtained copolymer is referred to as “copolymer (B-6)”.

Comparative Synthesis Example 1
In a 300 mL flask equipped with a stirrer, 30 g of toluene, 5.6 g of PME-200, 13.1 g of BzMA, 196 mg of AIBN and 506 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were added and dissolved, and nitrogen substitution was performed for 30 minutes. It was. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 60 ° C., and this temperature was maintained for 24 hours to perform living radical polymerization.
Next, a solution in which 607 mg of AIBN and 9.2 g of DAMA were dissolved in 20 g of toluene and then purged with nitrogen for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 60 ° C. for 24 hours. Then, it adjusted to the PGMEA solution of 40 mass% concentration by concentration under reduced pressure. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200 and BzMA was obtained. Let the obtained block copolymer be a "copolymer (b-1)."

Comparative Synthesis Example 2
To a 1000 mL flask equipped with a stir bar, 498.6 g of THF and 42.5 g of lithium chloride (4.1% by mass concentration THF solution) were added, and cooled to −60 ° C. Add 8.7 g of n-butyllithium (15.4% strength by weight hexane solution), stir for 10 minutes, then add 1.8 g of diisopropylamine and stir for 15 minutes, then add 1.8 g of methyl isobutyrate for another 15 minutes. Stir. A mixed solution of MMA 60.7 g, PME-200 33.6 g, and EEMA 11.8 g was dropped, and the reaction was continued for 15 minutes.
Next, 28.7 g of DAMA was dropped, and after the dropping, the reaction was continued for 30 minutes, and then 2.4 g of water was added to stop the reaction. After adjusting the obtained copolymer to a 25 mass% PGMEA solution, 135 g of water was added, and the mixture was heated to 100 ° C. and reacted for 8 hours. By this reaction, EEMA was hydrolyzed to generate a repeating unit derived from MA. The water was distilled off and adjusted to a 40 mass% PGMEA solution. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200, MMA, and MA was obtained. Let the obtained block copolymer be a "copolymer (b-2)."

Comparative Synthesis Example 3
To a 300 mL flask equipped with a stir bar, 20 g of toluene, 66 mg of AIBN, and 21.0 g of DAMA were added and dissolved, followed by nitrogen substitution for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 60 ° C., and this temperature was maintained for 24 hours to perform living radical polymerization.
Next, after dissolving 2.8 g of nBMA, 4.2 g of PME-200, 1259 mg of AIBN and 170 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester in 30 g of toluene, a solution in which nitrogen substitution was performed for 30 minutes was added to the reaction solution. Then, living radical polymerization was performed at 60 ° C. for 24 hours. Then, it adjusted to the PGMEA solution of 40 mass% concentration by concentration under reduced pressure. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200 and nBMA was obtained. Let the obtained block copolymer be a "copolymer (b-3)."

<Measurement of acid value>
The acid value of the (B) copolymer obtained in each of the above synthesis examples was measured as follows. Table 1 shows the measurement results.
0.5 g of the copolymer solution was precisely weighed to a unit of 1 mg and separated into a glass container. After diluting to 50 mL with propylene glycol monomethyl ether acetate, phenolphthalein was added, titrated with 0.1 N ethanolic potassium hydroxide aqueous solution, and the point colored in pink was the end point. Similarly, a blank test was performed. (B) The acid value (unit: mgKOH / g) was calculated from the amount of the copolymer and 0.1N ethanolic potassium hydroxide aqueous solution dropped in the blank test.

<Measurement of amine value>
The amine value of the (B) copolymer obtained in each of the above synthesis examples was measured as follows. Table 1 shows the measurement results.
0.5 g of the copolymer solution was precisely weighed to a unit of 1 mg and separated into a glass container. Acetic anhydride / acetic acid = 9/1 (volume ratio) 20 mL was added and dissolved, and left at room temperature for 3 hours. Thereafter, 30 mL of acetic acid was further added, and titration was performed with a 0.1 mol / L perchloric acid / acetic acid solution using a potentiometer AT-510 (manufactured by Kyoto Electronics Co., Ltd.). Similarly, a blank test was performed. (B) The amine value (unit: mgKOH / g) was calculated from the amount of the copolymer and the 0.1 mol / L perchloric acid / acetic acid solution dropped in the blank test.

<Preparation of pigment dispersion>
Preparation Example 1
As a coloring agent, C.I. I. Pigment Green 58 (manufactured by DIC) with 12 parts by mass and C.I. I. 3 parts by weight of Pigment Yellow 138, 10 parts by weight of copolymer (B-1) solution (nonvolatile component = 40% by weight), and 67 parts by weight of propylene glycol monomethyl ether acetate and 8 parts by weight of propylene glycol monomethyl ether as a solvent The pigment dispersion (A-1) was prepared by processing with a bead mill.

Preparation Examples 2-6 and Comparative Preparation Examples 1-3
In Preparation Example 1, pigment dispersions (A-2) to (A-9) were prepared in the same manner as Preparation Example 1, except that the type of (B) copolymer was changed as shown in Table 2.

<Evaluation of pigment dispersion>
The viscosity of the obtained pigment dispersion was measured using an E-type viscometer (manufactured by Tokyo Keiki). The obtained colorant dispersion was filled in a light-shielding glass container and allowed to stand at 23 ° C. for 14 days in a sealed state, and then the viscosity was measured again using an E-type viscometer (manufactured by Tokyo Keiki). Then, the increase rate of the viscosity after storage for 14 days with respect to the viscosity immediately after the preparation is calculated. When the increase rate is less than 5%, “A”, when 5% or more and less than 10%, “B”, 10% or more The case was evaluated as “C”. The evaluation results are shown in Table 2.

  In Table 2, “G58” means C.I. I. Pigment Green 58, “Y138” is C.I. I. Pigment Yellow 138, “PGMEA” means propylene glycol monomethyl ether acetate, and “PGME” means propylene glycol monomethyl ether.

<Synthesis of binder resin>
Synthesis example 7
In a flask equipped with a condenser and a stirrer, 30.0 g of BzMA, 20.0 g of nBMA, 15.0 g of hydroxyethyl methacrylate, 20.0 g of styrene, 15.0 g of MA and 200 g of PGMEA are added and dissolved, and 3.0 g of AIBN and α-methylstyrene are further added. Dimer 5.0 g was charged, and then nitrogen substitution was performed for 15 minutes. Thereafter, the reaction solution was heated to 80 ° C. with stirring and polymerized for 5 hours to obtain a solution containing 33% by mass of the binder resin (D-1). This binder resin (D-1) had a weight average molecular weight in terms of polystyrene measured by GPC (mobile phase: tetrahydrofuran) of 10,000, and the ratio of the weight average molecular weight to the number average molecular weight was 2.5.

Synthesis example 8
In a flask equipped with a condenser and a stirrer, 25.0 g of 3-methacryloyloxymethyl-3-ethyloxetane, 18.0 g of MA, 9.0 g of mono-2-acryloxyethyl succinate, 10.0 g of N-phenylmaleimide, 24 g of BzMA. 0 g, 14.0 g of hydroxyethyl methacrylate and 300 g of PGMEA were added and dissolved, and 6.0 g of AIBN and 6.0 g of α-methylstyrene dimer were added, and then the atmosphere was replaced with nitrogen for 15 minutes. Thereafter, the reaction solution was heated to 80 ° C. with stirring and polymerized for 5 hours to obtain a precursor copolymer solution.
To 200 g of the obtained precursor copolymer solution, 13.4 g of 2-methacryloyloxyethyl isocyanate and 0.2 g of 4-methoxyphenol as a polymerization inhibitor were added and reacted at 90 ° C. for 2 hours. The reaction solution was washed twice with 75 g of ion exchange water per time and then concentrated under reduced pressure to obtain a solution containing 33% by mass of the binder resin (D-2). This binder resin (D-2) had a polystyrene-equivalent weight average molecular weight of 11,000 and a ratio of the weight average molecular weight to the number average molecular weight measured by GPC (elution solvent: tetrahydrofuran) of 1.9.

<Preparation and evaluation of coloring composition>
Preparation of coloring composition Example 1
100 parts by mass of the pigment dispersion (A-1), 13.4 parts by mass of the binder resin (D-1) solution as the binder resin, and MAX-3510 (manufactured by Nippon Kayaku Co., Ltd.) as the crosslinking agent (mainly dipentaerythritol hexaacrylate) ) 5.0 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name: Irgacure 369, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator 2.8 parts by mass, 0.3 mass part of Megafac F-554 (manufactured by DIC Corporation) as a fluorosurfactant, and 126.5 parts by mass of ethyl 3-ethoxypropionate as a solvent are mixed to form a liquid. A colored composition was prepared.

Evaluation of chromaticity characteristics After the obtained colored composition was applied on a glass substrate using a spin coater, it was pre-baked for 2 minutes on a hot plate at 90 ° C., and three coating films with different film thicknesses were formed. Formed. Next, after these substrates are cooled to room temperature, a high-pressure mercury lamp is used for the coating film on the substrate, and radiation including each wavelength of 365 nm, 405 nm, and 436 nm is applied to each coating film without passing through a photomask. The exposure was performed at an exposure amount of 1,000 J / m ² . Thereafter, post baking was performed at 230 ° C. for 60 minutes to form a cured film on the substrate. Using the color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinate value (x, y) and the stimulus value in the CIE color system with a C light source and a 2-degree visual field for the three cured films obtained. (Y) was measured. From the measurement results, the chromaticity coordinate value x and the stimulus value (Y) when the chromaticity coordinate value y = 0.568 were obtained. The evaluation results are shown in Table 3. Note that the stimulus value (Y) indicates higher luminance as the value increases.

Contrast Evaluation Contrast of the three cured films obtained in the above “evaluation of chromaticity characteristics” was measured using a contrast meter (Contrast measuring instrument CT-1 manufactured by Aisaka Electric Co., Ltd.). From the measurement result, the contrast when the chromaticity coordinate value y = 0.568 was obtained. The evaluation results are shown in Table 3. In addition, it shows that contrast is so high that a value is large.

Examples 2-6 and Comparative Examples 1-3
Preparation of a colored composition in the same manner as in Example 1 except that the types and blending amounts of the pigment dispersion, binder resin, crosslinking agent, photopolymerization initiator and solvent were changed as shown in Table 3. And evaluated. The evaluation results are shown in Table 3.

In Table 3, each component is as follows.
C-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name MAX-3510, manufactured by Nippon Kayaku Co., Ltd.)
C-2: monoesterified product of dipentaerythritol pentaacrylate and succinic acid, dipentaerythritol hexaacrylate, and mixture of dipentaerythritol pentaacrylate (trade name TO-1382, manufactured by Toagosei Co., Ltd.)
E-1: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name IRGACURE OXE02, Ciba Specialty・ Made by Chemicals
E-2: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals)
EEP: ethyl 3-ethoxypropionate MBA: 3-methoxybutyl acetate

Claims (6)

The following components (A), (B) and (C);
(A) a colorant containing a quinophthalone pigment,
(B) including a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3) or a repeating unit having an acidic group. A coloring composition for a color filter, comprising a copolymer having an amine value of 143 to 232 mgKOH / g, and (C) a crosslinking agent.

[In Formula (1),
R ¹ represents a hydrogen atom or a methyl group,
Z represents —NR ² R ³ (wherein R ² and R ³ each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group) or a substituted or unsubstituted nitrogen-containing heterocyclic group. Show
X ¹ represents a divalent linking group. ]

[In Formula (2),
R ⁴ represents a hydrogen atom or a methyl group,
R ⁵ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group. ]

[In Formula (3),
R ⁶ represents a hydrogen atom or a methyl group,
R ⁷ , independently of each other, represents an alkanediyl group having 2 to 4 carbon atoms,
R ⁸ represents an alkyl group having 1 to 6 carbon atoms,
n shows the integer of 1-150. ] The quinophthalone pigment is C.I. I. The coloring composition for a color filter according to claim 1, which is CI Pigment Yellow 138. The coloring composition for a color filter according to claim 1 or 2 , further comprising (D) a binder resin (excluding the component (B)). The color filter provided with the colored layer formed using the coloring composition of any one of Claims 1-3 . A display element comprising the color filter according to claim 4 . The following components (a1), (B) and (F);
(A1) a quinophthalone pigment,
(B) including a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3) or a repeating unit having an acidic group. A pigment dispersion for a color filter, comprising a copolymer having an amine value of 143 to 232 mgKOH / g, and (F) a solvent.

[In Formula (1),
R ¹ represents a hydrogen atom or a methyl group,
Z represents —NR ² R ³ (wherein R ² and R ³ each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group) or a substituted or unsubstituted nitrogen-containing heterocyclic group. Show
X ¹ represents a divalent linking group. ]

[In Formula (2),
R ⁴ represents a hydrogen atom or a methyl group,
R ⁵ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group. ]

[In Formula (3),
R ⁶ represents a hydrogen atom or a methyl group,
R ⁷ , independently of each other, represents an alkanediyl group having 2 to 4 carbon atoms,
R ⁸ represents an alkyl group having 1 to 6 carbon atoms,
n shows the integer of 1-150. ]