TWI620800B - Pigment dispersion liquid, colored composition for color filter, color filter, liquid crystal display and organic electroluminescence display - Google Patents

Abstract

An object of the present invention is to provide a pigment dispersion liquid capable of achieving high contrast and dispersion stability at the same time when a micronized pigment is used, and use the pigment dispersion liquid to provide a color filter with good developability. Coloring composition. The invention provides a pigment dispersion liquid and uses thereof. The pigment dispersion liquid is characterized in that it contains a pigment, a solvent, and a dispersant. The dispersant contains a solvent-soluble A block and a functional group containing a nitrogen atom. For block copolymers composed of blocks, the amine value of the dispersant is 80 mgKOH / g or more and 150 mgKOH / g or less in terms of effective solid content.

Description

Pigment dispersion, coloring composition for color filter, color filter, liquid crystal display device, and organic EL display

The present invention relates to a pigment dispersion liquid, a coloring composition for a color filter, a color filter, a liquid crystal display device, and an organic EL display. More specifically, it relates to a pigment dispersion liquid for highly efficient and stable dispersion of highly micronized pigments, a coloring composition for color filters with excellent developability and excellent color characteristics suitable for plate-making processes, and A color filter of a pixel formed using the coloring composition, and a liquid crystal display device and an organic EL display including the color filter.

Conventionally, as a method for manufacturing a color filter used in a liquid crystal display device or the like, a pigment dispersion method, a dyeing method, a plating method, and a printing method are known. Among them, from the viewpoints of spectral characteristics, durability, pattern shape, and accuracy, a pigment dispersion method having excellent balance characteristics is most widely used.

In recent years, the trend of technological innovation has developed rapidly, and higher color penetration, higher contrast, and higher density requirements have been imposed on color filters. From the viewpoints of heat resistance and light resistance, a pigment is usually used as a coloring material that determines the color of a color filter. As the pigment, it is suitable to use a spectrum in which the intrinsic transmission absorption spectrum of the visible light wavelength region is consistent with the fluorescence spectrum of the back light. For example, as a green pigment, a copper halide phthalocyanine green pigment has been used in combination with various yellow pigments since ancient times.

On the other hand, in order to improve the contrast, it is important to suppress the light scattering in the color filter layer to a minimum. Usually, a solvent salt milling method, a dry milling method, etc. The pigment is used after being micronized to a size having a primary particle diameter of several 10 nm. However, the smaller the particle size is, the larger its surface area is. For example, due to insufficient adsorption amount of the dispersant, re-aggregation tends to occur, and the dispersion system tends to become unstable. Therefore, how to stably prepare a micronized pigment for improving the contrast to exist as a dispersion has become an extremely important technical issue in recent years.

However, in recent years, with regard to the enhancement of the brightness of green pixels, novel phthalocyanine green pigments having specific hue, as described in Patent Documents 1 and 2, have been proposed, thereby achieving differentiation from conventional copper halide phthalocyanine green pigments. However, this novel green pigment, that is, a zinc bromide phthalocyanine pigment, has the following problems: When miniaturization is performed in order to increase the contrast, the dispersion stability is extremely reduced. Due to the influence of light scattering caused by secondary aggregation, When used as a television, its contrast becomes insufficient.

In order to solve such a problem, for example, Patent Document 2 discloses the use of a (meth) acrylic (co) polymer Polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and Megaface F171. , F172, F173 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), Fluorad FC430, FC431 (manufactured by Sumitomo 3M), Solsperse 13240, 20000, 24000, 26000, 28000 and various Solsperse dispersants (manufactured by Avecia), Disperbyk 111, 161 , 162, 163, 164, 182, 2000, 2001 and other Disperbyk dispersants (manufactured by BYK Chemie), Ajisper PB711, PB411, PB111, PB821, PB822 and other Ajisper dispersants (Ajinomoto Precision Technology) (Manufactured by Ajinomoto Fine-Techno) as a dispersant for preparing a pigment dispersion liquid. In the embodiment, Among them, BYK-2001, an acrylic dispersant manufactured by BYK Chemical Co., was used. However, according to the inventors' verification, even with the use of these polymer dispersants, the dispersion stability of the above-mentioned micronized zinc bromide phthalocyanine pigment cannot be sufficiently maintained, and viscosity increases due to re-agglutination or due to time. Aggregation causes problems such as decreased contrast.

Patent Document 1: Japanese Patent Laid-Open No. 2004-70342

Patent Document 2: Japanese Patent Laid-Open No. 2004-70343

This invention was made in view of the said subject, The objective is as follows.

(1) Provide a small amount of additive to efficiently disperse highly pigmented pigments in recent years. As a result, pigment dispersions and coloring of color filters with high transmittance, high contrast, and low film thickness can be produced.组合 物。 Composition.

(2) In particular, it provides the problems that exist when using zinc bromide phthalocyanine green pigments for the purpose of increasing the brightness of green pixels, that is, pigment dispersions that have both high contrast and dispersion stability, and A coloring composition for a filter.

(3) Provide a coloring composition for a color filter having advantages such as good solubility in a developing solution, development in a specific time in a developing step, and non-remaining coloring on a non-image portion on a substrate The undissolved matter of the resin composition has excellent adhesion to the substrate, and does not reduce image forming ability such as hardenability, and can produce high transmittance. High contrast. Low film thickness color filter.

(4) Use of the coloring composition for color filters described above to provide high quality Color filters.

(5) Provide a high-quality liquid crystal display device and an organic EL display using the color filter.

The present inventors conducted diligent research in order to solve the above-mentioned problems, and as a result, they found that by using a block copolymer which is characterized by a block A having a lipophilic property and a block B having a functional group containing a nitrogen atom Moreover, the dispersant whose amine value is 80 mgKOH / g or more in terms of effective solid content conversion, can achieve sufficient dispersion stability even for micronized pigments, and can provide a liquid crystal television with sufficiently high contrast. A color filter, thereby finally completing the present invention.

The present invention is composed of a plurality of related inventions, and the gist of each invention is as follows.

[1] A pigment dispersion, characterized in that it contains a pigment, a solvent, and a dispersant. The dispersant contains a block composed of a solvent-soluble A block and a B block having a functional group containing a nitrogen atom. Copolymer. The amine value of the dispersant is 80 mgKOH / g or more and 150 mgKOH / g or less in terms of effective solid content.

[2] The pigment dispersion liquid according to the above [1], wherein the pigment contains zinc bromide phthalocyanine.

[3] The pigment dispersion liquid according to the above [1] or [2], further comprising an aromatic carboxylic acid-based compound.

[4] The pigment dispersion liquid according to the above [3], wherein the aromatic carboxylic acid-based compound is a compound represented by the following general formula (VI).

(In the above general formula (VI), Z ¹ represents a methylene group or -O-, and m represents an integer of 0 to 3. Where m is 2 or 3, m Z ¹ may be the same or different.

X ³ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, benzyl, phenethyl, benzyloxy, or -COOX ⁴ (wherein X ⁴ represents an alkyl group or a phenyl group having 1 to 7 carbon atoms), and each of these groups may have a substituent. )

[5] The pigment dispersion liquid according to the above [4], wherein the compound represented by the general formula (VI) is a phthalic acid monoester compound.

[6] The pigment dispersion liquid according to any one of the above [1] to [5], wherein in the block copolymer, 20 mol% or more of the repeating unit having a functional group containing a nitrogen atom is Repeating units of primary to tertiary amine groups.

[7] The pigment dispersion liquid according to any one of the above [1] to [6], wherein in the above block copolymer, the repeating unit having a functional group containing a nitrogen atom is a repeating unit having a tertiary amine group The repeating unit is derived from dimethylaminoethyl (meth) acrylate.

[8] The pigment dispersion liquid according to any one of the above [1] to [7], wherein in the block copolymer, the A block contains 5 to 40 mole% or less The partial structure represented by the general formula (IV) is described.

(In the above general formula (IV), n represents any integer from 1 to 5. R ⁵⁰ represents a hydrogen atom or a methyl group.)

[9] The pigment dispersion liquid according to any one of the above [1] to [8], wherein the average primary particle diameter of the pigment is 0.04 μm or less.

[10] A coloring composition for a color filter, comprising the pigment dispersion liquid according to any one of the above [1] to [9] and a binder resin.

[11] A coloring composition for a color filter, characterized in that it contains a pigment, a solvent, a dispersant, and a binder resin, and the dispersant contains a solvent-soluble A block and a function having a nitrogen atom. For block copolymers composed of basic B blocks, the amine value of the dispersant is 80 mgKOH / g or more and 150 mgKOH / g or less in terms of effective solid content.

[12] The coloring composition according to the above [11], wherein the pigment contains zinc bromide phthalocyanine.

[13] The coloring composition according to the above [11] or [12], further comprising an aromatic carboxylic acid-based compound.

[14] The coloring composition according to the above [13], wherein the aromatic carboxylic acid-based compound is a compound represented by the following general formula (VI).

(In the above general formula (VI), Z ¹ represents a methylene group or -O-, and m represents an integer of 0 to 3. Among them, when m is 2 or 3, m Z ¹ may be the same or different.

X ³ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, benzyl, phenethyl, benzyloxy, or -COOX ⁴ (wherein X ⁴ represents an alkyl group or a phenyl group having 1 to 7 carbon atoms), each of these groups may have a substituent. )

[15] The coloring composition according to the above [14], wherein the compound represented by the general formula (VI) is a phthalic acid monoester compound.

[16] The coloring composition according to any one of the above [11] to [15], wherein in the block copolymer, 20 mol% or more of the repeating unit having a functional group containing a nitrogen atom is Repeating units of primary to tertiary amine groups.

[17] The coloring composition according to any one of the above [11] to [16], wherein in the above block copolymer, the repeating unit having a functional group containing a nitrogen atom is a repeating unit having a tertiary amine group The repeating unit is derived from dimethylaminoethyl (meth) acrylate.

[18] The coloring composition according to any one of the above [11] to [17], wherein In the above block copolymer, the A block contains 5 to 40 mol% of a partial structure represented by the following formula (IV).

(In the above general formula (IV), n represents any integer from 1 to 5. R ⁵⁰ represents a hydrogen atom or a methyl group.)

[19] The coloring composition according to any one of the above [11] to [18], wherein the average primary particle diameter of the pigment is 0.04 μm or less.

[20] The coloring composition according to any one of the above [10] to [19], wherein the adhesive resin contains the following resins: (meth) acrylate containing epoxy groups and other radical polymerizable monomers A copolymer obtained by adding unsaturated monobasic acid to at least a part of the epoxy group possessed by the copolymer, or adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction The obtained alkali-soluble resin.

[21] The coloring composition according to any one of the above [10] to [20], further comprising at least one of a photopolymerization starting component and a thermal polymerization initiator.

[22] The coloring composition according to the above [21], wherein the photopolymerization starting component contains an oxime ester compound.

[23] The coloring composition according to the above [22], wherein the oxime ester compound is a compound represented by the following general formula (I).

[In the above general formula (I), R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms or 4 to 25 carbon atoms Heteroaralkyl, which may have a substituent. Alternatively, R ¹ may be bonded to X or Y to form a ring.

R ² represents an alkanoyl group having 2 to 20 carbon atoms, an alkenyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, and 2 carbon atoms Alkoxycarbonyl group of 10 to 10, aryloxycarbonyl group of 7 to 20 carbon atoms, heteroaryl group of 2 to 20 carbon atoms, heteroarylfluorenyl group of 3 to 20 carbon atoms or alkylamino group of 2 to 20 carbon atoms , These can have substituents.

X represents at least one of a divalent aromatic hydrocarbon group and an aromatic heterocyclic group which may have a substituent and which is obtained by condensing two or more rings. Y represents an aromatic group which may have a substituent. ]

[24] The coloring composition according to the above [23], wherein the compound represented by the general formula (I) is a compound represented by the following structural formula (i).

[In the general formula (i), R ¹ , R ² and Y have the same meanings as in the general formula (I). The ring X ² represents a ring condensed with a benzene ring X ¹ , and may be a single ring or a condensed ring composed of two or more rings. X ² may be condensed at any position of the benzene ring X ¹ . The benzene ring X ¹ and the ring X ² condensed therewith may further have a substituent. ]

[25] The coloring composition according to any one of the above [10] to [24], further comprising a polymerizable monomer.

[26] The coloring composition according to the above [25], wherein the polymerizable monomer is an addition polymerizable compound having at least one ethylenic double bond, and the molecular weight of the compound is 650 or less and the double bond equivalent is 150 the following.

[27] A color filter including a substrate and a pixel formed on the substrate, wherein a part or all of the pixel is formed using the coloring composition of any one of [10] to [26] form.

[28] A liquid crystal display device including the color filter of [27].

[29] An organic EL display including the color filter according to the above [27].

The present invention exhibits the effects listed below.

(1) A pigment dispersion liquid that can efficiently disperse highly micronized pigments in recent years can be provided with a small amount of additive. As a result, a pigment dispersion liquid with high transmittance, high contrast, and low film thickness And colored composition.

(2) In particular, it can provide the problems existing in the use of zinc bromide phthalocyanine green pigment for the purpose of achieving high brightness of green pixels, that is, it has both high Contrast and dispersion stability pigment dispersions and coloring compositions for color filters.

(3) A coloring composition for a color filter having advantages such as good solubility in a developing solution, development in a specific time in a developing step, and no colored resin remaining on non-image portions on a substrate The undissolved material of the composition has excellent adhesion to the substrate, and does not reduce image forming ability such as hardenability, and can produce high transmittance. High contrast. Low film thickness color filter.

(4) The coloring composition for a color filter can be used to provide a high-quality color filter.

(5) A high-quality liquid crystal display device and an organic EL display using the above color filters can be provided.

Hereinafter, the constituent elements and the like of the present invention will be described in detail, but these constituent elements are examples of implementation aspects of the present invention, and the present invention is not limited to these contents.

In addition, "(meth) acryl" and the like mean "at least one of acryl and methacryl"; "(meth) acrylate" and the like mean "of an acrylate and a methacrylate At least one "and the like, for example," (meth) acrylic acid "means" at least one of acrylic acid and methacrylic acid ".

In addition, the "total solid content" means the total component other than the solvent component mentioned later contained in a pigment dispersion liquid or a coloring composition.

In the present invention, the weight-average molecular weight refers to the weight average molecular weight by GPC method (gel permeation chromatography) The measured polystyrene-equivalent weight average molecular weight (Mw).

In the present invention, unless otherwise specified, the "amine value" means the amine value in terms of effective solid content, which is expressed by the weight of KOH equivalent to the alkali amount per 1 g of the solid content of the dispersant. value. The measurement method will be described later.

[1] Pigment dispersion

Hereinafter, each component of the pigment dispersion liquid of this invention is demonstrated. The pigment dispersion liquid of the present invention contains a pigment, a solvent, and a dispersant as essential components, and may further contain additives other than the above components, if necessary.

Hereinafter, each component will be described.

[1-1] pigment

As the pigment, pigments of various colors such as blue pigment, green pigment, red pigment, yellow pigment, purple pigment, orange pigment, brown pigment, and black pigment can be used. In addition, as its structure, azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, In addition to organic pigments such as (dioxazine), indanthrene, and perylene, various inorganic pigments can also be used. Hereinafter, specific examples of pigments that can be used are represented by pigment numbers. Terms such as "CI Pigment Red 2" mentioned below mean color index (CI).

Examples of the red pigment include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, etc. Among them, preferably, CI Pigment Red 48: 1, 122, 166, 168, 177, 202, 206, 207, 209, 224, 242, 254, etc., and more preferably, CI Pigment Red 166 , 177, 209, 224, 242, 254, etc.

Examples of the blue pigment include CI Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19 , 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76 , 78, 79, etc. Among these, C. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and the like are more preferable, and C. I. Pigment Blue 15: 6 is more preferable.

Examples of the green pigment include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54 , 55 and 58 are representative of zinc bromide phthalocyanine and the like. Among them, zinc bromidephthalein represented by C.I. Pigment Green 7, 36, and 58 is preferable. Cyan, etc., particularly preferred is C. I. Pigment Green G58. The details of the zinc bromide phthalocyanine represented by C.I pigment green G58 will be described later.

Examples of the yellow pigment include CI Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, etc. Among them, CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, etc. are preferable, and CI Pigment Yellow 83, 138, 139, 150 are more preferable. , 180, etc.

Examples of the orange pigment include CI pigment orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 and so on. Among these, C.I. Pigment Orange 38, 71, and the like are preferable.

Examples of the purple pigment include: CI Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, pigment blue 80, etc. Among these, C. I. Pigment Violet 19, 23, and the like are preferable, and C. I. Pigment Violet 23 is more preferable.

As the black pigment, a black pigment alone or a black pigment obtained by mixing red, green, and blue pigments can be used. These black pigments can be appropriately selected from inorganic or organic pigments and dyes, and they can be used alone or in combination.

Examples of the single black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black. Among these, carbon black and titanium black are particularly preferable from the viewpoints of light shielding rate and image characteristics. Examples of commercially available products of carbon black include the following brands.

Manufactured by Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA220, MA230, # 52, # 50, # 47, # 45, # 2700, # 2650, # 2200, # 1000, # 990, # 900, etc.

Made by Degussa: Printex95, Printex90, Printex85, Printex75, Printex55, Printex45, Printex40, Printex30, Printex3, PrintexA, PrintexG, Special Black550, Special Black350, Special Black250, Special Black100, etc.

Made by Cabot: Monarch460, Monarch430, Monarch280, Monarch120, Monarch800, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, BLACK PEARLS 480, PEARLS130 Wait.

Manufactured by Columbian Carbon: RAVEN11, RAVEN15, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, etc.

Next, the black pigment mixed will be described. Specific examples of the color material to be used as the base material for mixing include Victoria Pure Blue (42595), Aumine O (41000), Cathilon Brilliant Flavin (Basic 13), Rose Red 6GCP (45160), and Rose B (45170), Saffron OK70: 100 (50240), Wool Poppy X (42080), No. 120 / Leonor Yellow (21090), Leonor Yellow GRO (21090), Symuler Fast Yellow 8GF (21105), Benzidine yellow 4T-564D (21095), Symuler Fast Red 4015 (12355), Leonor Red 7B4401 (15850), Fastogen Blue TGR-L (74160), Leonor Blue SM (26150), Leonor Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Leonor Green 2YS (Pigment Green 36), and the like (in addition, the numbers in the above () means color index (CI)).

In addition, the CI number is used to indicate other pigments that can be used in combination. Examples include CI yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, and 154. , 166, etc .; CI orange pigments 36, 43, 51, 55, 59, 61, etc .; CI red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223 , 224, 226, 227, 228, 240, etc .; CI purple pigments 19, 23, 29, 30, 37, 40, 50, etc .; CI blue pigments 15, 15: 1, 15: 4, 22, 60, 64, etc .; C. I. Green pigment 7; C. I. Brown pigment 23, 25, 26, etc.

In addition, the above carbon black may be used in combination with other black or colored inorganic and organic pigments. Compared with carbon black, other pigments have lower light-shielding properties or image characteristics, so the mixing ratio is naturally limited.

As a method for producing titanium black, there are the following methods: a method of heating and reducing a mixture of titanium dioxide and metallic titanium in a reducing environment (Japanese Patent Laid-Open No. 49-5432), and hydrolyzing titanium tetrachloride by high temperature A method for reducing the obtained ultrafine titanium dioxide in a hydrogen-containing reducing environment (Japanese Patent Laid-Open No. 57-205322), and a method for reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. Sho 52-205322) 60-65069, Japanese Unexamined Patent Publication No. 61-201610), a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide, and performing high-temperature reduction in the presence of ammonia (Japanese Patent Laid-Open Publication No. 61-201610); It is not limited to these methods.

Examples of commercially available products of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, and the like manufactured by MITSUBISHI MATERIALS CORPORATION.

These pigments may be used individually by 1 type, and may use 2 or more types together. The average primary particle diameter of these pigments is usually 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.04 μm or less, particularly preferably 0.025 μm or less, and usually 0.005 μm or more.

When the pigment is micronized, a method such as a solvent salt milling method described later is suitably used.

As the green pigment, zinc bromide phthalocyanine pigment is particularly preferred.

Generally, a zinc phthalocyanine has 16 hydrogen atoms in one molecule, and those hydrogen atoms are replaced with a bromine atom or a chlorine atom, which are zinc bromide phthalocyanine pigments preferably used in the present invention. Among them, zinc bromide phthalocyanine having an average of 13 or more bromine atoms in one molecule is preferable in terms of showing extremely high transmittance and suitable for forming green pixels of a color filter. More preferably, it is a zinc bromide phthalocyanine having 13 to 16 bromine atoms in one molecule and no chlorine atom in one molecule or having an average of 3 or less chlorine atoms, and particularly preferably 14 to 16 bromines in one molecule on average. A zinc bromide phthalocyanine having one atom and containing no chlorine atom in one molecule or having an average of two or less chlorine atoms.

Such a zinc bromide phthalocyanine pigment can be produced by a known production method disclosed in Japanese Patent Laid-Open No. Sho 50-130816 and the like.

For example, there can be mentioned a method in which phthalic acid or phthalonitrile obtained by replacing a part or all of hydrogen atoms on an aromatic ring with halogen atoms such as bromine and chlorine, or phthalonitrile is suitably used as a starting material to synthesize a pigment. In this case, a catalyst such as ammonium molybdate may be used if necessary.

As another method, there can be mentioned a method in which zinc phthalocyanine is brominated with bromine gas in a melt composed of a mixture of aluminum chloride, sodium chloride, sodium bromide, and the like at about 110 to 170 ° C. In this method, the ratio of various zinc bromide phthalocyanines having different bromine contents can be arbitrarily controlled by adjusting the ratio of chloride to bromide in the molten salt, or changing the amount of chlorine gas introduced or the reaction time.

After completion of the reaction, if the obtained mixture is put into an acidic aqueous solution such as hydrochloric acid, the generated zinc bromide phthalocyanine will precipitate. After that, filtering, Post-treatments such as washing and drying give zinc bromide phthalocyanine.

If necessary, the zinc bromide phthalocyanine pigment thus obtained is dry-milled in a pulverizer such as an attritor, a ball mill, a vibration mill, a vibration ball mill, and then pigmented by a solvent salt milling method or a solvent boiling method. Thereby, a green light-emitting zinc bromide phthalocyanine pigment with high transmittance or contrast is obtained. The pigmentation method is not particularly limited, and a solvent salt milling method is preferably used because it can easily suppress crystal growth and obtain pigment particles having a large specific surface area.

The so-called solvent salt milling method means that the crude pigment immediately after synthesis is kneaded and ground with an inorganic salt and an organic solvent. Specifically, a coarse pigment, an inorganic salt, and an organic solvent that does not dissolve it are added to a kneader, and kneaded and ground in the kneader. As the kneading machine at this time, for example, a kneader or a kneader is suitably used, or a pulverizing space formed by a gap between a ring-shaped fixed disk and a concentric rotating disk as described in Japanese Patent Laid-Open No. 2006-77062. Continuous kneading machine and so on.

As said inorganic salt, a water-soluble inorganic salt can be used suitably, For example, it is preferable to use inorganic salts, such as sodium chloride, potassium chloride, and sodium sulfate. The particle diameter of these inorganic salts is more preferably 0.5 to 50 μm. Such an inorganic salt system can be easily obtained by finely pulverizing a common inorganic salt.

The zinc bromide phthalocyanine thus obtained may be used alone, or it may be different from the zinc bromide phthalocyanine having a different bromination rate or chlorination rate, or the central metal is replaced with another metal within the range not impairing the effect of the present invention. Brominated phthalocyanine and the like are used in combination. By changing the chlorination rate and bromination rate or changing the central metal, the hue as a pigment is changed, and an increase in reproducible hue changes can be expected. In addition, even the same green pigment can be combined with C. I. Pigment Green (P. G.) 36 Or 7 and other halogenated copper phthalocyanine.

The average primary particle diameter of the green pigment containing zinc bromide phthalocyanine is usually 0.1 μm or less, preferably 0.04 μm or less, more preferably 0.03 μm or less, particularly preferably 0.025 μm or less, and usually 0.005 μm or more.

If the average primary particle diameter is too large, the depolarization characteristics will deteriorate and the contrast will become insufficient. In severe cases, there may be a case where the transmittance decreases and the fundamental color characteristics are deteriorated, or coarse particles are formed. Protruded foreign matter is generated, which may reduce the yield of the color filter, or cause production problems such as process filter blocking. Conversely, if the average primary particle diameter is too small, problems such as a decrease in dispersion stability due to an increase in the specific surface area of the pigment, or a deterioration in heat resistance and light resistance due to the pigment's close molecular state will occur.

The average primary particle diameter of the pigment can be determined by the following method. That is, the pigment is ultrasonically dispersed in chloroform, added dropwise to the grid attached to the cotton wool film, dried, and observed with a transmission electron microscope (TEM) to obtain a primary particle image of the pigment. . The primary particle size is measured from this image, and a single average value is calculated according to the calculation formula below, and the average particle size is obtained.

In the case of organic pigments, the particle diameter of each pigment particle is calculated as the area circle equivalent diameter converted to the diameter of a circle of the same area, and the particle diameter of a plurality of pigment particles, usually about 200 to 300, is obtained. , Calculate the single average value according to the calculation formula below, and find the average particle size.

Particle size of each pigment particle: X ₁ , X ₂ , X ₃ , X ₄ , ..., X _i , ... X _m

Average particle size = ΣX _i / m

Moreover, in order to mix to a desired color, you may mix and use 2 or more types of each said pigment. For example, when preparing a red or green pigment dispersion or a coloring composition, in order to adjust the hue, at least one yellow pigment may be combined with a red pigment or a green pigment, respectively. Examples of such yellow pigments include the various yellow pigments described above. In addition, in order to prepare a blue pigment dispersion liquid or a coloring composition, a blue pigment may be combined with at least one or more purple pigments. In addition to these, pigments of various colors can be appropriately mixed and used according to the desired chromaticity.

The pigment content in the pigment dispersion liquid of the present invention is usually 90% by weight or less, preferably 85% by weight or less, more preferably 80% by weight or less, and usually 20% by weight or more with respect to the total solid content. , Preferably 30% by weight or more, and more preferably 40% by weight or more.

In addition, the pigment content in the coloring composition for a color filter of the present invention is usually 75% by weight or less, preferably 70% by weight or less, and more preferably 60% by weight or less with respect to the total solid content. It is usually 10% by weight or more, preferably 20% by weight or more, and more preferably 25% by weight or more.

If the amount of the pigment is too large, it is difficult to maintain the dispersed state of the pigment, thereby causing aggregation or sedimentation, and as a result, problems such as an increase in viscosity or a decrease in brightness and contrast may occur. On the other hand, if the amount of the pigment is too small, the color density becomes light, and there is a possibility that the function as a color filter cannot be fully exerted.

[1-2] Solvent

The solvent in the pigment dispersion liquid of the present invention or a coloring composition described later has the following functions: in addition to pigments and dispersants, it can also be formulated as appropriate. Components other than the above are dissolved or dispersed, and viscosity is adjusted.

The solvent may be any one that can dissolve or disperse each component.

Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono-n-butyl ether. Ether, propylene glycol tertiary butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, two Glycol monoalkyl ethers such as propylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol monomethyl ether; Glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether and the like Glycol dialkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethyl acetate Alcohol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, Glycol alkyl ether acetates such as triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate; ethylene glycol diacetate, 1, 3-butane Glycol diacetates such as alcohol diacetate and 1,6-hexanediol diacetate; Alkyl acetates such as cyclohexanol acetate; pentyl ether, propyl ether, diethyl ether, and dipropyl ether , Diisopropyl ether, butyl ether, dipentyl Ethers such as ether, ethyl isobutyl ether, dihexyl ether; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone , Diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethylpentyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone, etc. Ketones; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, Mono- or polyhydric alcohols such as glycerol, benzyl alcohol; n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane Hydrocarbons; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl; aromatics such as benzene, toluene, xylene, cumene Hydrocarbons; pentyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, Butyl butyrate, isobutyrate Butyl ester, methyl isobutyrate, ethyl octoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxypropionate Chain or cyclic esters such as methyl ester, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as chlorobutane and chloropentane; ether ketones such as methoxymethylpentanone Types; nitriles such as acetonitrile and benzonitrile.

Examples of commercially available solvents that meet the above requirements include mineral spirit, Varsol # 2, Apco # 18 Solvent, Apco thinner, Socal Solvent No. 1 and No. 2, Solvesso # 150, Shell TS28 Solvent, Carbitol, ethyl carbitol, butyl carbitol, methylcellulose, ethylcellulose, ethylcellulose acetate, methylcellulose acetate, diethylene glycol Diglyme (both trade names) and the like. These solvents may be used individually by 1 type, and may use 2 or more types together.

＜ Case of forming pixels of color filter by photolithography method ＞

In the case of forming a pixel of a color filter by the photolithography method, it is preferable to select a range of a boiling point of 100 to 200 ° C. (at a pressure of 1013.25 [hPa] as the solvent. Hereinafter, the boiling points are all the same.). By. More preferably, it has a boiling point of 120 to 170 ° C.

In terms of good balance between coatability and surface tension, and relatively high solubility of constituent components in the composition, among the above solvents, glycol alkyl ether acetates are preferred.

The glycol alkyl ether acetates may be used alone or in combination with other solvents. As the solvent used in combination, ethylene glycol monoalkyl ethers are particularly preferred. Among these, propylene glycol monomethyl ether is preferred in terms of the solubility of the constituents in the composition. In addition, ethylene glycol monoalkyl ethers have high polarity. If the amount is too large, the pigment tends to agglomerate and the viscosity of the subsequent colored composition tends to decrease, such as storage stability. Therefore, ethylene glycol in the solvent The proportion of the monoalkyl ethers is preferably 5 to 30% by weight, and more preferably 5 to 20% by weight.

It is also preferable to use a solvent having a boiling point of 150 ° C or higher in combination. By The use of such a high-boiling-point solvent makes it difficult to dry the coloring composition, and has the effect that it is difficult to cause defects in the correlation of the pigment dispersion due to rapid drying. The content of the high boiling point solvent is preferably 3% to 50% by weight, more preferably 5% to 40% by weight, and particularly preferably 5% to 30% by weight relative to the solvent. If the amount of the high-boiling-point solvent is too small, precipitation of color material components, etc. may occur at the tip of the slit nozzle, for example. Foreign matter defects caused by curing, and if too much, the drying speed of the composition will be slowed down, which may cause poor tack or pre-baked needles in the reduced-pressure drying process in the color filter manufacturing step described later. Trace problem.

In addition, the solvent having a boiling point of 150 ° C or higher may be a glycol alkyl ether acetate or a glycol alkyl ether. In this case, a solvent having a boiling point of 150 ° C or higher may not be included. .

<Case of forming a color filter by an inkjet method>

In the case of forming a pixel of a color filter by an inkjet method, as a solvent, a boiling point that is usually 130 ° C or higher and 300 ° C or lower, and preferably 150 ° C or higher and 280 ° C or lower is more suitable. If the boiling point is too low, the uniformity of the obtained coating film tends to deteriorate. Conversely, if the boiling point is too high, as described below, the drying inhibition effect of the curable resin composition is high. Many solvents remain in the coating film even after thermal firing, which may cause quality problems or due to vacuum. The drying time such as drying becomes longer, which causes problems such as an increase in viscosity time.

From the viewpoint of the uniformity of the obtained coating film, a solvent having a vapor pressure of usually 10 mmHg or less, preferably 5 mmHg or less, and more preferably 1 mmHg or less can be used.

Furthermore, in the manufacture of color filters using the inkjet method, the ink discharged from the nozzle is very fine to several tens of pL. Therefore, before the ink is ejected to the periphery of the nozzle opening or into the pixel bank , The solvent evaporates and the ink is concentrated. Tendency to dry. In order to avoid this phenomenon, it is preferable that the boiling point of the solvent is high, and specifically, it is preferable to contain a solvent having a boiling point of 180 ° C or higher. More preferably, it contains a solvent having a boiling point of 200 ° C or higher, and particularly preferably contains a solvent having a boiling point of 220 ° C or higher. The high-boiling point solvent having a boiling point of 180 ° C or higher is preferably 50% by weight or more, and more preferably 70% by weight, based on the total solvent contained in the pigment dispersion liquid and / or the coloring composition for a color filter. Above, preferably 90% by weight or more. In the case where the content of the high-boiling-point solvent is less than 50% by weight, the effect of preventing the solvent from evaporating from the liquid droplet may not be sufficiently exerted.

Examples of preferred high-boiling solvents include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, and 3-butanediol diacetate, 1,6-hexanediol diacetate, glycerol triacetate, and the like.

Furthermore, in order to adjust the viscosity or the solubility of the solid content of the pigment dispersion liquid or the coloring composition, it is effective to partially contain a solvent having a boiling point lower than 180 ° C. As such a solvent, solvents having low viscosity, high solubility, and low surface tension are preferred, and ethers, esters, or ketones are preferred. Among them, particularly preferred are cyclohexanone, dipropylene glycol dimethyl ether, cyclohexanol acetate, and the like.

On the other hand, if the solvent contains alcohols, the discharge stability in the inkjet method may be deteriorated. Therefore, the content of the alcohol in the total solvent is preferably 20% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight. the following.

＜ Solvent content ＞

The content of the solvent in the coloring composition of the present invention is not particularly limited, and the upper limit is usually 99% by weight or less. When the solvent content exceeds 99% by weight, pigments, dispersants, and the like become too small, which is not suitable for forming a coating film. On the other hand, considering the viscosity and the like suitable for coating, the lower limit of the solvent content is usually 75% by weight or more, preferably 80% by weight or more, and more preferably 82% by weight or more.

[1-3] Dispersant:

The dispersant used in the present invention contains a block copolymer composed of an A-block having a lipophilic property and a B-block having a functional group containing a nitrogen atom, and the amine value thereof is 80 mgKOH in terms of effective solid content. / g to 150 mgKOH / g.

The block copolymer is preferably a (meth) acrylic block copolymer. Hereinafter, the dispersant of the present invention will be centered on the case where the block copolymer is a (meth) acrylic block copolymer. Explain.

The B block system has a nitrogen atom-containing functional group. As the functional group, a primary to tertiary amine group is preferred. The content ratio of the primary to tertiary amine groups is preferably 20 mol% or more, and more preferably 50 mol% or more, of the entire nitrogen atom-containing functional group. Among the tertiary amino groups, tertiary amino groups are particularly preferred. As the tertiary amine group, particularly preferred is -NR ⁴¹ R ⁴² (wherein R ⁴¹ and R ⁴² each independently represent a cyclic or chain alkyl group which may have a substituent, an aryl group which may have a substituent, Alternatively, the group represented by an aralkyl group which may have a substituent.) The partial structure (repeating unit) containing the tertiary amine group is preferably, for example, represented by the following formula.

(Wherein R ⁴¹ and R ⁴² have the same meanings as R ⁴¹ and R ⁴² described above, R ⁴³ represents an alkylene group having 1 or more carbon atoms, and R ⁴⁴ represents a hydrogen atom or a methyl group.)

Among them, R ⁴¹ and R ^{42 are} preferably methyl, R ^{43 is} preferably methylene and ethylene, and R ^{44 is} preferably a hydrogen atom or a methyl group. As such a partial structure, a structure derived from dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate represented by the following formula is particularly suitably used.

(In the formula, R ⁴⁴ has the same meaning as above.)

One B block may contain two or more types of amine group-containing partial structures as described above. In this case, the B block may be in any form of random copolymerization or block copolymerization, and may contain two or more kinds of amine group-containing partial structures. Again, B The block may partially contain a partial structure not containing an amine group. Examples of such a partial structure include a partial structure derived from a (meth) acrylate-based monomer. The content of the amine group-free partial structure in the B block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight, but the best B block does not contain the amine group-free Partial structure.

On the other hand, if the oleophilic A block of the block copolymer constituting the dispersant does not contain the nitrogen atom-containing functional group such as the amine group, it can be copolymerized with the monomer constituting the B block. There are no particular restrictions on the composition of the monomers.

Examples of the oleophilic A block include styrene-based monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) Propyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, propylene oxide (meth) acrylate Esters, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethacrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, etc. ) Acrylic acid ester monomers; (meth) acrylic acid chloride monomers such as (meth) acrylic acid chloride; vinyl acetate monomers; allyl glycidyl ether, butylene glycidyl ether, etc. A polymer structure obtained by copolymerizing a comonomer such as a glycidyl ether-based monomer.

Among them, as the A block, it is preferable to contain a polyalkylene glycol (meth) acrylate such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and the like as a copolymerization component (that is, a polymer derived from It is particularly preferred that the polyalkylene glycol (meth) acrylate has a portion represented by the following formula (IV). Structure of the A block.

(In the formula, n represents an integer of 1 to 5, and R ⁵⁰ represents a hydrogen atom or a methyl group.)

It is particularly preferred that the A block contains 5 to 40 mol% of a partial structure represented by the above formula (IV).

Although the detailed mechanism of action is unknown, it is generally believed that the mechanism of action is that by having a partial structure derived from a polyalkylene glycol (meth) acrylate, particularly a partial structure represented by the above formula, the dispersant molecule can be improved. Hydrogen bonding, which enhances the affinity with the dispersion solvent, and increases the stability of the dispersion.

The dispersant used in the present invention contains a copolymer composed of such A block and B block, and preferably contains an AB block or ABA block copolymer. Among these, an AB block copolymer is preferable. Such a block copolymer can be prepared by the living polymerization method shown below, for example.

The living polymerization method includes anionic living polymerization method, cationic living polymerization method, and radical living polymerization method. The polymerization active species of the anion living polymerization method are anions, and are shown in the following scheme, for example.

[Chemical 10]

The polymerization active species of the radical living polymerization method (nitroxyl method, ATRP method (Atom Transfer Radical Polymerization)) is a radical, as shown in the following scheme, for example.

When synthesizing such a (meth) acrylic block copolymer, Japanese Patent Laid-Open No. 60-89452; Japanese Patent Laid-Open No. 9-62002; P. Lutz, P. Masson et al, Polym. Bull can be used. 12, 79 (1984); BC Anderson, GD Andrews et al, Macromolecules, 14, 1601 (1981); K. Hatada, K. Ute, et alwPolym. J. 17, 977 (1985); K. Hatada, K Ute, et al, Polym. J. 18, 1037 (1986); Right-hand Koichi, Puta Kenichi, Polymer Processing, 36, 366 (1987); Tomura Toshiyuki, Enomoto Masao, Polymer Papers, 46, 189 ( 1989); M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987); Takuza Aida, Inoue Inoue, Organic Synthetic Chemistry, 43, 300 (1985); DY Sogoh, WR Hertler et al , Macromolecules, 20, 1473 (1987); K. Matyaszewski et al, Chem. Rev. 2001, 101, 2921-2990, and other known methods.

The amine value in 1 g of the solid content of the dispersant containing the above-mentioned block copolymer of the present invention is 80 mgKOH / g or more and 150 mgKOH / g or less in terms of effective solid content conversion, preferably 90 to 150 mgKOH / g, more It is preferably 100 ~ 140 mgKOH / g.

If the amine value is too low, the adsorption force of the dispersant molecules on the pigment surface becomes insufficient, and sufficient dispersion stability cannot be obtained. On the other hand, when the amine value is too high, the molecular weight of the A block is relatively small, and the dispersion stability becomes insufficient. In other words, in order to exhibit the best dispersibility, the amine value is set to the above range.

The amine value (effective solid content conversion) of the dispersant is expressed by the weight of KOH equivalent to the amount of alkali per 1 g of the solid content of the solvent in the dispersant sample, and is measured by the following method. In a 100 mL beaker, accurately weigh 0.5 to 1.5 g of the dispersant sample and dissolve it with 50 mL of acetic acid. Using an automatic titration device with a pH electrode, this solution was neutralized and titrated with a 0.1 mol / L HClO ₄ acetic acid solution. The inflection point of the titration pH curve was used as the end point of the titration, and the amine value was calculated according to the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S) (where, W is the dispersant sample weighing amount [g], V is the titration end point of the titration [mL], S is the dispersant sample Solid content concentration [wt%].)

In addition, the acid value of the block copolymer also depends on the existence and type of the acidic group that is the basis of the acid value. Generally, a low acid value is preferred, and it is usually 50. mgKOH / g or less, preferably 40 mgKOH / g or less, and more preferably 30 mgKOH / g or less.

In the present invention, a commercially available (meth) acrylic block copolymer having the same structure as the aforementioned compound can also be applied.

In the pigment dispersion liquid of the present invention, it is necessary to use a dispersant containing the above-mentioned copolymer composed of A blocks and B blocks. By using such a block copolymer as a dispersant, it is possible to satisfy both the strong adsorption of the pigment surface and the higher solvent affinity, and therefore, higher dispersion stability can be achieved. In addition, by increasing the amine value of the dispersant, especially the adsorption force on the surface of the acid-treated pigment increases, so that the dispersion stability can be further improved.

Particularly preferably, 20 mol% or more of the repeating unit having a functional group containing a nitrogen atom in the B block is a repeating unit having a primary to tertiary amine group. When the amount of the amine group is less than 20 mol%, even if the amine value is 80 mgKOH / g or more, sufficient adsorption force cannot be obtained, and high dispersion stability cannot be obtained in some cases.

Furthermore, when the average primary particle diameter of the pigment is small, the specific surface area is increased, so the amount of dispersant adsorbed per unit surface area of the pigment becomes smaller. In this case, the dispersant containing the above-mentioned block copolymer exhibits a significant difference in effect compared with dispersants of other structures, and is therefore particularly suitable for use. The amount of the dispersant used in the present invention is preferably about 5 to 200% by weight, and more preferably about 10 to 100% by weight, relative to the total amount of the pigment in the pigment dispersion or the coloring composition.

The pigment dispersion liquid and the coloring composition of the present invention may contain a dispersant other than the above-mentioned block copolymer, as long as the effect of the present invention is not impaired. Examples of such a dispersant include: Japanese Patent Laid-Open No. 2006-343648 Various dispersants and the like described in the publication.

[1-4] Dispersion aid

The pigment dispersion liquid and the coloring composition of the present invention may also contain a dispersing auxiliary agent for improving the dispersibility of the pigment and improving the dispersion stability. Examples of the dispersion aid include pigment derivatives.

Examples of the pigment derivative include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, and Derivatives, such as anthraquinone-based, indanthrene-based, perylene-based, perinone-based, diketopyrrolopyrrole-based pigments, and the like.

Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamido group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, Hydrazone and the like. These substituents may be directly bonded to the pigment skeleton, or may be bonded through an alkyl group, an aryl group, a heterocyclic group, and the like. Among the above-mentioned substituents, a sulfonamido group, a quaternary salt thereof, and a sulfonic acid group are preferable, and a sulfonic acid group is more preferable.

The substituents may be substituted multiple times on one pigment skeleton, or may be a mixture of compounds having different substitution numbers.

Specific examples of the pigment derivative include a sulfonic acid derivative of an azo pigment, a sulfonic acid derivative of a phthalocyanine pigment, a sulfonic acid derivative of a quinophthalone pigment, and a sulfonic acid of an anthraquinone pigment. Derivatives, sulfonic acid derivatives of quinacridone pigments, sulfonic acid derivatives of diketopyrrolopyrrole pigments, Sulfonic acid derivatives of pigments. Among them, sulfonic acid derivatives of pigment yellow 138, sulfonic acid derivatives of pigment yellow 139, sulfonic acid derivatives of pigment red 254, sulfonic acid derivatives of pigment red 255, and sulfonic acid of pigment red 264 are preferable. Acid derivatives, sulfonic acid derivatives of pigment red 272, sulfonic acid derivatives of pigment red 209, sulfonic acid derivatives of pigment orange 71, sulfonic acid derivatives of pigment violet 23.

In addition, the dispersing assistant may be a compound having a similar chemical structure even if it is not a derivative of the pigment itself mentioned above.

The addition amount of the dispersing aid is usually 0.1% by weight or more relative to the pigment, and usually 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less. . The reason for this is that if the added amount is small, the effect tends to be difficult to exhibit. On the other hand, if the added amount is too large, the dispersibility and dispersion stability tend to deteriorate.

[1-5] dispersion resin

The pigment dispersion liquid of the present invention may contain part or all of a resin selected from the binder resins described later. Specifically, in the dispersion treatment step in the preparation of the pigment dispersion liquid described below, since the binder resin is contained together with the dispersant, the binder resin exhibits a multiplicative effect with the dispersant, thereby contributing to the dispersion stability of the pigment. Sex. As a result, it is possible to reduce the amount of the dispersant added, which is preferable. In addition, it is also preferable to exhibit the effects of improving the developability, leaving no dissolved matter in the non-pixel portion of the substrate, and improving the adhesion of the pixel to the substrate.

The binder resin thus used in the dispersion treatment step is referred to as a dispersion resin.

Relative to the total amount of the pigment in the pigment dispersion, the amount of the dispersing resin used is preferably about 5 to 200% by weight, and more preferably about 10 to 100% by weight.

As the dispersing resin, various binder resins described below can be used. [2-1-2] (meth) acrylic resin described later.

The acid value of the dispersion resin is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, most preferably 50 mgKOH / g or more, and still more preferably 500 mgKOH / g or less, and more preferably 300 mgKOH / g. g or less, preferably 200 mgKOH / g or less. If the acid value is too high, it will have a high viscosity, which tends to be difficult to synthesize or handle, and if the acid value is too low, it may be difficult to apply to alkaline development.

In addition, the weight average molecular weight of polystyrene conversion measured by the GPC method of the dispersing resin is preferably 1,000 or more, more preferably 1,500 or more, most preferably 2,000 or more, and still more preferably 200,000 or less, more preferably Below 50,000, preferably below 30,000. If the molecular weight is too large, it tends to be difficult to apply to alkaline development, and if the molecular weight is too small, dispersion stability may decrease.

[1-6] Aromatic carboxylic acid compounds

At least one of the pigment dispersion liquid and the coloring composition of the present invention preferably contains an aromatic carboxylic acid-based compound.

The dispersant containing the above-mentioned block copolymer used in the present invention can disperse the micronized pigment with high efficiency, so it is preferable. However, the pigment dispersion liquid and the coloring composition for color filters are used for Sexual viscosity tends to increase. In addition, a pixel formed using the coloring composition tends to have defects.

Therefore, by containing at least one of the pigment dispersion liquid and the coloring composition of the present invention with an aromatic carboxylic acid-based compound, the increase in viscosity over time can be suppressed, and the defects of the obtained pixels can be prevented. .

In addition, by incorporating the aromatic carboxylic acid compound when preparing a pigment dispersion liquid, the increase in viscosity of the pigment dispersion liquid itself over time can be suppressed, and the coloring composition for a color filter prepared by using the pigment dispersion liquid can be suppressed. The viscosity of the material increases over time. In addition, when various components are added to the pigment dispersion to prepare a coloring composition for a color filter, the coloring composition for a color filter is contained as one of the components to be added later, so that the time-lapse of the coloring composition for a color filter can be suppressed. Increased viscosity. Furthermore, when a component constituting a coloring composition for a color filter is prepared all at once or sequentially without preparing a pigment dispersion liquid, thereby preparing the coloring composition, as one of the constituents, it may be any one of the constituents. Timing for deployment.

Hereinafter, the aromatic carboxylic acid-based compound will be described.

As an aromatic carboxylic acid type compound, if it has an aromatic group and a carboxyl group, it may have an arbitrary structure. Examples of the aromatic group include a phenyl group and a naphthyl group. Of these, particularly preferred is phenyl.

These aromatic groups may have a substituent, and the type or number of the substituents is not particularly limited. Specifically, for example, a substituent represented by X ^{3 in} the general formula (VI) described below is preferred. The number of carboxyl groups may be one or plural, for example, two to three, but in terms of the effect of the compound described above, it is preferably one in one molecule.

The molecular weight of the aromatic carboxylic acid-based compound is usually 500 or less, preferably 350 or less, and usually 150 or more. By setting the molecular weight to 500 or less, as described later, the compound is easily accessible to the pigment, and the effect of suppressing an increase in viscosity can be reliably exhibited.

The aromatic carboxylic acid compound is particularly preferably represented by the following general formula (VI). Shown compounds

(In the above general formula (VI), Z ¹ represents a methylene group or -O-, and m represents an integer of 0 to 3. However, when m is 2 or 3, m Z ¹ may be the same or different.

X ³ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, benzyl, phenethyl, benzyloxy, or -COOX ⁴ (wherein X ⁴ represents an alkyl group or a phenyl group having 1 to 7 carbon atoms), each of these groups may have a substituent. ).

X ³ in the general formula (VI) represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, benzyl group, and phenethyl Group, benzyloxy group, or -COOX ⁴ (wherein X ⁴ represents an alkyl group or a phenyl group having 1 to 7 carbon atoms).

Hereinafter, specific examples of the alkyl group having 1 to 4 carbon atoms, the alkenyl group having 2 to 5 carbon atoms, and the alkoxy group having 1 to 4 carbon atoms in the definition of X ^{3 will} be described.

Examples of the alkyl group having 1 to 4 carbon atoms include alkyl groups having 4 or less carbon atoms such as methyl, ethyl, n-propyl, and isopropyl.

Alkenyl groups having 2 to 5 carbon atoms, for example: vinyl groups such as vinyl, allyl, 1-propenyl, 2-butenyl, 1,3-butadienyl and other alkenyl groups having 2 to 5 carbon atoms.

1 to 4 carbon alkoxy groups, such as: methoxy, ethoxy, propoxy An alkoxy group having a carbon number of about 4 or less such as an isopropyl group and an isopropoxy group.

Further, in the definition of the X ^3, COOX ⁴ in the X ⁴ is an alkyl group having 1 to 7 carbon atoms or the phenyl group. Examples of the alkyl group having 1 to 7 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, n-pentyl, iso Amyl, neopentyl, third pentyl, n-hexyl, isohexyl, 5-methylhexyl and the like.

Each of these groups may have a substituent. Specific examples of the substituent include the following groups.

Hydroxyl Lower alkyl; for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, n-pentyl, isopentyl, neopentyl, third pentyl Alkyl groups having 7 or less carbon atoms, such as alkyl, n-hexyl, isohexyl, and 5-methylhexyl.

Lower alkoxy; for example: such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, second butoxy, third butoxy, n-hexyloxy, isohexyloxy Alkoxy groups having a carbon number of 7 or less such as 5-methylhexyloxy.

Lower alkenylcarbonyloxy groups; for example, alkenylcarbonyloxy groups having 3 or less carbon atoms in alkenyl moieties such as propenyloxy and butenyloxy.

Phenyl; benzyl; phenoxy; benzyloxy.

Further, in the compound represented by the general formula (VI), in terms of the above-mentioned effects of the compound being more significant, the substituent X ^{3 is} preferably one having 1 to 4 carbon atoms which may have a substituent. An alkyl group, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and a group selected from -COOX ⁴ . More specific examples of the substituent X ³ include benzyloxycarbonyl, methoxycarbonyl, vinylcarbonyloxy and ethyloxycarbonyl, isopropyl, third butyl, methylol, and vinyl. Wait.

Furthermore, the position of the substituent X ³ is not particularly limited if it is within a possible range, and is preferably ortho or para with respect to the-(Z ¹ ) _m -COOH group on the benzene ring, and particularly preferably only Ortho.

Among the substituents X ³ , those which are not specifically described above may be arbitrarily combined with the listed ones, or may be selected based on commonly known common sense.

The compound represented by the general formula (VI) is particularly preferably a phthalic acid monoester compound. Specifically, for example, the following are mentioned, but they are not limited to these.

[Chemical 14]

The aromatic carboxylic acid compound, more specifically, the aromatic carboxylic acid compound represented by the general formula (VI) can be easily obtained by purchasing a commercially available product or synthesizing it by a known method.

The content of the aromatic carboxylic acid compound in the pigment dispersion liquid or the coloring composition of the present invention is not particularly limited as long as it does not impair the effect of the coloring composition, but it is relative to the coloring composition finally prepared. The total solid content of the material is usually 20% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, and usually 0.1% by weight or more.

By containing an aromatic carboxylic acid compound within this range, it is possible to prevent the viscosity of the pigment dispersion liquid or the coloring composition from increasing, and to form a "defect". Fewer pixels and excellent linearity.

Although not limited to any theory and its details are unknown, the reason for containing an aromatic carboxylic acid-based compound to prevent an increase in viscosity is presumed as follows. That is, the block copolymer used as the dispersant in the present invention contains many nitrogen atom-containing functional groups such as amine groups. In a certain composition, the amine groups and the like of the dispersant may react with other components to increase viscosity. .

Here, the pigment is usually present as fine particles, and the dispersant is adsorbed on the pigment particles to exert the dispersing ability. The pigment is usually a compound having an aromatic group and has an affinity with other aromatic groups.

It is generally believed that due to the aromatic group affinity of the aromatic carboxylic acid compound of the present invention, if the compound is close to the pigment particles, the carboxyl group is also necessarily close to the pigment, and may interact with the dispersant adsorbed on the pigment. It is generally considered that the viscosity of the amine group of the dispersant is inhibited from increasing due to the interaction between the carboxyl group of the aromatic carboxylic acid compound on the pigment surface and the amine group of the dispersant. Furthermore, it is generally considered that it is difficult for a polymer compound to approach a pigment particle system, and in order to make it easy, a molecular weight of 500 or less is effective.

[2] Coloring composition

The coloring composition of this invention contains at least the said pigment, a solvent, a dispersing agent, and the binder resin mentioned later as a component which comprises a pigment dispersion liquid. In addition, the coloring composition of the present invention can be prepared by mixing other ingredients in a pigment dispersion liquid prepared in advance, and all of the ingredients can be mixed simultaneously or sequentially.

As ingredients other than these essential ingredients, In addition to the various components described, those which can also be used as a color filter forming material can be used without particular limitation.

[2-1] Adhesive resin

The binder resin used in the present invention can be used without particular limitation as long as it can be used for a color filter.

Examples include a thermosetting resin composition used in a so-called lift-off color filter manufacturing process described in Japanese Patent Laid-Open No. 60-184202, and Japanese Patent Laid-Open No. 2004 A thermosetting resin composition, a photopolymerizable resin composition described later, and the like used in the process of producing an inkjet-type color filter described in JP-220036 and the like. Depending on which method is used to harden the coloring composition to produce a color filter, an appropriate type of resin composition may be selected. When a coloring composition is a photopolymerizable composition, it is preferable to contain a photopolymerization starter component mentioned later.

Hereinafter, a case where the colored composition of the present invention is a photopolymerizable resin composition will be described in detail as an example, but the present invention is not limited thereto.

When the colored composition of the present invention is a photopolymerizable resin composition, as the binder resin, for example, Japanese Patent Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 10-300922, Known polymer compounds described in various publications such as Japanese Patent Application Laid-Open No. 11-140144, Japanese Patent Application Laid-Open No. 11-174224, Japanese Patent Application Laid-Open No. 2000-56118, Japanese Patent Application Laid-Open No. 2003-233179, Japanese Patent Application Laid-Open No. 2007-270147, and the like are preferred. Examples include: [2-1-1]: For epoxy-containing (meth) acrylates and other A copolymer of a base polymerizable monomer, a resin obtained by adding an unsaturated monobasic acid to at least a part of an epoxy group of the copolymer, or at least a part of a hydroxyl group generated by the addition reaction Alkali-soluble resins obtained by adding a polybasic acid anhydride, [2-1-2] (meth) acrylic resins, and the like.

Each of these resins will be described below.

[2-1-1] For copolymers of (meth) acrylates containing epoxy groups and other radical polymerizable monomers, at least a part of the epoxy groups contained in the copolymer is unsaturated. Monobasic acid resin, or alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups generated by the addition reaction

In the present invention, as one of the particularly preferable binder resins, "a copolymer of a (meth) acrylate containing an epoxy group and other radical polymerizable monomers is included in the copolymer. A resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy group, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction "(hereinafter, Called "[2-1-1] resin"). More specifically, "a copolymer of 5 to 90 mol% of an epoxy-containing (meth) acrylate and 10 to 95 mol% of other radical polymerizable monomers, 10-100 mol% of epoxy group is added with unsaturated monobasic acid, or 10-100 mol% of hydroxyl group produced by the addition reaction is added with polybasic acid anhydride. The obtained alkali-soluble resin. "

A coloring composition for a color filter containing a micronized pigment, particularly a micronized zinc bromide phthalocyanine pigment, having poor solubility in a developing solution There is a tendency that, in practice, it may be difficult to produce a color filter by applying, drying, exposing, and developing the composition.

In general, even if, for example, the viscosity stability of a pigment dispersion is low and the viscosity is increased with time, if a binder resin or a solvent is added to the pigment dispersion to prepare a coloring composition for a color filter, it is often the case. The composition has a reduced viscosity and improves viscosity stability. However, it is known that when a pigment dispersion liquid containing a zinc bromide phthalocyanine pigment is used as a coloring composition for a color filter, the viscosity tends to increase rapidly, and it is difficult to ensure viscosity stability. Furthermore, the colored composition for a color filter tends to have the following tendency during storage: Foreign matter is easily generated over time. Increasing the contrast also decreases with time.

In order to solve such a problem, and to achieve a coloring composition for a pigment dispersion liquid or a color filter containing a micronized pigment, particularly a micronized zinc bromide phthalocyanine pigment: ‧ Raising a pigment dispersion or a color filter The viscosity stability of the coloring composition for light film, ‧ improves the solubility of the coloring composition in the developing solution, and suppresses the decrease in contrast or the generation of foreign matter over time, thereby ‧ preventing the defects of the obtained pixels and improving the linearity, etc. The [2-1-1] resin described below is used.

Examples of the "epoxy-containing (meth) acrylate" constituting the [2-1-1] resin include propylene oxide (meth) acrylate and 3, 4-epoxy (meth) acrylate. Butyl ester, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like. Of which Glycidyl (meth) acrylate is preferred.

These (meth) acrylates containing an epoxy group may be used individually by 1 type, and may use 2 or more types together.

As the other radical polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate, a mono (meth) acrylate having a structure represented by the following general formula (1) is preferable.

In the general formula (1), R ³¹ to R ³⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, but R ³⁷ and R ³⁸ may be connected to each other to form a ring.

In the general formula (1), the ring formed by connecting R ³⁷ and R ³⁸ is preferably an aliphatic ring, which may be saturated or unsaturated, and the number of carbons is preferably 5 to 6.

Among them, the structure represented by the general formula (1) is preferably a structure represented by the following formula (1a), (1b), or (1c).

When such a structure is introduced into a binder resin and the colored composition of the present invention is used in a color filter or a liquid crystal display element, the heat resistance of the colored composition can be improved, or the colored composition can be used more. The intensity of the pixels formed by the coloring composition.

The mono (meth) acrylate having a structure represented by the general formula (1) may be used alone or in combination of two or more.

As the mono (meth) acrylate having a structure represented by the general formula (1), various known ones can be used as long as the mono (meth) acrylate has the structure, but it is particularly preferably represented by the following general formula (2).

In formula (2), R ³⁹ represents a hydrogen atom or a methyl group, and R ⁴⁰ represents a structure represented by the general formula (1).

In the copolymer of the epoxy-containing (meth) acrylate and other radical polymerizable monomers, the repeating unit derived from a mono (meth) acrylate having a structure represented by the general formula (1) From "Other Freedom The content of the repeating unit of the "based polymerizable monomer" is preferably 5 to 90 mole%, more preferably 10 to 70 mole%, and particularly preferably 15 to 50 mole%.

The "other radically polymerizable monomer" other than the mono (meth) acrylate having a structure represented by the general formula (1) is not particularly limited. Specifically, for example, styrene, and derivatives of α, ortho, meta, or para positions of styrene substituted with alkyl, nitro, cyano, amido, and ester groups And other vinyl aromatics; butadiene, 2, 3-dimethylbutadiene, isoprene, chloroprene and other diene; methyl (meth) acrylate, ethyl (meth) acrylate Ester, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, ( Amyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) Lauryl acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, (methyl Dicyclohexyl acrylate, (meth) acrylic acid Ester, adamantane (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracene (meth) acrylate, o- (meth) acrylate Aminobenzyl, piperonyl (meth) acrylate, o-hydroxybenzyl (meth) acrylate, furan (meth) acrylate, methyl furan (meth) acrylate, tetrahydrofuran (meth) acrylate, (formyl) ) Pyranyl acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, toluene (meth) acrylate, -1, 1, 1-trifluoroethyl (meth) acrylate, ( Perfluoroethyl (meth) acrylate, Perfluoron-propyl (meth) acrylate, Perfluoroisopropyl (meth) acrylate, Triphenylmethyl (meth) acrylate, Cumene (meth) acrylate Ester, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. (methyl ) Acrylic esters; (meth) acrylamide, (meth) acrylic acid-N, N-dimethylammoniumamine, (meth) acrylic acid-N, N-diethylammoniumamine, (meth) acrylic acid -N, N-dipropylamidamine, (meth) acrylic acid -N, N-diisopropylamidamine, ( (Meth) acrylamide, such as anthracene methacrylate; aniline (meth) acryl, methacrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride , N-vinylpyrrolidone, vinylpyridine, vinyl acetate and other vinyl compounds; diethyl citrate, diethyl maleate, diethyl fumarate, diethyl itaconic acid, etc. Carboxylic diesters; N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide And other monomaleimide imines; N- (meth) acrylfluorenylphthalimide and the like.

In order to impart excellent heat resistance and strength to the colored composition, it is more effective to use styrene, benzyl (meth) acrylate, and monomaleic acid among these "other radically polymerizable monomers". At least one selected from imines. In particular, among the repeating units derived from "other radically polymerizable monomers", those derived from at least one repeating unit selected from the group consisting of styrene, benzyl (meth) acrylate, and monomaleimide. The content ratio is preferably 1 to 70 mole%, and more preferably 3 to 50 mole%.

In the copolymerization reaction of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer, a known solution polymerization method can be applied. The solvent used is not particularly if it is inert to free radical polymerization By definition, an organic solvent generally used can be used.

Examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellulose acetate, and butylcellulose acetate; diethylene glycol monoalkyl ether; Diethylene glycol monoalkyl ether acetates such as methyl ether acetate, carbitol acetate, and butyl carbitol acetate; propylene glycol monoalkyl ether acetates; dipropylene glycol monoalkyl ether acetate Acetates such as esters; ethylene glycol dialkyl ethers; methyl carbitol, ethyl carbitol, butyl carbitol and other diethylene glycol dialkyl ethers; triethylene glycol dioxane Ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; 1, 4-di Ethers such as alkane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; hydrocarbons such as benzene, toluene, xylene, octane, decane; petroleum ether, petroleum brain , Hydrogenated petroleum naphtha, solvent petroleum naphtha and other petroleum-based solvents; lactates such as methyl lactate, ethyl lactate, butyl lactate; dimethylformamide, N-methylpyrrolidone and the like. These solvents may be used alone or in combination of two or more.

Relative to 100 parts by weight of the copolymer obtained, the usage amount of these solvents is usually 30 to 1,000 parts by weight, preferably 50 to 800 parts by weight. If the amount of the solvent used is outside this range, it is difficult to control the molecular weight of the copolymer.

In addition, the radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and an organic peroxide catalyst or an azo compound catalyst that is generally used can be used. Examples of the organic peroxide catalyst include ketone peroxides, ketal peroxides, hydrogen peroxide, diallyl peroxide, diethylammonium peroxide, peroxyesters, and peroxides. Dicarbonate.

Specific examples thereof include benzamidine peroxide and diisopropyl peroxide. Benzene, diisopropyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-hexyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, peroxy Tert-hexyl 2-ethylhexanoate, 1, 1-bis (third butylperoxy) -3, 3, 5-trimethylcyclohexane, 2, 5-dimethyl-2, 5 -Bis (third butylperoxy) hexyl-3,3-isopropyl hydroperoxide, third butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, peroxide Acetamidine, bis (4-tert-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, 3, 3, 5-trimethylhexanonium peroxide, Lauryl oxide, 1, 1-bis (third butylperoxy) 3, 3, 5-trimethylcyclohexane, 1, 1-bis (third hexyl peroxy) 3, 3, 5- Trimethylcyclohexane and the like.

Examples of the azo compound catalyst include azobisisobutyronitrile, azobiscarbonamide, and the like.

Among these, one or two or more kinds of radical polymerization initiators having an appropriate half-life can be used depending on the polymerization temperature. The amount of the radical polymerization initiator used is 0.5 to 20 parts by weight, and preferably 1 to 10 parts by weight, with respect to 100 parts by weight of the total of the monomers used in the copolymerization reaction.

The copolymerization reaction can be carried out by dissolving the monomers used in the copolymerization reaction and the radical polymerization initiator in a solvent and heating the mixture while stirring; the monomer added with the radical polymerization initiator can also be added dropwise. It is carried out by heating and stirring the solvent. Alternatively, a radical polymerization initiator may be added to the solvent, and the monomer may be added dropwise during the temperature rise. The reaction conditions can be freely changed according to the target molecular weight.

In the present invention, as the copolymer of the epoxy-containing (meth) acrylate and the other radical polymerizable monomer, it is preferred that The repeating unit of epoxy (meth) acrylate is 5 to 90 mole%, and the repeating unit from other radical polymerizable monomers is 10 to 95 mole%; more preferably, the former is 20 to 80 Mohr% and the latter 80 to 20 Mohr%; particularly good is the former 30 to 70 Mohr% and the latter 70 to 30 Mohr%.

If the (meth) acrylate containing an epoxy group is too small, the addition amount of the polymerizable component and the alkali-soluble component described later may be insufficient; on the other hand, if the (meth) acrylate containing an epoxy group is too much When there are too few other radical polymerizable monomers, the heat resistance or strength may be insufficient.

Then, an unsaturated monobasic acid (polymerizable component), a polybasic acid anhydride (alkali-soluble component), and an epoxy group portion of a copolymer of an epoxy-containing (meth) acrylate and another radical polymerizable monomer are reacted. .

As the "unsaturated monobasic acid" added to the epoxy group, a known one can be used, and examples thereof include an unsaturated carboxylic acid having an ethylenically unsaturated double bond.

Specific examples include (meth) acrylic acid, butenoic acid, o-, m-, or p-vinylbenzoic acid, an alkyl group halogenated at the α-position, an alkoxy group, a halogen atom, a nitro group, or a cyano group. Substituted monocarboxylic acids such as (meth) acrylic acid. Among these, (meth) acrylic acid is preferred. One of these may be used alone, or two or more of them may be used in combination.

By adding such a component, polymerizability can be imparted to the binder resin used in the present invention.

The unsaturated monobasic acids are usually added to 10 to 100 mole% of the epoxy group of the copolymer, preferably 30 to 100 mole%, and more preferably 50 to 100 mole%. If the addition ratio of unsaturated monobasic acid is too small, then The residual epoxy groups in the heart adversely affect the stability of the colored composition over time. As a method for adding an unsaturated monobasic acid to the epoxy group of the copolymer, a known method can be adopted.

Further, as the "polyacid anhydride", which is added to a hydroxyl group generated when an unsaturated monobasic acid is added to an epoxy group of a copolymer, a known one can be used.

Examples include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chloric anhydride; trimellitic anhydride, trimesene Tetracarboxylic anhydride, diphenyl ketone tetracarboxylic anhydride, biphenyltetracarboxylic anhydride, etc. Among them, tetrahydrophthalic anhydride and succinic anhydride are preferred. These polybasic acid anhydrides may be used singly or in combination of two or more kinds.

By adding such a component, it is possible to impart alkali solubility to the binder resin used in the present invention.

These polybasic acid anhydrides are usually added to 10 to 100 mol%, preferably 20 to 90 mol%, of the hydroxyl group generated by the addition of an unsaturated monoacid to the epoxy group of the copolymer. , More preferably 30 ~ 80 mole%. If the addition ratio is too large, the residual film rate during development may decrease, and if it is too small, the solubility may be insufficient. As a method for adding a polybasic acid anhydride to the hydroxyl group, a known method can be adopted.

Furthermore, in order to improve the sensitivity to light, after the above-mentioned polybasic acid anhydride is added, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group may be added to a part of the carboxyl group formed. on.

In order to improve developability, a glycidyl ether compound having no polymerizable unsaturated group may be added to a part of the carboxyl group formed.

It is possible to add both.

Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include a glycidyl ether compound having a phenyl group or an alkyl group. Commercial products include, for example, "Denacol EX-111", "Denacol EX-121", "Denacol EX-141", "Denacol EX-145", "Denacol" manufactured by NagasechemteX Corporation. EX-146 "," Denacol EX-171 "," Denacol EX-192 ", etc.

The structure of such a resin is described in, for example, Japanese Patent Laid-Open No. 8-297366 or Japanese Patent Laid-Open No. 2001-89533.

The weight average molecular weight (Mw) of the above-mentioned adhesive resin by polystyrene conversion measured by the GPC method is preferably 3,000 to 100,000, and particularly preferably 5,000 to 50,000. If the molecular weight is less than 3,000, heat resistance or film strength may be poor, and if the molecular weight is more than 100,000, the solubility in the developing solution may be insufficient. Moreover, as a molecular weight distribution criterion, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

[2-1-2] (meth) acrylic resin

In the present invention, as one of the particularly preferable binder resins, "(meth) acrylic resin" (hereinafter, referred to as "[2-1-2] resin") is mentioned. The "(meth) acrylic resin" in the present invention means a copolymer obtained by polymerizing a monomer component containing a compound represented by the following general formula (V) as an essential component.

[Chemical 18]

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

As mentioned above, pigment dispersions containing micronized pigments, especially micronized zinc bromide phthalocyanine pigments, or coloring compositions for color filters are prone to increase in viscosity over time, and are therefore useful for Since the solubility of the developer is relatively low, it is sometimes difficult to manufacture a color filter. Suppose that by using a method such as adjusting the developer or developing for a long time, even if the color filter pattern is made, the obtained pixels are easily defective, and the fragments are reattached to the surface of the pixels, or the defects of the straight parts of the pixels become sharp. Therefore, it can be seen that light leakage from the panel is easily caused.

In order to solve such a problem and achieve a coloring composition for a pigment dispersion liquid or a color filter containing a micronized pigment, especially a micronized zinc bromide phthalocyanine pigment: ‧ The pigment dispersion or the color filter is improved The viscosity stability of the coloring composition for light films, ‧ improving the solubility of the coloring composition in the developing solution, ‧ further preventing the defects of the obtained pixels, improving the linearity, etc., it is particularly effective to use the following [2-1 -2] resin.

Hereinafter, a compound represented by the general formula (V) will be described first.

In the ether dimer represented by the general formula (V), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ^1b and R ^2b is not particularly limited, and examples thereof include: Linear, branched or branched, such as ethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, third butyl, third pentyl, octadecyl, lauryl, 2-ethylhexyl Chain alkyl; aryl such as phenyl; cyclohexyl, third butyl cyclohexyl, dicyclopentadienyl, tricyclodecyl, iso Cycloaliphatic groups such as alkyl, adamantyl and 2-methyl-2-adamantyl; alkyls substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; and benzyl And so on. In terms of heat resistance, particularly preferred among these are methyl, ethyl, cyclohexyl, benzyl, and the like, which are difficult to remove from the primary or secondary carbon with an acid or heat. In addition, R ^1b and R ^2b may be the same substituent or different substituents.

Specific examples of the ether dimer include, for example, dimethyl 2, 2 '-[oxybis (methylene)] bis-2-propionate, and 2, 2'-[oxybis ( Methylene)] di-2-propionic acid diethyl ester, 2, 2 '-[oxybis (methylene)] bis-2-propionic acid di (n-propyl) ester, 2, 2'-[ Oxybis (methylene)] bis-2-propanoic acid di (isopropyl) ester, 2, 2 '-[oxybis (methylene)] bis-2-propionic acid bis (n-butyl) Ester, 2, 2 '-[oxybis (methylene)] bis (isobutyl) propionate, 2, 2'-[oxybis (methylene)] bis-2- Di (third butyl) propionate, 2, 2 '-[oxybis (methylene)] bis-2-tertiary propionate, 2, 2'-[oxybis (Methylene)] bis (octadecyl) bis-2-propionate, 2, 2 '-[oxybis (methylene)] bis (lauryl) propionate, 2 , 2 '-[oxybis (methylene)] bis (2-ethylhexyl) propanoate, 2, 2'-[oxybis (methylene)] bis-2-propane Bis (1-methoxyethyl) acid ester, 2, 2 '-[oxybis (methylene)] bis-2-propionic acid bis (1-ethoxyethyl) ester, 2, 2' -[Oxybis (methylene)] bis-2-propionic acid dibenzyl ester, 2, 2 '-[oxybis (methylene)] bis-2-propionic acid diphenyl ester, 2, 2' -[Oxybis (methylene)] bis-2-propionic acid di Hexyl ester, 2, 2 '-[oxybis (methylene)] bis (tertiary butylcyclohexyl) bis-2-propionate, 2, 2'-[oxybis (methylene)] Bis-2-propionic acid di (dicyclopentadienyl) ester, 2, 2 '-[oxybis (methylene)] bis-2-propionic acid di (tricyclodecyl) ester, 2, 2 '-[Oxybis (methylene)] bis-2-propionic acid di (iso (Yl) ester, 2, 2 '-[oxybis (methylene)] bisdamantane bis-2-propionate, 2, 2'-[oxybis (methylene)] bis-2-propane Acid bis (2-methyl-2-adamantyl) ester and the like.

Among these, 2, 2 '-[oxybis (methylene)] bis-2-propionic acid dimethyl, 2, 2'-[oxybis (methylene)] bis- Diethyl 2-propionate, 2, 2 '-[oxybis (methylene)] dicyclohexyl bis-2-propionate, 2, 2'-[oxybis (methylene)] bis Dibenzyl propionate.

These ether dimers may be used individually by 1 type, and may use 2 or more types together.

When the above [2-1-2] resin is obtained, the proportion of the ether dimer in the monomer component is not particularly limited, but the proportion of the ether dimer in the total monomer component is usually 2 to 60 weight %, Preferably 5 to 55% by weight, and more preferably 5 to 50% by weight. If the amount of the ether dimer is too large, it may be difficult to obtain a low molecular weight at the time of polymerization, or it may be easily gelled. On the other hand, if the amount of the ether dimer is too small, it may be coated with transparency or heat resistance. The film performance becomes insufficient.

[2-1-2] The resin preferably has an acid group. Since it has an acid group, the obtained coloring composition is formed by a crosslinking reaction in which an acid group and an epoxy group react to form an ester bond (hereinafter, referred to as acid-epoxy curing) to form a hardenable coloring composition. Or you can develop the unhardened part in an alkaline developer. 组合 物。 Composition. The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group.

[2-1-2] The acid groups contained in one molecule of the resin may be only one kind, or two or more kinds.

In order to introduce an acid group into [2-1-2] resin, for example, a monomer having an acid group and / or a "monomer capable of providing an acid group after polymerization" (hereinafter also referred to as "for introducing an acid group Monomer. ") Can be used as the monomer component. Furthermore, in the case where "a monomer capable of providing an acid group after polymerization" is used as a monomer component, a treatment for providing an acid group as described later must be performed after polymerization.

Examples of the monomer having an acid group include monomers having a carboxyl group such as (meth) acrylic acid or itaconic acid; monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide; horses Monocarboxylic anhydride, itaconic anhydride, and other monomers having a carboxylic acid anhydride group; especially preferred among these is (meth) acrylic acid.

Examples of the monomer capable of providing an acid group after the polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, and epoxy groups such as propylene oxide (meth) acrylate. Monomers; monomers having isocyanate groups such as ethyl 2-isocyanate (meth) acrylate and the like.

The monomers used to introduce these acid groups may be only one kind, or two or more kinds.

In the case where the monomer component when obtaining the [2-1-2] resin also contains the above-mentioned monomer for introducing an acid group, its content ratio is not particularly limited, and is usually 5 to 70 weight of the total monomer component %, Preferably 10 to 60% by weight. If the amount of the monomer used to introduce the acid group is too large, it will become highly viscous and it may be difficult to form a coating film, or the alkali solubility will become excessive and the pattern or coating film will be formed. Chemical resistance may decrease; on the other hand, if it is too small, the acid value of the obtained copolymer may become low, and the advantages brought about by the introduction of the acid value may not be fully utilized.

[2-1-2] The resin may be one having a radical polymerizable double bond.

In order to introduce a radical polymerizable double bond into the above-mentioned [2-1-2] resin, for example, "a monomer capable of imparting a radical polymerizable double bond after polymerization" (hereinafter also referred to as "for introducing free A monomer having a polymerizable double bond ".) After polymerization as a monomer component, a treatment for imparting a radical polymerizable double bond as described below may be performed.

Examples of the monomer capable of imparting a radical polymerizable double bond after polymerization include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; and monomers having a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride. Monomers: Glycidyl (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, ortho (or meta, or para) vinyl benzyl glycidyl ether, etc. Oxygen monomers and the like. These monomers for introducing a radical polymerizable double bond may be only one kind, or two or more kinds.

In the case where the monomer component at the time of obtaining the [2-1-2] resin also contains the above-mentioned monomer for introducing a radical polymerizable double bond, its content ratio is not particularly limited, but it is usually in the total monomer component 5 to 70% by weight, preferably 10 to 60% by weight.

Furthermore, the [2-1-2] resin of the present invention preferably has an epoxy group.

In order to introduce an epoxy group, for example, a monomer having an epoxy group (hereinafter also referred to as "monomer for introducing an epoxy group") may be polymerized as a monomer component.

Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, cyclohexylmethyl-3,4-epoxy, and ) Vinyl benzyl glycidyl ether and the like. These monomers for introducing an epoxy group may be only one kind, or two or more kinds.

In the case where the monomer component when obtaining the [2-1-2] resin also contains the above-mentioned monomer for introducing an epoxy group, the content ratio is not particularly limited, but it is usually 5 to 5 of the total monomer component. 70% by weight, preferably 10 to 60% by weight.

The monomer component at the time of obtaining [2-1-2] resin may contain other copolymerizable monomers in addition to the above-mentioned monomer components, if necessary.

Examples of other copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) N-butyl acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, (methyl) ) (Meth) acrylates such as benzyl acrylate, 2-hydroxyethyl (meth) acrylate; aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene; N-phenyl maleate N-substituted maleimines such as fluorenimine, N-cyclohexylmaleimide, etc .; butadiene or substituted butadiene compounds such as butadiene, isoprene; ethylene, propylene, vinyl chloride, Ethylene such as acrylonitrile or substituted ethylene compounds; vinyl esters such as vinyl acetate.

Among them, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferred in terms of good transparency and less susceptible to deterioration of heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more.

In addition, in the case where a part or all of the [2-1-2] resin is used as the above-mentioned dispersing resin (that is, in the case of being used in the dispersing treatment step described later), (meth) acrylic acid is preferably used The content of benzyl ester is usually 1 to 70% by weight, preferably 5 to 60% by weight of the total monomer components.

In the case where the monomer component when the above [2-1-2] resin is obtained also contains the above-mentioned copolymerizable other monomers, the content ratio is not particularly limited, preferably 95% by weight or less, and more preferably 85 % By weight or less.

Furthermore, as the [2-1-2] resin of the present invention, it is particularly preferably a copolymer consisting essentially of the following monomers: a monomer represented by the above general formula (V), a monomer having an acid group Monomers and / or monomers which can impart acid groups after polymerization, and ‧ other polymerizable monomers.

The production method (polymerization method) of [2-1-2] resin will be described below.

The polymerization method of the above-mentioned monomer component is not particularly limited, and various conventionally known methods can be adopted, but a solution polymerization method is particularly preferred. In addition, the polymerization temperature or polymerization concentration (polymerization concentration = [total weight of monomer components / (total weight of monomer components + solvent weight)] × 100), due to the type or ratio of the monomer components used, the target polymerization The molecular weight of the material varies. The polymerization temperature is preferably 40 to 150 ° C, and more preferably 60 to 130 ° C. The polymerization concentration is preferably 5 to 50%, and more preferably 10 to 40%.

When a solvent is used during the polymerization, a solvent generally used in a radical polymerization reaction may be used. Specific examples include tetrahydrofuran, dihydrofuran, Ethers such as alkane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, Ester such as propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; toluene, Aromatic hydrocarbons such as xylene and ethylbenzene; chloroform; These solvents may be used alone or in combination of two or more.

When polymerizing the above-mentioned monomer components, a polymerization initiator may be used as necessary. The polymerization initiator is not particularly limited, and examples thereof include cumene hydroperoxide, dicumyl hydroperoxide, di-tert-butyl peroxide, lauryl peroxide, benzamidine peroxide, and peroxide. Organic peroxides such as tert-butyl isopropyl carbonate, tert-pentyl 2-ethylhexanoate, tert-butyl 2-ethylhexanoate, etc .; 2, 2'-azobis (iso Butyronitrile), 1, 1'-azobis (cyclohexanecarbonitrile), 2, 2'-azobis (2, 4-dimethylvaleronitrile), 2, 2'-azobis (2 -Azo compounds such as methyl propionate) dimethyl. These polymerization initiators may be used alone or in combination of two or more thereof.

In addition, the amount of the initiator used may be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, and the like, and is not particularly limited, but a weight average can be obtained without gelation The polymer having a molecular weight of several thousands to tens of thousands is usually 0.1 to 15% by weight, and more preferably 0.5 to 10% by weight based on the total monomer component.

In addition, in order to adjust the molecular weight, a chain transfer agent may be added. Examples of the chain transfer agent include thiol-based chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid, and methyl mercaptoacetate; α-methylstyrene dimer; and the like, and a chain transfer effect is preferred. Higher n-dodecane that reduces residual monomers and is also easily available Thiol, mercaptoacetic acid. When a chain transfer agent is used, the amount used may be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, and the like, and is not particularly limited, but it does not require gelation In terms of obtaining a polymer having a weight average molecular weight of several thousands to tens of thousands, it is usually 0.1 to 15% by weight, and more preferably 0.5 to 10% by weight based on the total monomer component.

Furthermore, it is generally considered that, when a compound of the general formula (V) is used as an essential monomer component, in the above polymerization reaction, the cyclization reaction of the ether dimer is also performed simultaneously. The cyclization rate is not necessarily 100 mol%.

When the above-mentioned [2-1-2] resin is obtained, when an acid group is introduced by using the monomer capable of imparting an acid group as a monomer component, a treatment for imparting an acid group must be performed after polymerization. This treatment differs depending on the type of monomer used. For example, when a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate is used, succinic anhydride and tetrahydrophthalic acid can be added. Acid anhydrides, such as maleic anhydride. When using monomers having epoxy groups such as glycidyl (meth) acrylate, N-methylaminobenzoic acid, N-methylaminophenol and the like having amine and acid groups can be added. The compound, or (meth) acrylic acid is first added, and then acid anhydrides such as succinic anhydride, tetrahydrophthalic anhydride, and maleic anhydride are added to the resulting hydroxyl group. When a monomer having an isocyanate group such as ethyl 2-isocyanate (meth) acrylate is used, for example, a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid may be added.

When the above-mentioned [2-1-2] resin is obtained, radical polymerizability is introduced by using the monomer capable of imparting a radical polymerizable double bond as a monomer component. In the case of a double bond, a treatment for imparting a radically polymerizable double bond must be performed after polymerization.

This treatment differs depending on the type of monomer used. For example, when a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid is used, glycidyl (meth) acrylate, Compounds) having epoxy groups and radical polymerizable double bonds, such as 3,4-epoxycyclohexyl methyl acrylate, ortho (or meta, or para) vinyl benzyl glycidyl ether. When a monomer having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride is used, a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth) acrylate can be added. Epoxy (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, ortho (or meta, or para) vinyl benzyl glycidyl ether, etc. In the case of a monomer having a basic group, a compound having an acid group and a radical polymerizable double bond such as (meth) acrylic acid can be added.

The weight average molecular weight of the above [2-1-2] resin is not particularly limited, but the weight average molecular weight by polystyrene conversion measured by GPC is preferably 2,000 to 200,000, and more preferably 4,000 to 100,000. When the weight average molecular weight exceeds 200000, the viscosity may become too high and it may become difficult to form a coating film. On the other hand, when the weight average molecular weight is less than 2,000, it tends to be difficult to express sufficient heat resistance.

In the case where the above [2-1-2] resin has an acid group, the acid value of the resin is preferably 5 to 500 mgKOH / g, and more preferably 10 to 400 mgKOH / g. When the acid value is less than 5 mgKOH / g, it sometimes becomes difficult to apply to alkaline development. When the acid value exceeds 500 mgKOH / g, the viscosity tends to become too high and it is difficult to form a coating film.

Furthermore, when the acid value is relatively high, the change over time (viscosity increase) in the viscosity of the coloring composition containing it is not easy to occur, so it is better; when the acid value is relatively low, the contrast of the coloring composition containing it It is preferable that the change (fall) over time is not easy to occur.

In addition, [2-1-2] a resin, that is, a copolymer of a compound represented by the general formula (V) as an essential monomer component includes, for example, Japanese Patent Laid-Open No. 2004-300203 and Japanese Patent Laid-Open No. 2004 The compound described in -300204.

The pigment dispersion liquid of the present invention is preferably obtained by using [2-1-2] resin as the above-mentioned dispersion resin (that is, used together with a dispersant or a dispersant in a dispersion treatment step described later).

By using [2-1-2] resin as the dispersing resin, the viscosity of the pigment dispersion liquid will not increase over time, so that stable dispersibility can be obtained. In addition, coloring for color filters using the pigment dispersion liquid A composition is preferable because it exhibits high contrast.

[2-1-2] A color filter obtained by using [2-1-2] resin as a resin for pattern formation and then adding it to a pigment dispersion liquid or using it in a coloring composition manufactured without using a pigment dispersion liquid. It is preferable that the viscosity of the coloring composition is stable, and a pattern formed using the coloring composition for a color filter is difficult to be obtained.

Furthermore, the pigment dispersion liquid and the coloring composition for a color filter of the present invention may contain resins other than the above-mentioned [2-1-1] and [2-1-, as long as the effects of the present invention are not impaired. 2] Adhesive resin other than resin.

As the adhesive resin of the present invention, the above-mentioned various adhesives can be used alone One kind of resin may be used in combination of two or more kinds.

In the coloring composition of the present invention, the content ratio of the binder resin in the total solid content is usually 0.1% by weight or more, preferably 1% by weight or more, and usually 80% by weight or less, and preferably 60% by weight. %the following. If the content of the binder resin is less than this range, the film becomes brittle and the adhesion to the substrate is reduced. Conversely, if it exceeds this range, the permeability of the developing solution to the exposed portion becomes high, and the surface smoothness or sensitivity of the pixel may be deteriorated.

[2-2] other ingredients

The coloring composition for color filters of this invention may contain components other than the above as needed. Examples of such components include polymerizable monomers, photopolymerization initiating components and / or thermal polymerization initiators, surfactants, thermal polymerization inhibitors, plasticizers, storage stabilizers, surface protective agents, Adhesion improver, development improver, dye, etc.

[2-2-1] polymerizable monomer

The polymerizable monomer of the present invention is not particularly limited as long as it is a polymerizable low-molecular compound, but it is preferably a polymerizable compound having at least one ethylenic double bond (hereinafter, referred to as an "ethylenic compound") . The ethylenic compound means that when the colored composition of the present invention is irradiated with active light, it is added under the action of a photopolymerization initiating component described later or by heating under the action of a thermal polymerization initiator described later. A compound having an ethylenic double bond that is hardened by polymerization. In addition, the monomer of the present invention means a concept with respect to a polymer substance, and means a concept including a dimer, a trimer, and an oligomer in addition to the monomer in a narrow sense.

Examples of ethylenic compounds include: unsaturated carboxylic acids; Esters of hydroxy compounds; Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; By unsaturated carboxylic acids and polycarboxylic acids and the above-mentioned aliphatic polyhydroxy compounds, aromatic An ester obtained by an esterification reaction of a polyhydroxy compound such as a family polyhydroxy compound; an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a hydroxy compound containing a (meth) acrylfluorenyl group, etc. .

Examples of the ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolethane triacrylate. Acrylates, acrylates such as pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glyceryl acrylate and the like. In addition, the methacrylic acid ester obtained by replacing the acrylic acid part of these acrylates with a methacrylic acid part, the itaconic acid ester obtained by replacing the itaconic acid part, and the acrylic acid part obtained by replacing with a butenoic acid part Butyrate is also a maleate obtained by replacing with a maleic acid moiety.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, and resorcinol diacrylate. Methacrylate, pyrogallol triacrylate, etc.

The ester obtained by the esterification reaction of an unsaturated carboxylic acid, a polycarboxylic acid, and a polyhydroxy compound is not necessarily a single substance, but may be a mixture. Typical examples include: condensates of acrylic acid, phthalic acid, and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; methacrylic acid, terephthalic acid Condensate of formic acid and pentaerythritol; condensate of acrylic acid, adipic acid, butanediol, glycerol, etc.

Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a hydroxy compound containing a (meth) acrylfluorenyl group include hexamethylene diisocyanate and trimethylhexa Aliphatic diisocyanates such as methylene diisocyanate, alicyclic diisocyanates such as cyclohexane diisocyanate, isophorone diisocyanate, aromatic diisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, etc., and acrylic acid- 2-hydroxyethyl ester, 2-hydroxyethyl methacrylate, 3-hydroxy (1, 1, 1-tripropenyloxymethyl) propane, 3-hydroxy (1, 1, 1-trimethylpropene) A reactant obtained by reacting a (meth) acrylfluorenyl-containing hydroxy compound such as methoxymethyl) propane.

In addition, as the ethylenic compound used in the present invention, for example, acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; phthalic acid Divinyl ester-containing compounds and the like.

The ethylenic compound may be a monomer having an acid group. The monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and it is preferred that a non-aromatic carboxylic acid anhydride reacts with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to make it have an acid group. The polyfunctional monomer is particularly preferably at least one of pentaerythritol and dipentaerythritol in the ester.

These monomers can be used alone, but it is difficult to use a single compound in production. Therefore, two or more monomers can be used in combination. Also, if necessary, A polyfunctional monomer having no acid group as a monomer and a polyfunctional monomer having an acid group are used in combination.

The acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. If the acid value of the polyfunctional monomer is too low, the developing and dissolving characteristics are lowered. If it is too high, the manufacturing or handling becomes difficult, the photopolymerization performance is lowered, and the hardening properties such as the surface smoothness of the pixels tend to be poor. Therefore, when two or more kinds of polyfunctional monomers having different acid groups are used in combination, or in the case where two or more polyfunctional monomers having no acid group are used in combination, the acid groups of the polyfunctional monomers as a whole are preferably used. Adjust to within the above range.

In the present invention, a more preferred polyfunctional monomer having an acid group is succinic acid, which is commercially available as TO1382 manufactured by Toa Kosei Co. and commercially available as dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate A mixture of esters as the main component. A polyfunctional monomer other than the polyfunctional monomer may be used in combination.

In the present invention, the vinyl compound is preferably one having a molecular weight of 650 or less, preferably 550 or less, more preferably 400 or less, and a double bond equivalent of 150 or less, preferably 140 or less, and more preferably 110 or less . The lower limit is not particularly limited, and may be within a range where a chemical structure capable of addition polymerization is obtained.

In terms of reducing the "defects" of pixels and forming pixels with more excellent linearity, among these, compounds having a relatively small molecular weight and a small double bond equivalent are preferred. For example, preferably, a molecular weight of 400 or less and a double bond equivalent of 110 or less, an aliphatic polyhydroxy compound and an unsaturated carboxylic acid are mentioned. Examples of the ester include, more specifically, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and the like.

Furthermore, in terms of the sensitivity of the obtained coloring composition for a color filter, it is preferable to use an ethylenic compound having a molecular weight exceeding 400. As such a compound, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are particularly preferred. These compounds are preferably used in combination with an ethylene compound having a molecular weight of 400 or less and a double bond equivalent of 150 or less (more preferably 110 or less) to obtain a composition with good balance.

The blending ratio of the polymerizable monomer in the total solids content of the coloring composition of the present invention is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and usually 80% by weight or less. It is preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less. The ratio to the color material is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, particularly preferably 20% by weight or more, and usually 200% by weight or less, preferably It is 100% by weight or less, and more preferably 80% by weight or less.

[2-3] Photopolymerization initiators, thermal polymerization initiators

In order to harden the coating film, the coloring composition of the present invention preferably contains at least one of a photopolymerization initiating component and a thermal polymerization initiator. Among them, the method of hardening may be a method other than the method using these initiators.

In particular, when the colored composition of the present invention contains a resin having an ethylenic double bond as a binder resin component, or when it contains an ethylenic compound as the polymerizable monomer, it is preferable to include a photopolymerization starting system. At least one of a component and a thermal polymerization initiator. The photopolymerization starting component has a function of directly absorbing light or photosensitizing to cause a decomposition reaction or a dehydrogenation reaction and to generate a polymerization-active radical. The initiator is a polymer that generates polymerization-active radicals by heat.

[2-3-1] Photopolymerization starting system components

The photopolymerization initiator is usually used as a mixture (photopolymerization initiating component) with an additive such as an accelerator. The photopolymerization starting system component is a component having a function of directly absorbing light or causing a decomposition reaction or a dehydrogenation reaction by photosensitization, and generating a polymerization-active radical.

Examples of the photopolymerization initiator constituting the photopolymerization initiating component include titanocene-containing compounds described in various publications such as Japanese Patent Laid-Open No. 59-152396 and Japanese Patent Laid-Open No. 61-151197. The second metallocene compound; or the hexaaryl biimidazole derivative and halomethyl are described in Japanese Patent Laid-Open No. 10-39503 Free radicals such as derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters Active agent, α-amino alkyl phenone compound; oxime ester compound described in Japanese Patent Laid-Open No. 2006-36750, Japanese Patent Laid-Open No. 2002-323762, Japanese Patent Laid-Open No. 2000-80068, and the like.

Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.

2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) , 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) , 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) , 2- (4-ethoxycarbonylnaphthyl) -4, 6-bis (trichloromethyl) Isohalomethyl mesity Derivatives; 2-trichloromethyl-5- (2'-benzofuranyl) -1, 3, 4- Diazole, 2-trichloromethyl-5- [β- (2'-benzofuranyl) vinyl] -1, 3, 4- Diazole, 2-trichloromethyl-5- [β- (2 '-(6 "-benzofuranyl) vinyl)]-1, 3, 4- Diazole, 2-trichloromethyl-5-furyl-1, 3, 4- Halomethylation Diazole derivatives; 2- (2'-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4, 5-bis (3'-methoxy Phenyl) imidazole dimer, 2- (2'-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4, 5-di Imidazole derivatives such as phenylimidazole dimer, (4'-methoxyphenyl) -4, 5-diphenylimidazole dimer; benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl Ethers such as benzoin alkyl ethers; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone; diphenyl ketone, Michelin Ketone (Michler's Ketone), diethylaminodiphenyl ketone, 2-methyldiphenyl ketone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, 2-chlorodiphenyl ketone, Diphenyl ketone derivatives such as 4-bromodiphenyl ketone and 2-carboxydiphenyl ketone; 2,2-dimethoxy-2-phenylacetophenone, 2, 2-diethoxyphene Ketone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (P-dodecylphenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2- Acetophenone derivatives such as phosphonopropane-1-one, 1, 1, 1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone, 2-ethylthioxanthone, 2 -Isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc. Tonone derivatives; benzoate derivatives such as ethyl paradimethylaminobenzoate and ethyl paradiethylaminobenzoate; 9-phenylacridine, 9- (p-methoxyphenyl) acryl Acridine derivatives such as pyridine; 9, 10-dimethylbenzophene Isorphine (phenazine) derivatives; anthrone derivatives such as benzoxanthone; dicyclopentadienyl titanium dichloride, dicyclopentadienyl bisphenyl titanium, dicyclopentadienyl bis-2 , 3, 4, 5, 6-pentafluorobenzene-1-yl titanium, dicyclopentadienyl bis-2, 3, 5, 6-tetrafluorobenzene-1-yl titanium, dicyclopentadienyl bis -2, 4, 6-trifluorobenzene-1-yl titanium, dicyclopentadienyl-2, 6-difluorobenzene-1-yl titanium, dicyclopentadienyl-2, 4-difluorobenzene -1-yl titanium, dimethylcyclopentadienyl bis-2, 3, 4, 5, 6-pentafluorobenzene-1-yl titanium, dimethyl cyclopentadienyl bis-2, 6-di Titanocene derivatives such as fluorobenzene-1-yl titanium, dicyclopentadienyl-2, 6-di-fluoro-3- (pyrrole-1-yl) -benzene-1-yl titanium; 2-methyl -1- [4- (methylthio) phenyl] -2- Linylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4- (Phenylphenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4- (Phenylphenyl) butane-1-one, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4-diethylaminoacetophenone, 4-dimethylamine Phenyl acetone, 1,4-dimethylaminobenzoic acid-2-ethylhexyl ester, 2, 5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3 -(4-Diethylaminobenzyl) coumarin, 4- (diethylamino) chalcone and other α-aminoalkyl phenone compounds; 1- [9-ethyl-6- (2-methylbenzyl) -9.H.-carbazol-3-yl] ethane-1-oxime-O-acetate, 1- (4-phenylaminebenzenesulfonyl-phenyl ) Oxime ester compounds such as octane-1,2-dione-2-oxime-O-benzoate.

The photopolymerization initiating component used in the present invention preferably contains an oxime ester-based compound as a photopolymerization initiator. Among them, particularly preferred are oxime ester-based compounds represented by the following general formula (I): Compound.

[In formula (I), R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a heteroarylalkane having 4 to 25 carbon atoms. These may each have a substituent. Alternatively, R ¹ may be bonded to X or Y to form a ring.

R ² represents an alkylfluorenyl group having 2 to 20 carbon atoms, an alkenyl group having 3 to 25 carbon atoms, a cycloalkylfluorenyl group having 4 to 8 carbon atoms, an arylfluorenyl group having 7 to 20 carbon atoms, or 2 to 10 carbon atoms Alkoxycarbonyl, aryloxycarbonyl with 7 to 20 carbons, heteroaryl with 2 to 20 carbons, heteroarylfluorenyl with 3 to 20 carbons or alkylaminocarbonyl with 2 to 20 carbons, etc. It may have a substituent.

X represents a divalent aromatic hydrocarbon group and / or an aromatic heterocyclic group which may have a substituent and is obtained by condensing two or more rings.

Y represents an aromatic group which may have a substituent. ]

A coloring composition for a color filter containing a micronized pigment, especially a micronized brominated phthalocyanine pigment, is liable to generate extremely fine foreign matter. foreign matter These are those observed immediately after the coloring composition is manufactured, and those produced during the preservation of the composition. It is clear from the research results that the generation of foreign matter is particularly closely related to the photopolymerization initiator.

In addition, in the coloring composition for color filters, the green color has the highest sensitivity to irradiated light, and it is the most difficult color. One of the reasons is that, compared with pigments of other colors, the pigment itself has a lower coloring power, so the content of the pigment is necessarily higher.

The maximum transmittance wavelength of the green composition is approximately 530 nm, and the transmittance at a wavelength of 450 nm or less is approximately zero. In the manufacture of color filters using photolithography, the exposure machine usually used is a high-pressure mercury lamp. Among the corresponding photopolymerization initiators, there are those who can cause a hardening reaction to the light from the ultraviolet part to the vicinity of 410nm. However, for green, the light energy of the long wavelength portion cannot be used.

If the sensitivity of the coloring composition is insufficient, the specified line width cannot be obtained. In extreme cases, the hardening property of the coating film is poor, and a phenomenon that a transparent coating film cannot be formed may be caused. In addition, the color filter is applied with an alignment film during panel formation. However, if the coating film has a low hardening property, a pigment is used as the N-methylpyrrolidone (NMP) which is generally used as a solvent for the alignment film. The precipitate of the Lord.

In short, to obtain a coloring composition for a color filter containing a micronized pigment, a green pigment, especially a zinc bromide phthalocyanine pigment, sufficient sensitivity to light exposed to light, and suppression of foreign matter generation, very difficult.

In view of this situation, among several photopolymerization initiators, an oxime ester compound, particularly an oxime compound represented by the general formula (I), is used. A photopolymerization initiator is preferable because it can solve the above problems.

In the oxime ester compound (I), the YC (= O) -X moiety forms a light-absorbing portion, and the oxime structure portion: -C (-R ¹ ) = N-OR ² moiety forms a radical generating site. Light absorption part: YC (= O) -X efficiently absorbs light and efficiently transfers the absorbed energy to the oxime structure part, thereby achieving high sensitivity. It is generally believed that the light-absorbing portion represented by the YC (= O) -X portion, especially when it is added to the composition at a high concentration, the molecules will be combined with each other, and a plurality of molecules will become A single molecule moves, so the absorbance and absorption efficiency tend to decrease. In addition, the oxime ester compound (I) of the present invention is preferable because the Y moiety forms a bulky group, and therefore, it can have high absorbance even when added at a high concentration.

In addition, it is important that the YC (= O) -X part efficiently generates triplet energy that is easily used in the oxime structure to generate free radicals. In order to achieve efficient intramolecular energy transfer, it is important to make YC (= The O) -X part is as close to the oxime structure as possible in space.

The compound represented by the above general formula (I), because the YC (= O) -X part contains a diphenyl ketone structure or a structure similar thereto, which has a high change efficiency from the singlet state to the triplet state. The absorbed light is efficiently transformed into triplet energy.

Furthermore, the compound represented by the general formula (I) is a compound which is a diphenyl ketone structure or a structure similar thereto, and is easily overlapped with the oxime structure portion by spatial rotation in the molecule, so it can be in the molecule. Efficient energy transfer and higher sensitivity.

In the general formula (I), X represents a group which may have a substituent and consists of two or more rings A divalent aromatic hydrocarbon group and / or an aromatic heterocyclic group.

Specific examples of X include naphthalene ring, anthracene ring, (chrysene) ring, phenanthrene ring, azulene ring, florene ring, acenaphthylene ring, indene ring and other condensed ring groups composed of aromatic hydrocarbon rings; derived from acridine ring, Phenanthridine ring, xanthene ring, carbazole ring, brown Ring, dibenzothia (phenothiazine) ring, brown A phenoxazine ring, a benzothiazole ring, and the like are formed from a condensed ring composed of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.

These may have arbitrary substituents. This "arbitrary substituent" will be described later.

Among the compounds represented by the general formula (I), the compounds represented by the following general formula (i) are particularly preferred, that is, the X group in the general formula (I) is a benzene ring X ¹ in the general formula (i). And a compound having a structure represented by a ring X ² condensed therewith.

[Wherein, R ^1, R ^2, and Y, in the general formula (Ⅰ) in R ^1, R ² and Y have the same meaning of. The ring X ² represents a ring condensed with a benzene ring X ¹ , and may be a single ring or a condensed ring composed of two or more rings. The ring X ² may be condensed at any position of the benzene ring X ¹ . The benzene ring X ¹ and the ring X ² condensed therewith may further have a substituent. ]

The compound represented by the general formula (i), because the benzene ring X ¹ can form a diphenyl ketone structure or a structure similar thereto with -C (= O) -Y, so the absorbance is high, and the singlet to triplet State excitation efficiency is higher, so it is better.

As X in the general formula (I), a group containing an aromatic heterocyclic ring is preferable, and the case where the ring X ² condensed with the benzene ring X ¹ in the general formula (i) is a heterocyclic ring is particularly preferable.

In addition, X is usually a divalent group derived from a 2 to 4 condensed ring. In terms of a relatively small molecular weight, it is preferably a divalent group derived from a 2 or 3 condensed ring, which is easily suitable for light curing of a composition. In terms of the wavelength of the irradiation light used, a divalent radical derived from a 3-condensed ring is more preferred.

As the structure of X in the general formula (I) and the structure formed by the benzene ring X ¹ and the ring X ² in the general formula (i), a group derived from a carbazole ring is particularly preferred. In the case where X is a carbazolyl-based group, it is not only suitable for irradiating light during exposure, but also a strong skeleton, so it is preferable.

In the general formula (I), R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a heteroaryl group having 4 to 25 carbon atoms. Alkyl, such alkyl, alkenyl, heteroaryl, and heteroaralkyl groups may have a substituent. By making R ¹ such a group, the sensitivity to light is higher than that of a compound in which R ¹ is a phenyl group or the like. In addition, since the synthesis of the compound is easy, it is also preferable from the viewpoint of industrial production.

Examples of the alkyl group having 1 to 20 carbon atoms of R ¹ include methyl, ethyl, propyl, and butyl. An alkyl group having 1 to 12 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. alkyl.

Examples of the alkenyl group having 2 to 25 carbon atoms of R ¹ include vinyl, propenyl, and the like, preferably an alkenyl group having 3 to 12 carbon atoms such as a propenyl group, and more preferably an alkenyl group having 2 to 5 carbon atoms.

Examples of the heteroaryl group having 3 to 20 carbon atoms of R ¹ include thionyl, furanyl, imidazolyl, benzothiazolyl, and benzo The azole group and the like are preferably a heteroaryl group having 3 to 15 carbon atoms, and more preferably 4 to 10 carbon atoms.

Examples of the heteroaralkyl group having 4 to 25 carbon atoms of R ¹ include thionylmethyl, furanmethyl, imidazolylmethyl, benzothiazolylmethyl, and benzo The azolylmethyl group and the like are preferably a heteroaralkyl group having 4 to 18 carbon atoms, and more preferably 4 to 10 carbon atoms. .

Each of the above-mentioned groups may have a substituent. This substitution will be described later.

R ^{1 is} particularly preferably an alkyl group which may have a substituent. Among these, in terms of ease of production, an unsubstituted alkyl group is preferred. When a compound represented by the general formula (I) is used in a photopolymerizable composition as described later, it is preferable to substitute the amino group from the viewpoint of the adhesion of the composition to the substrate. The substituted alkyl group is preferably an alkyl group substituted with N-acetylfluorenyl-N-ethoxyamino.

In the general formula (I), R ² represents an alkylfluorenyl group having 2 to 20 carbon atoms, an alkenyl group having 3 to 25 carbon atoms, a cycloalkylfluorenyl group having 4 to 8 carbon atoms, and an arylfluorene having 7 to 20 carbon atoms. Group, alkoxycarbonyl group with 2 to 10 carbon atoms, aryloxycarbonyl group with 7 to 20 carbon atoms, heteroaryl group with 2 to 20 carbon atoms, heteroarylfluorenyl group with 3 to 20 carbon atoms, alkane with 2 to 20 carbon atoms Alkylaminocarbonyl, the alkylalkynyl, alkenyl, cycloalkylfluorenyl, arylfluorenyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryl, heteroarylfluorenyl, and alkylaminocarbonyl groups may have substitution base. By making R ² such a group, the oxime portion is easily cleaved, so that it is easy to obtain an increase in sensitivity due to the generation of free radicals.

Examples of the alkanyl group having 2 to 20 carbon atoms of R ² include ethanoyl, propionyl, butylamyl, etc., preferably 2 to 12 carbons such as ethynyl, and more preferably 2 to 7 carbons. Its alkyl group.

Examples of the alkenyl group having 3 to 25 carbon atoms of R ² include butenefluorenyl group, acrylfluorenyl group, and the like, preferably 3 to 12 carbon atoms such as butenefluorenyl group, and more preferably 3 to 7 carbon atoms. Alkenyl.

Examples of the cycloalkanoyl group having 4 to 8 carbon atoms of R ² include cyclohexylcarbonyl, methylcyclohexylcarbonyl, cyclopentylcarbonyl, and the like, and preferably 4 to 8 carbons such as cyclohexylcarbonyl, and more preferably A cycloalkanoyl group having 4 to 7 carbon atoms.

Examples of the arylfluorenyl group having 7 to 20 carbon atoms of R ² include benzylfluorenyl, methylbenzylmethyl, naphthylmethyl, and the like. Preferably, carbon atoms such as naphthylmethyl are 7 to 12, and more Aromatic groups having 7 to 10 carbon atoms are preferred.

Examples of the alkoxycarbonyl group having 2 to 10 carbon atoms in R ² include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group. Preferably, the alkoxycarbonyl group has a carbon number of 2 to 10, and more preferably a carbon number of 2 to 10. 8 of alkoxycarbonyl.

Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms in R ² include a phenoxycarbonyl group, a p-methylphenoxycarbonyl group, and a naphthyloxycarbonyl group. A carbon number such as a naphthyloxycarbonyl group is preferably 7 to 15, and more preferably a carbon atom. Aryloxycarbonyl groups of 7 to 10.

Examples of the heteroaryl group having 2 to 20 carbon atoms in R ² include thienyl, pyrrolyl, and pyridyl, and preferably 2 to 12 carbon atoms such as thienyl, and more preferably 2 to 7 carbon atoms. base.

Examples of the heteroarylfluorenyl group having 3 to 20 carbon atoms of R ² include a thiophene carbonyl group, a pyrrole carbonyl group, a pyridine carbonyl group, and the like, preferably a thiophene carbonyl group having 5 to 15 carbon atoms, and more preferably a 7 to 10 carbon atom. Aromatic group.

Examples of the alkylaminocarbonyl group having 2 to 20 carbon atoms of R ² include Phenolinylcarbonyl, dimethylaminocarbonyl, methylaminocarbonyl and the like are preferably alkylaminocarbonyl groups having 2 to 12 carbon atoms, and more preferably 2 to 10 carbon atoms such as dimethylaminocarbonyl group.

Among the above groups, in terms of exposure sensitivity, R ^{2 is} preferably an alkylfluorenyl group, a cycloalkylfluorenyl group, or an arylfluorenyl group, and more preferably an alkylfluorenyl group or an arylfluorenyl group.

In addition, the substitution that each of the above-mentioned groups as R ² may have will be described later. As each of the above-mentioned groups, those having no substituent are particularly preferred.

In the general formula (I), Y represents an aromatic group which may have a substituent. More specifically, Y is a monovalent group derived from an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and these may each have a substituent. When Y is a monovalent group derived from an aromatic heterocyclic ring, one or more rings may be condensed on a phenyl group, or one or more rings may be condensed on 5 or 6 members. A radical formed on a heteroaryl group of a ring.

The compound represented by the general formula (I) is, as described above, a phenyl or aromatic heterocyclic part of Y and a part of X via a-(C = O)-group to form a diphenyl ketone structure. Or a similar structure, so it is preferred.

In addition, as described above, the compound represented by the general formula (I) is a compound having a diphenyl ketone structure or a structure similar thereto, which is likely to overlap with the oxime structure portion due to spatial rotation in the molecule. It is better to perform efficient energy transfer in the molecule and achieve higher sensitivity.

In the case of a condensed ring group in which one or more rings of the Y system are condensed to a phenyl group, it is preferred that one to three 5 or 6-membered rings are condensed at the 2, 3-position, 3, 4- to 4- and 4- to 5-positions with 2 to 4 reductions The foundation of the ring. The ring condensed on the phenyl group in Y is preferably a hydrocarbon ring, or an aromatic hydrocarbon ring and / or an aromatic heterocyclic ring. In terms of higher quantum yield, a ring condensed on a phenyl group in Y is preferably a hydrocarbon ring, and in terms of a wider light absorption wavelength range, an aromatic ring is preferable.

As the ring of Y, a monocyclic ring or a 2 to 4 condensed ring group is preferred, and in terms of the molecular weight not becoming too large, a monocyclic ring or a 2 to 3 condensed ring group is more preferred, and a monocyclic ring and a 2 condensed ring are particularly preferred. Ring base. In addition, in the case where Y is a base derived from a 3 to 4 condensation ring, the absorption wavelength region becomes longer in wavelength, and it is also suitable for an inexpensive light source, so it is industrially preferable.

Specific examples of the ring of Y include a group derived from a benzene ring, a group derived from a naphthalene ring, an anthracene ring, Ring, phenanthrene ring, fluorene ring, fluorene ring, fluorene ring, indene ring and other condensed aromatic hydrocarbon ring groups; thienyl, pyridyl, furyl, Azole group, thiazolyl group and other groups derived from 5- or 6-membered aromatic heterocyclic rings; or from acridine ring, phenanthridine ring, dibenzopiperan ring, carbazole ring, morphine Ring, dibenzothia Ring, brown Benzene ring, benzothiazole ring, benzo A base of a condensed ring composed of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, such as an azole ring.

As the ring group of Y, phenyl, naphthyl, thienyl, furyl, and 2-pyridyl are particularly preferred, and in terms of sensitivity, phenyl, naphthyl, and thienyl are most preferred.

Examples of the substituent which the cyclic group in Y may have include alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, and propyl; and alkyl groups having 1 to 20 carbon atoms such as methylthio and ethylthio. Alkylthio groups; alkyl sulfonate groups represented by -SO ₃ R (where R is an alkyl group having 1 to 20 carbon atoms such as methyl and ethyl); 5 carbon atoms such as pentyloxy and hexyloxy ~ 20 alkoxy groups; cyclopentyl, cyclohexyl and other cycloalkyl groups having 5 to 20 carbons; cyclopentyloxy and cyclohexyloxy groups having 5 to 20 carbon groups; 5 to 20 cyclic amine groups such as phosphono, piperidinyl, and pyrrolidinyl groups; dialkylamino groups having 4 to 20 carbon atoms such as diisopropylamino group and di-tert-butylamino group; phenyl, Aryl groups such as naphthyl; heteroaryl groups such as pyridyl; aralkyl groups such as benzyl and phenethyl; halogen atoms such as Cl, Br, I, F; and tetrahydrothienyl oxide.

Among these, an alkyl group, an alkoxy group, -SO ₃ R, a cyclic amino group, or a dialkylamino group is preferable. In terms of further improving the sensitivity, a cyclic amino group or a dialkyl group is particularly preferable. Amino group.

Among the compounds represented by the general formula (I), X is a compound derived from a carbazole ring group which may have a substituent, and is represented by the following general formula (III).

[Wherein, R ^1, R ² and Y in the general formula (Ⅰ) in the R ^1, R ² and Y have the same meaning of. R ³ to R ⁹ each independently represent a hydrogen atom or a group selected from a substituent group Z described later. ]

As the substituent that X may have in the general formula (I) (the substituent that the benzene ring X ¹ and the ring X ² condensed with in the general formula (i) may have), the general formula (I), (i) And the substituents that R ¹ and R ² in (III) may have, and R ³ to R ⁹ in general formula (III) are each independently selected from the group selected from the following substituent group Z.

[Substituent Group Z]

Examples thereof include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group; a nitro group; a cyano group; or an arbitrary organic group.

Examples of the arbitrary organic group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, third butyl, pentyl, third pentyl, n-hexyl, and n- Heptyl, n-octyl, third octyl, etc. linear or branched alkyl groups having 1 to 18 carbons; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl and other carbons 3 to 18 Cycloalkyl; vinyl, propenyl, hexenyl, straight or branched alkenyl with 2 to 18 carbon atoms; cyclopentenyl, cyclohexenyl, 3 to 18 carbon alkenyl; Oxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, second butoxy, third butoxy, n-pentoxy, third pentoxy, n-hexyloxy, n- Heptyloxy, n-octyloxy, third octyloxy and other straight or branched alkoxy groups having 1 to 18 carbon atoms; methylthio, ethylthio, n-propylthio, isopropylthio, n-butyl Carbon number such as thio, second butylthio, third butylthio, n-pentylthio, third pentylthio, n-hexylthio, n-heptylthio, n-octylthio, third octylthio, etc. 1 ~ 18-chain straight or branched alkylthio; phenyl, tolyl, xylyl, mesityl, etc. 6 to 18 alkyl-substituted aryl groups; benzyl, phenethyl, and other aryl alkyl groups having 7 to 18 carbon atoms; vinyloxy, propyleneoxy, and hexenyl groups such as straight chain or 2 to 18 carbon atoms Branched alkenyloxy groups; straight or branched chain alkenylthio groups with 2 to 18 carbon atoms, such as ethylenethio, propylenethio, and hexenethio; fluorenyl groups represented by -COR ¹⁷ ; carboxyl groups; -OCOR ¹⁸ Represented by fluorenyloxy; amine represented by -NR ¹⁹ R ²⁰ ; fluorenamine represented by -NHCOR ²¹ ; carbamate represented by -NHCOOR ²² ; represented by -CONR ²³ R ²⁴ Amidomethyl group represented by; carboxylic acid ester group represented by -COOR ²⁵ ; amine sulfonyl group represented by -SO ₃ NR ²⁶ R ²⁷ ; sulfonate group represented by -SO ₃ R ²⁸ ; 2 -Thienyl, 2-pyridyl, furyl, Oxazolyl, benzo Oxazolyl, thiazolyl, benzothiazolyl, Saturated or unsaturated aromatic heterocyclic groups such as phosphono, pyrrolidinyl, and tetrahydrothienyl dioxide; trialkylsilyl groups such as trimethylsilyl group and the like.

Furthermore, the aforementioned R ¹⁷ to R ²⁸ each independently represent a hydrogen atom, an alkyl group which may be substituted, an alkyl group which may be substituted, an alkylcarbonyloxy group which may be substituted, an alkenyl group which may be substituted, and a substituted one Aryl, or optionally substituted aralkyl. These positional relationships are not particularly limited, and when there are a plurality of substituents, the substituents may be the same or different.

In the above, a plurality of substituents may be bonded to each other to form a ring, and the formed ring may be a saturated or unsaturated aromatic hydrocarbon ring or aromatic heterocyclic ring. Each ring may further have each substituent, and the substituent may further form ring.

In the general formula (III), R ³ to R ⁹ are each independently a hydrogen atom or a member selected from the above-mentioned substituent group Z. Among the substituent group Z, preferably, a methyl group which may have a substituent, Alkyl group having 1 to 20 carbons such as ethyl, aryl group having 6 to 20 carbons such as phenyl having a substituent, heteroaryl group having 3 to 20 carbons such as pyridyl having a substituent, and may have a substituent An aralkyl group having 7 to 18 carbon atoms may have a trialkylsilyl group having a substituent; an alkyl group is particularly preferred.

Furthermore, as a substituent that X may have in the general formula (I) (a substituent that the benzene ring X ¹ in the general formula (i) and the ring X ² condensed with may have), it is preferably The same as R ³ to R ⁹ is preferred.

As a substituent that R ¹ may have, an amine group and an aryl group represented by -NR ¹⁹ R ²⁰ are preferable, and as R ¹⁹ and R ²⁰ , a substituted alkyl group and a substituted alkyl group are preferred. Carbonyloxy. As mentioned above, since the adhesion improvement to the composition is also effective, it is particularly preferably an amine group represented by -NR ¹⁹ R ²⁰ such as N-acetylamyl-N-acetamyloxyamino group.

Among the compounds represented by the general formula (I) in the present invention, the compounds represented by the following general formula (II) are most preferred.

In the formula, R ^1a represents an alkyl group having 1 to 3 carbon atoms, or a group represented by the following formula (II a).

(In the formulas, R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom, a phenyl group, or an N-ethenyl-N-ethenyloxyamino group.)

R ^2a represents an alkylfluorenyl group having 2 to 4 carbon atoms, and X ^a represents ^a divalent carbazolyl group in which ^a nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms. Y ^a represents a phenyl group which may be substituted by an alkyl group, or Phenyl substituted naphthyl. ]

The following illustrates the best oxime esterification as the photopolymerization initiator of the present invention.

Specific examples of the compounds, but the photopolymerization initiator used in the present invention are not limited to any of the following specific examples. In addition, the following Me represents a methyl group.

The oxime ester compound represented by the general formula (I) can be synthesized according to methods described in, for example, WO2002 / 100903, WO2005 / 080337, Japanese Patent Laid-Open No. 2006-36750, and the like.

The oxime ester compound represented by the general formula (I) may be used alone or in combination of two or more. Further, these oxime ester compounds (I) may be used in combination with other photopolymerization initiators, and if necessary, high sensitivity can be expected by using them in combination.

As the accelerator constituting the photopolymerization starting system component, for example, N, N-dialkylaminobenzoic acid alkyl esters such as ethyl N, N-dimethylaminobenzoic acid ester, 2-mercaptobenzothiazole can be used. 2-mercaptobenzo A heterocyclic mercapto compound, such as an azole, or an aliphatic polyfunctional mercapto compound.

These other photopolymerization initiators or accelerators may be used singly or in combination of two or more kinds.

In consideration of the type of the radical generated by the compound, it is preferable to use a plurality of photopolymerization initiators in combination, and examples thereof include an oxime ester compound represented by the general formula (I) and an acetophenone derivative. , A combination of an α-aminoalkyl phenone compound, or a thioxanthone derivative. In this case, the acetophenone derivative is preferably 2-methyl-1- [4- (methylthio) phenyl] -2- Phenolinylpropane-1-one; As the α-aminoalkyl phenone compound, 2-dimethylamino-2- (4-methyl-benzyl) -1- (4- Phenyl-4-yl-phenyl) butane-1-one, 2-benzyl-2-dimethylamino-1- (4- Phenylphenyl) butanone-1; As the thioxanthone derivative, thioxanthone, 2,4-diethylthioxanthone and the like are preferable.

The blending ratio of the photopolymerization starting system components (that is, the total amount of the photopolymerization initiator and accelerator) is in the total solid content of the coloring composition for a color filter of the present invention, and is usually 0.1 to 40 weight %, Preferably 0.5 to 30% by weight. If the blending ratio is significantly low, the sensitivity to exposure light will be reduced. On the other hand, if the blending ratio is significantly high, the solubility of the unexposed portion in the developing solution will be reduced, and poor development will be caused.

In order to improve the sensing sensitivity, a sensitizing dye corresponding to the wavelength of the light source of the image exposure can be blended in the components of the photopolymerization starting system as needed. Examples of such sensitizing dyes include dibenzopiperan pigments described in Japanese Patent Laid-Open No. 4-221958 and Japanese Patent Laid-Open No. 4-219756, Japanese Patent Laid-Open No. 3-239703, and Japanese Patent Laid-Open No. Hei. Coumarin pigments having a heterocyclic ring described in Japanese Patent No. 5-289335, 3-ketocoumarin compounds described in Japanese Patent Laid-Open No. 3-239703 and Japanese Patent Laid-Open No. 5-289335 , Japanese Patent Laid-Open No. 6-19240 The pyrromethene pigment described in the newspaper; others include: Japanese Patent Laid-Open No. 47-2528, Japanese Patent Laid-Open No. 54-155292, Japanese Patent Laid-Open No. 45-37377, Japanese Patent Laid-Open No. 48 -84183, JP 52-112681, JP 58-15503, JP 60-88005, JP 59-56403, JP 2-69, and A pigment having a dialkylaminobenzene skeleton described in JP-A-57-168088, JP-A-H107-107761, JP-A-H210-210240, and JP-A-H4-288818.

Among these sensitizing dyes, preferred are sensitizing dyes containing an amine group, and more preferred are compounds having an amine group and a phenyl group in the same molecule. Particularly preferred are, for example, 4, 4'-dimethylaminodiphenyl ketone, 4, 4'-diethylaminodiphenyl ketone, 2-aminodiphenyl ketone, 4-aminodiphenyl ketone , 4, 4'-diamino diphenyl ketone, 3, 3'-diamino diphenyl ketone, 3, 4-diamino diphenyl ketone and other diphenyl ketone compounds; 2- (p Dimethylaminophenyl) benzo Azole, 2- (p-diethylaminophenyl) benzo Azole, 2- (p-dimethylaminophenyl) benzene [4, 5] benzo Azole, 2- (p-dimethylaminophenyl) benzo [6, 7] benzo Azole, 2, 5-bis (p-diethylaminophenyl) 1, 3, 4- Azole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- ( P-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1, 3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diamino Ethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) Compounds such as p-pyrimidine and the like containing p-dialkylaminophenyl. The best of these is 4, 4'-dialkylamino diphenyl ketone.

Moreover, a sensitizing dye may be used individually by 1 type, and may mix and use 2 or more types.

The compounding ratio of the sensitizing pigment in the coloring composition of the present invention is usually 0% by weight or more, preferably 0.2% by weight or more, and more preferably 0.5% by weight or more in the total solid content of the coloring composition. It is usually 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less.

[2-3-2] Thermal polymerization initiator

Specific examples of the thermal polymerization initiator that can be contained in the coloring composition of the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Among these, an azo-based compound is suitably used.

Examples of the azo compound include 2, 2'-azobisisobutyronitrile, 2, 2'-azobis (2-methylbutyronitrile), and 1, 1'-azobis (cyclohexyl) Ene-1-carbonitrile), 2, 2'-azobis (2, 4-dimethylvaleronitrile), 1-[(1-cyano-1-methylethyl) azo] formamidine (2- (aminomethylamidoazo) isobutyronitrile), 2, 2-azobis (2-methyl-N- [1, 1-bis (hydroxymethyl) -2-hydroxyethyl) propane Hydrazine}, 2, 2'-azobis [N- (2-propenyl) -2-methylpropanamide], 2, 2'-azobis [N- (2-propenyl) -2 -Ethylpropylamidamine], 2, 2'-azobis [N-butyl-2-methylpropylamidamine], 2, 2'-azobis (N-cyclohexyl-2-methylpropyl) Hydrazine), 2, 2'-azobis (dimethyl-2-methylpropionamine), 2, 2'-azobis (dimethyl-2-methylpropionate), 2, 2'-azobis (2, 4, 4-trimethylpentene), etc. Among these, 2, 2'-azobisisobutyronitrile, 2, 2'-azobis (2 , 4-dimethylvaleronitrile) and the like.

Examples of the organic peroxide include benzamidine peroxide and diperoxide. Third butyl, cumene hydroperoxide and the like. Specific examples include diisobutylammonium peroxide, cumyl peroxyneodecanoate, di-n-propyl peroxide dicarbonate, diisopropyl peroxydicarbonate, and diperoxy peroxide. Di second butyl carbonate, neodecanoic acid-1, 1, 3, 3-tetramethylbutyl ester, bis (4-third butylcyclohexyl) peroxydicarbonate, neodecanoic acid- 1-cyclohexyl-1-methylethyl ester, bis (2-ethoxyethyl) peroxydicarbonate, bis (2-ethylhexyl) peroxydicarbonate, third hexadecanoate Ester, dimethoxybutyl peroxydicarbonate, third butyl peroxydecanoate, third hexyl pervalerate, third butyl pervalerate, di (3, 5 , 5-trimethylhexamidine), di-n-octyl peroxide, dilauryl peroxide, distearyl peroxide, 2-ethylhexanoic acid-1, 1, 3, 3-tetramethyl Butyl ester, 2, 5-dimethyl-2, 5-bis (2-ethylhexylperoxy) hexane, tert-hexyl peroxide 2-ethylhexanoate, bis (4-methyl peroxide) Methyl benzamidine), tert-butyl 2-ethylhexanoate, dibenzyl peroxide, tert-isobutyric acid Butyl ester, 1, 1-bis (third butylperoxy) -2-methylcyclohexane, 1, 1-bis (third hexylperoxy) -3, 3, 5-trimethyl ring Hexane, 1, 1-bis (third hexylperoxy) cyclohexane, 1, 1-bis (third butylperoxy) cyclohexane, 2, 2-bis (4, 4-bis ( Third butyl peroxy) cyclohexyl) propane, third hexyl isopropyl peroxide, third butyl peroxymaleate, third butyl peroxide 3, 5, 5-trimethylhexanoate Butyl ester, tertiary butyl perlaurate, 2,5-dimethyl-2,5-di (3-methylbenzyl peroxide) hexane, isopropyl peroxy monobutyl carbonate Ester, 2-ethylhexyl monocarbonate tert-butyl carbonate, tert-hexyl peroxybenzoate, 2, 5-dimethyl-2, 5-bis (benzidine peroxy) Hexane, third butyl peracetate, 2,2-bis (third butyl peroxy) butane, third butyl peroxybenzoate, 4, 4-bis (third butyl peroxy) ) N-butyl valerate, bis (2-third-butylperoxyisopropyl) benzene, dicumyl peroxide, di-tert-hexyl peroxide, 2,5-dimethyl-2, 5- Di (third butyl peroxy) hexane, di-third butyl peroxide, hydrogen peroxide p-menthane, 2, 5-dimethyl-2, 5-bis (third butyl peroxy) Hexyne-3, dicumyl hydrogen peroxide, 1, 1, 3, 3-tetramethylbutyl hydrogen peroxide, cumene hydrogen peroxide, third butyl hydrogen peroxide, third butyl peroxide Trimethylsilyl, 2, 3-dimethyl-2, 3-diphenylbutane, bis (3-methylbenzidine) and benzamidine peroxide (3-methylbenzyl) Ii) and a mixture of benzophenazine peroxide.

Furthermore, among the photopolymerization initiators described in [2-3-1], for example, α-aminoalkyl phenone-based compounds and the like also function as thermal polymerization initiators. Therefore, as the thermal polymerization initiator, a compound selected from the examples can be used as an example of the photopolymerization initiator.

These thermal polymerization initiators may be used individually by 1 type, and may use 2 or more types together.

When the proportion of the thermal polymerization initiators in the colored resin composition is too small, the film is not sufficiently hardened, and the durability as a color filter may be insufficient. If it is too large, the degree of thermal shrinkage becomes large, and there is a possibility that cracks or cracks may occur after thermal curing. Moreover, the tendency for storage stability to fall was seen. Therefore, the content ratio of the thermal polymerization initiators in the total solid content of the colored resin composition of the present invention is preferably from 0 to 30% by weight, and particularly preferably from 0 to 20% by weight.

[2-2-4] Surfactant

Various surfactants, such as anionic, cationic, nonionic, and amphoteric surfactants, can be used as the surfactant. However, since the possibility of adversely affecting various characteristics is low, it is preferable to use a nonionic surfactant. Surfactant. The concentration range of the surfactant is usually 0.001% by weight or more, preferably 0.005% by weight or more, more preferably 0.01% by weight or more, and most preferably 0.03% by weight or more relative to the total composition amount. 10% by weight or less, preferably 1% by weight or less, more preferably 0.5% by weight or less, and most preferably 0.3% by weight or less.

[2-2-5] Thermal polymerization inhibitor

As the thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, catechol, catechol, 2, 6-tert-butyl-p-cresol, β-naphthol, and the like can be used. The blending amount of the thermal polymerization inhibitor is preferably in the range of 0% by weight or more and 3% by weight or less with respect to the total solid content of the composition.

[2-2-6] Plasticizer

As the plasticizer, for example, dioctyl phthalate, di (dodecyl) phthalate, triethylene glycol dicaprylate, dimethylethylene phthalate ( dimethylglycol phthalate), tricresyl phosphate, dioctyl adipate, dibutyl sebacate, glyceryl triacetate, and the like. The blending amount of these plasticizers is preferably in the range of usually 10% by weight or less with respect to the total solid content of the composition.

[3] Preparation of coloring composition

Next, a method for preparing the colored composition of the present invention will be described.

As described above, the coloring composition for a color filter of the present invention can be obtained by It is prepared by mixing other ingredients into a pigment dispersion liquid prepared in advance, and all ingredients may be mixed simultaneously or sequentially. Hereinafter, a case where the preparation is performed according to the former method will be described as an example, but it is not limited thereto.

The coloring composition for a color filter of the present invention may be photocurable (photopolymerizable) or thermally polymerizable depending on the process to be applied. Hereinafter, a case of a photopolymerizable composition (hereinafter referred to as a "photoresist") will be described as an example, but the present invention is not limited thereto.

First, each specific amount of pigment, dispersant and solvent are weighed out, and the pigment is dispersed in the dispersing treatment step to prepare a pigment dispersion liquid. In this dispersion processing step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, and the like can be used. By performing the dispersion treatment to make the color material micronized, the coating characteristics of the coloring composition can be improved, and the transmittance of the pixels in the color filter of the product can be improved.

When dispersing a pigment, as described above, it is preferable to use a dispersing resin or a dispersing aid in combination as appropriate.

In the case of using a sand mill for dispersion treatment, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature at which the dispersion treatment is performed is usually set to 0 ° C or higher, preferably room temperature or higher, and is usually set to a range of 100 ° C or lower, preferably 80 ° C or lower. In addition, the appropriate time of the dispersion time varies depending on the composition of the pigment dispersion liquid, the size of the sand mill device, and the like, and must be appropriately adjusted.

The pigment dispersion liquid obtained by the above-mentioned dispersion treatment is mixed with a solvent and a polymerizable monomer, and if necessary, further mixed with a binder resin and photopolymerization. A coloring composition is obtained by combining a starting system component, components other than the above, etc., and preparing a uniform dispersion solution. In addition, since fine impurities are mixed in each of the dispersing treatment step and the mixing step, it is preferable to filter the obtained pigment dispersion liquid with a filter or the like.

[4] Manufacturing of color filters

Next, the color filter of the present invention will be described.

The color filter of the present invention is characterized by having a pixel formed on the substrate using the coloring composition.

[4-1] Transparent substrate (support)

The material of the transparent substrate used as the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, and thermoplastic resins such as polycarbonate, polymethyl methacrylate, and polyfluorene. Sheets; thermosetting resin sheets such as epoxy resins, unsaturated polyester resins, and poly (meth) acrylic resins; or various types of glass. Among these, from the viewpoint of heat resistance, glass or a heat-resistant resin is preferred.

In order to improve surface properties such as adhesion, the transparent substrate and the black matrix-forming substrate may be subjected to a thin film forming treatment of various resins such as corona discharge treatment, ozone treatment, silane coupling agent, or urethane resin, if necessary. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, and preferably 7 mm or less. In addition, in the case of performing a thin film forming treatment of various resins, the film thickness is usually 0.01 μm or more, preferably 0.05 μm or more, and usually 10 μm or less, preferably in a range of 5 μm or less.

[4-2] black matrix

A black matrix is provided on the transparent substrate to form pixel images that are usually red, green, and blue, thereby manufacturing the color filter of the present invention.

The black matrix is formed on a transparent substrate using a light-shielding metal film or a photosensitive colored resin composition for a black matrix. As the light-shielding metal material, chromium compounds such as metallic chromium, chromium oxide, and chromium nitride, alloys of nickel and tungsten, and the like can be used. Those laminated layers may be a plurality of layers.

These metal light-shielding films are usually formed by a sputtering method. After forming a desired pattern in a film shape using a positive-type photoresist, an etching solution obtained by mixing ammonium cerium nitrate with perchloric acid and / or nitric acid is used. The chromium is etched, and other materials are etched using an etching solution corresponding to the material. Finally, the positive photoresist is peeled off with a special stripper, thereby forming a black matrix.

In this case, first, a thin film of the metal or metal ‧ metal oxide is formed on a transparent substrate by evaporation or sputtering. Then, after a coating film of a colored composition is formed on the film, a photomask is used to expose and develop the coating film using a photomask having a repeating pattern such as a stripe, a mosaic, and a triangle to form a photoresist image. Thereafter, an etching process is performed on the coating film to form a black matrix.

In the case of using a photosensitive colored resin composition for a black matrix, a black matrix is formed by using a colored resin composition containing a black color material. For example, use one or more black color materials including carbon black, graphite, iron black, aniline black, cyanine black, titanium black, or other inorganic or organic pigments. A coloring composition of a black color material, which is a mixture of red, green, and blue selected from materials, dyes, and the like, can form a black matrix in the same manner as the method of forming red, green, and blue pixels described later.

[4-3] Formation of pixels

The method of forming a pixel differs depending on the type of coloring composition used. As described above, a case where a photopolymerizable composition is used as the coloring composition is described as an example.

A coloring composition of one of red, green, and blue is coated on a transparent substrate provided with a black matrix. After drying, a photomask is superposed on the coating film, and the image is exposed and developed through the photomask. It is necessary to perform thermal curing or light curing to form pixels. This operation is performed on the colored composition of three colors of red, green, and blue, respectively, so as to form a color filter image.

The coloring composition for a color filter of the present invention can be used to prepare a coating liquid for forming a pixel (photoresist pattern) of at least one color among red, green, and blue pixels. As described above, The effects and advantages of green pixel formation materials, especially green pixel formation materials containing zinc bromide phthalocyanine pigments, are most significant.

The coloring composition for a color filter can be applied by a spinner method, a wire-bar coating method, a flow coat method, a die coat method, or a roll coating method. A roll coat method, a spray coat method, or the like is performed. Among them, if the die coating method is used, the use amount of the coating liquid can be greatly reduced, and there is no effect of mist or the like attached when the spin coating method is used, and the generation of foreign substances can be suppressed. good.

If the coating film is too thick, it is difficult to develop, or it is difficult to make the liquid crystal cell Clearance adjustment is performed. On the other hand, if the coating film is too thin, it is difficult to increase the pigment concentration, and the desired color cannot be developed. The thickness of the coating film is generally 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably, based on the film thickness after drying. The range is 5 μm or less.

[4-4] Drying of coating film

The coating film formed on the substrate using the colored composition is preferably dried using a hot plate, an infrared (IR) oven, a convection oven, or the like. Normally, after preliminary drying, reheating is performed to dry.

The conditions for preliminary drying can be appropriately selected according to the type of the above-mentioned solvent components, the performance of the dryer used, and the like. The drying temperature and drying time can be selected according to the type of the solvent component, the performance of the dryer used, etc. Specifically, the drying temperature is usually 40 ° C or higher, preferably 50 ° C or higher, and usually 80 ° C or lower. The range is preferably 70 ° C or lower; the drying time is usually 15 seconds or longer, preferably 30 seconds or longer, and usually 5 minutes or shorter, and preferably 3 minutes or shorter.

The temperature conditions for reheating and drying are preferably higher than the pre-drying temperature, and specifically, usually 50 ° C or higher, preferably 70 ° C or higher, and usually 200 ° C or lower, preferably 160 ° C or lower, Particularly preferred is a range below 130 ° C. Although the drying time also depends on the heating temperature, it is usually 10 seconds or longer, preferably 15 seconds or longer, and usually 10 minutes or shorter, and preferably 5 minutes. The higher the drying temperature, the better the adhesion to the transparent substrate, but if the drying temperature is too high, the adhesive resin will develop. Biodegradation may induce thermal polymerization and cause poor development. In addition, as the drying step of the coating film, a reduced-pressure drying method in which drying is performed in a reduced-pressure chamber without increasing the temperature may be adopted.

[4-5] Exposure steps

The exposure step is to superimpose a negative matrix pattern on the coating film of the colored composition, and irradiate ultraviolet or visible light through the mask pattern. At this time, in order to prevent polymerization obstacles caused by oxygen, if necessary, an oxygen barrier layer such as a polyvinyl alcohol layer may be formed on the coating film before exposure.

The light source used in the image exposure is not particularly limited. Examples of the light source include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, and fluorescent lamps; or argon ions Lasers, YAG (Yttrium Aluminum. Garnet) lasers, Excimer Lasers, nitrogen lasers, helium-cadmium lasers, semiconductor lasers, and other laser light sources. When a specific wavelength of light is used for irradiation, an optical filter may be used.

[4-6] Development steps

As for the color filter of the present invention, after the image exposure of the coating film using the colored composition of the present invention is performed by using the light source described above, development is performed using an organic solvent or an aqueous solution containing a surfactant and a basic compound, thereby enabling It is manufactured by forming an image on a substrate. The aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye, or a pigment.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, and silicic acid. Inorganic basic compounds such as sodium, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; or single. Di or triethanolamine, mono. Dimethyl or trimethylamine, mono. Di or triethylamine, mono or diisopropylamine, n-butylamine, mono. Organic basic compounds such as di- or triisopropanolamine, ethyleneimine, ethylenediimide, tetramethylammonium hydroxide (TMAH), and choline.

These basic compounds may be a mixture of two or more kinds.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters. And other nonionic surfactants; anionic interfacial activities such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkylsulfonates, sulfosuccinates, etc. Agents; Alkyl betaines; Amino acid and other amphoteric surfactants.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethylcellulose, butylcellulose, phenylcellulose, propylene glycol, diacetone alcohol, and the like. The organic solvent may be used alone or in combination with an aqueous solution.

The conditions for the development process are not particularly limited, and the development temperature is usually 10 ° C or higher, preferably 15 ° C or higher, more preferably 20 ° C or higher, and usually 50 ° C or lower, and preferably 45 ° C or lower, more preferably It is the range below 40 degreeC. As the development method, any method such as a dip development method, a spray development method, a brush development method, and an ultrasonic development method can be adopted.

[4-7] Thermal hardening

The developed color filter is heat-cured. Heat hardening The processing conditions are generally selected from a temperature of 100 ° C or higher, preferably 150 ° C or higher, and usually 280 ° C or lower, preferably 250 ° C or lower, and a time of 5 minutes or longer and 60 minutes or shorter. After these series of steps, a monochromatic patterned image is formed. This step is performed sequentially in sequence, and black, red, green, and blue are patterned to form a color filter. Moreover, the order of the patterning of the four colors is not limited to the above order.

Furthermore, in addition to the above-mentioned manufacturing method, the color filter of the present invention may be coated on a substrate by (1) applying a coloring composition containing a polyimide resin as a binder resin, and then using an etching method. A method of forming a pixel. In addition, (2) a method of using the colored composition of the present invention as a coloring ink to directly form a pixel image on a transparent substrate using a printer, or (3) using the colored composition of the present invention as a plating solution, A method in which a substrate is immersed in this plating solution, and a colored film is deposited on an ITO electrode having a specific pattern. Furthermore, (4) a method of attaching a film coated with the coloring composition of the present invention to a transparent substrate, peeling it, performing image exposure and development, and forming a pixel image; or (5) using The coloring composition of the present invention is used as a coloring ink, a method of forming a pixel image using an inkjet printer, and the like. The manufacturing method of a color filter is based on the composition of the coloring composition for color filters, and employ | adopts the method suitable for it.

[4-8] Formation of transparent electrodes

The color filter of the present invention is formed by forming a transparent electrode such as ITO on a pixel in an original state, and is used as a part of an organic EL display or a liquid crystal display device. However, in order to improve the surface smoothness or durability, if necessary, If necessary, a surface coating such as polyimide or polyimide may be provided on the pixel. In some applications, such as a planar alignment drive method (IPS mode), a transparent electrode may not be formed in some of them.

[5] Liquid crystal display (panel)

Next, a method for manufacturing a liquid crystal display device (panel) according to the present invention will be described. As for the liquid crystal display device of the present invention, an alignment film is usually formed on the above-mentioned color filter of the present invention, and a spacer is spread on the alignment film, and then is bonded to the opposite substrate to form a liquid crystal cell, and then the liquid crystal is formed. The injection into the formed liquid crystal cell is completed by wiring with the counter electrode. The alignment film is preferably a resin film such as polyimide. The alignment film is usually formed by a gravure printing method and / or a flexographic printing method, and the thickness of the alignment film is set to several tens of nm. After hardening the alignment film by thermal firing, surface treatment is performed by ultraviolet irradiation or a treatment using an abrasive cloth, and the surface state can be adjusted by adjusting the slope of the liquid crystal.

As the spacer, a size corresponding to the gap of the opposing substrate can be used, and usually, it is preferably 2 to 8 μm. It is also possible to use a photolithography method to form a photosensitive spacer (PS, photo spacer) of a transparent resin film on a color filter substrate, and use it instead of a spacer. As the counter substrate, an array substrate is generally used, and a TFT (thin film transistor) substrate is particularly preferred.

The gap to be bonded to the opposite substrate varies depending on the application of the liquid crystal display device, and is usually selected within a range of 2 μm or more and 8 μm or less. After bonding to the counter substrate, a portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin. Harden the sealing material by UV irradiation and / or heating To seal the periphery of the liquid crystal cell.

After the sealed liquid crystal cell is cut into panel units, a decompressed state is formed in the vacuum chamber. The liquid crystal injection port is immersed in the liquid crystal, and then the room is leaked, thereby injecting the liquid crystal into the liquid crystal cell. The degree of decompression in the liquid crystal cell is usually 1 × 10 ^-2 Pa or more, preferably 1 × 10 ^-3 Pa or more, and usually 1 × 10 ^-7 Pa or less, preferably 1 × 10 ^-6 Pa The following range. In addition, the liquid crystal cell is preferably heated under reduced pressure. The heating temperature is usually 30 ° C or higher, preferably 50 ° C or higher, and usually within a range of 100 ° C or lower, preferably 90 ° C or lower.

The heating and holding time during decompression is usually set to a range of 10 minutes or more and 60 minutes or less, and then immersed in liquid crystal. The liquid crystal cell into which the liquid crystal is injected is to seal the liquid crystal injection port by curing the UV curing resin to complete the liquid crystal display device (panel).

The type of liquid crystal is not particularly limited, and it is a conventional liquid crystal such as an aromatic system, an aliphatic system, and a polycyclic compound, and may be a lyotropic liquid crystal, a thermotropic liquid crystal, or the like. Either. Among thermotropic liquid crystals, nematic liquid crystals, smectic liquid crystals, and cholesteric liquid crystals are known, and any of them can be used.

[6] organic EL display

When an organic EL display is manufactured using the color filter of the present invention, for example, as shown in FIG. 1, a color of the present invention in which a resin black matrix (not shown) is formed on a transparent support substrate 10 is first produced. Filter Sheet, the resin black matrix is provided between the pixel 20 (wherein at least a portion of the pixel 20 is formed using the coloring composition of the present invention) and the adjacent pixel 20 with an organic protective layer 30 and an inorganic oxide film interposed therebetween. 40. The organic light-emitting body 500 is laminated on the color filter, thereby fabricating an organic EL element.

As a method for stacking the organic light emitting body 500, a method in which a transparent anode 50, a hole injection layer 51, a hole injection layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on a color filter is mentioned. Method; or a method of attaching the organic light emitting body 500 formed on another substrate to the inorganic oxide film 40, and the like. By using the organic EL device 100 thus produced, an organic EL device 100 can be produced by, for example, the method described in "Organic EL Display" (published by Ohm Corporation on August 20, 2004, and then by Jingshi, Anda Chihaya, and Hideyuki Murata). EL display.

Furthermore, the color filter of the present invention can be applied to both the organic EL display of the passive driving method and the organic EL display of the active driving method.

[Example]

Next, the present invention will be described more specifically with reference to production examples, examples, and comparative examples, but the present invention is not limited to the following examples as long as the gist is not exceeded.

In addition, Examples 1 to 4 and Comparative Examples 1 to 2 are examples using CI Pigment Green 36 as a pigment, and Examples 5 to 36 and Comparative Examples 3 to 7 are examples using a zinc bromide phthalocyanine pigment as a pigment. Examples 37 to 43 are examples using a red pigment such as CI Pigment Red 254 as the pigment.

In these examples, Examples 7 to 15 and Comparative Examples 5 to 6 use "a copolymer of (meth) acrylate containing epoxy groups and other radically polymerizable monomers in the copolymer A resin obtained by adding an unsaturated monobasic acid to at least a part of an epoxy group, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of a hydroxyl group generated by the addition reaction "(equivalent to [2-1-1] resin in the specification of the present application. Hereinafter, referred to as [2-1-1] resin) as an example of the binder resin.

Examples 16 to 20 and Comparative Example 7 use a copolymer obtained by polymerizing a monomer component containing the compound represented by the general formula (V) as an essential part, that is, "(meth) acrylic resin" ( This corresponds to [2-1-2] resin in the description of the present application. Hereinafter, referred to as [2-1-2] resin) as an example of the binder resin.

Examples 21 to 29 are examples in which an oxime ester compound is used as a photopolymerization initiator (photopolymerization initiation component).

Examples 30 to 36 are examples in which an aromatic carboxylic acid compound is used.

[Synthesis Example 1: Synthesis of zinc bromide phthalocyanine]

Zinc phthalocyanine is produced using phthalodinitrile and zinc chloride as raw materials. The obtained 1-chloronaphthalene solution of zinc phthalocyanine has light absorption at 600-700 nm.

As for the halogenation, 3.1 parts by weight of sulfonium chloride, 3.7 parts by weight of anhydrous aluminum chloride, 0.46 parts by weight of sodium chloride, and 1 part by weight of zinc phthalocyanine were mixed at 40 ° C, and 4.4 parts by weight of bromine was added dropwise. After reacting at 80 ° C. for 15 hours, the reaction mixture was poured into water to precipitate a zinc bromide phthalocyanine crude pigment. This aqueous slurry was filtered, washed with hot water at 80 ° C, and then washed at 90 ° C. It was dried to obtain 3.0 parts by weight of a crude zinc bromide phthalocyanine pigment.

1 part by weight of the above crude zinc bromide phthalocyanine pigment, 12 parts by weight of crushed sodium chloride, 1.8 parts by weight of diethylene glycol, and 0.09 parts by weight of xylene were added to the double-wrist kneader, and kneaded at 70 ° C. 10 hours. After that, it was taken out of 100 parts by weight of water at 80 ° C. and stirred for 1 hour, and then filtered, washed with hot water, dried, and pulverized to obtain a zinc bromide phthalocyanine pigment.

According to the analysis of the halogen content in the mass analysis, it can be known that the average composition of the obtained zinc bromide phthalocyanine pigment system is ZnPcBr ₁₄ Cl ₂ (Pc: phthalocyanine), and one molecule contains 14 bromine atoms on average. The average value of the primary particle diameter measured with a transmission electron microscope ("H-9000UHR" manufactured by Hitachi, Ltd.) was 0.023 μm.

In addition, the average primary particle size of the pigment is obtained by ultrasonic dispersing the pigment in chloroform, and the dispersion liquid is added dropwise to the grid attached with a cotton wool film, and dried by a transmission electron microscope ( TEM) Observation of the primary particle image of the pigment was obtained, and the primary particle diameter was measured based on the image to obtain a single average value (average particle diameter).

[Synthesis Example 2: Synthesis of Dispersant A ']

Except that the amine group (dimethylamine group) in the copolymer is not quaternized, a methacrylic AB block having a tertiary amine group is synthesized in accordance with Example 1 of Japanese Patent Laid-Open No. 1-229014. Copolymer.

The weight average molecular weight Mw of the obtained copolymer was 9000, the amine value was 121 mgKOH / g, and the acid value was 0 mgKOH / g. The "repeating unit having an amine group on the side chain" in the B-block has a structure represented by the following formula (a), and the repeating unit represented by the following formula (b) is in the A-block The ratio is 11 Mohr%.

The amine value and the acid value were measured by the following methods.

[Determination of amine value]

In a 100mL beaker, accurately weigh 0.5 ~ 1.5g of dispersant and dissolve with 50mL acetic acid. Using an automatic titration device with a pH electrode, the solution was neutralized and titrated with a 0.1 mol / L HCLO ₄ acetic acid solution. The inflection point of the titration pH curve was used as the end point of the titration, and the amine value was calculated according to the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S) (where, W is the dispersant sample weighing amount [g], V is the titration end titration amount [mL], S is the dispersant sample Solid content concentration [wt%].)

[Synthesis Example 3: Synthesis of Dispersant C]

50 parts by weight of polyethyleneimine having a weight average molecular weight of about 5000, 40 parts by weight of polycaprolactone at n = 5, and 6 parts by weight of stearic acid were mixed with 300 parts by weight of propylene glycol monomethyl ether acetate, and Stir at 150 ° C for 3 hours under a nitrogen atmosphere. The dispersant C thus synthesized had an amine value of 54 mgKOH / g and an acid value of 10 mgKOH / g.

[Synthesis Example 4: Synthesis of Binder Resin D]

A separable flask with a cooling tube was prepared as a reaction tank, 400 parts by weight of propylene glycol monomethyl ether acetate was added, and after nitrogen substitution, the temperature was increased to 90 ° C. with an oil bath while stirring.

On the other hand, 30 parts by weight of dimethyl 2,2 '-[oxybis (methylene)] bis-2-propionate, 60 parts by weight of methacrylic acid, and a methylpropanoic acid ring were added to the monomer tank 110 parts by weight of hexyl ester, 5.2 parts by weight of third ethyl 2-ethylhexanoate, 40 parts by weight of propylene glycol monomethyl ether acetate, and 5.2 parts by weight of n-dodecyl mercaptan were added to the chain transfer agent tank. 2. 27 parts by weight of propylene glycol monomethyl ether acetate. The temperature of the reaction tank was stabilized at 90 ° C, and then the reactants were added dropwise from the monomer tank and the chain transfer agent tank to start polymerization. While the temperature was maintained at 90 ° C, the dropwise addition was performed for 135 minutes, and 60 minutes after the end of the dropwise addition, the temperature was increased to bring the reaction tank to 110 ° C.

After maintaining the temperature at 110 ° C for 3 hours, the gas introduction tube was mounted on a separable flask, and the blowing of a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, 39.6 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2, 2′-methylenebis (4-methyl-6-tert-butylphenol), and 0.8 parts by weight of triethylamine were added to the reaction tank. And reacted directly at 110 ° C for 9 hours.

After cooling to room temperature, a polymer solution having a polystyrene-equivalent weight average molecular weight of 8000 and an acid value of 101 mgKOH / g as measured by the GPC method was obtained.

[Synthesis Example 5: Synthesis of Binder Resin E]

A separable flask with a cooling tube was prepared as a reaction tank, 400 parts by weight of propylene glycol monomethyl ether acetate was added, and after nitrogen substitution, the temperature was increased to 90 ° C. with an oil bath while stirring.

On the other hand, 30 parts by weight of dimethyl 2,2 '-[oxybis (methylene)] bis-2-propionate, 60 parts by weight of methacrylic acid, and benzyl methacrylate were added to the monomer tank. 110 parts by weight, 5.2 parts by weight of third ethyl 2-ethylhexanoate, 40 parts by weight of propylene glycol monomethyl ether acetate, 5.2 parts by weight of n-dodecyl mercaptan, and propylene glycol were added to the chain transfer agent tank. 27 parts by weight of monomethyl ether acetate, the temperature of the reaction tank was stabilized at 90 ° C, and then the reactants were added dropwise from the monomer tank and the chain transfer agent tank to start polymerization. While the temperature was maintained at 90 ° C, the dropwise addition was performed for 135 minutes, and 60 minutes after the end of the dropwise addition, the temperature was increased to bring the reaction tank to 110 ° C.

After maintaining the temperature at 110 ° C. for 3 hours, a gas introduction tube was mounted on the separable flask, and the blowing of a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, 39.6 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2, 2′-methylenebis (4-methyl-6-tert-butylphenol), and 0.8 parts by weight of triethylamine were added to the reaction tank. And reacted directly at 110 ° C for 9 hours.

After cooling to room temperature, a polymer solution having a polystyrene-equivalent weight average molecular weight of 8000 and an acid value of 103 mgKOH / g as measured by the GPC method was obtained.

[Synthesis Example 6: Synthesis of Binder Resin F]

While nitrogen substitution was performed, 145 parts by weight of propylene glycol monomethyl ether acetate was stirred, and the temperature was raised to 120 ° C. 20 parts by weight of styrene, 57 parts by weight of propylene methacrylate, and 82 parts by weight of a monoacrylate ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto, and further 120 hours Stirring was continued at 2 ° C for 2 hours. Then, the inside of the reaction vessel was changed to air, and 0.7 parts by weight of ginsyl (dimethylaminomethyl) phenol and 0.12 parts by weight of hydroquinone were added to 27 parts by weight of acrylic acid, and the reaction was continued at 120 ° C. for 6 hours. Thereafter, 52 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added, and the mixture was reacted at 120 ° C for 3.5 hours.

The polystyrene-equivalent weight average molecular weight Mw of the thus obtained adhesive resin F measured by the GPC method was about 15,000.

[Synthesis Example 7: Synthesis of Binder Resin G]

35 parts by weight of propylene glycol monomethyl ether acetate, 8.8 parts by weight of 1-methoxy-2-propanol, and an azo-based polymerization initiator ("V-59" manufactured by Wako Pure Chemical Industries, Ltd. were added to the reaction vessel. 1.5 parts by weight, the temperature was raised to 80 ° C in a nitrogen environment.

9.5 parts by weight of benzyl methacrylate, 6.5 parts by weight of methyl methacrylate, 3.5 parts by weight of 2-hydroxyethyl methacrylate, and 10.7 parts by weight of methacrylic acid were added dropwise thereto over 2 hours, and further stirred for 4 hours, A polymerization reaction solution was obtained.

25.5 parts by weight of propylene glycol monomethyl ether acetate, 0.05 parts by weight of p-methoxyphenol, and 0.3 parts by weight of triphenylphosphine were added to the polymerization reaction solution,

Let it dissolve. Then, 17.5 parts by weight of (3,4-epoxycyclohexyl) methyl acrylate was added dropwise and reacted at 85 ° C. for 24 hours to obtain a resin solution having an ethylenically unsaturated group on the side chain.

The polymerization average molecular weight of the thus obtained adhesive resin G measured by the GPC method was 18,000 in terms of polystyrene. The acid value measured by the neutralization titration method was 50.

In addition, from the acid value before and after the reaction, it was found that the introduction rate of the (3, 4-epoxycyclohexyl) methyl acrylate into the carboxyl group was 66%.

[Synthesis Example 8: Synthesis of Binder Resin H]

10 parts by weight of a monoacrylate ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton, 43.5 parts by weight of cyclohexyl methacrylate, 3.0 parts by weight of methyl methacrylate, and methacrylic acid 43.5 parts by weight was dissolved in 150 parts by weight of propylene glycol monomethyl ether acetate, and 1.25 parts by weight of azobisisobutyronitrile was added in a nitrogen atmosphere, and reacted at 80 ° C. for 7 hours.

The polystyrene-equivalent weight-average molecular weight Mw of the thus obtained adhesive resin H measured by the GPC method was about 7,200, and the acid value was 84.

[Synthesis Example 9: Synthesis of Binder Resin I]

While nitrogen substitution was performed, 145 parts by weight of propylene glycol monomethyl ether acetate was stirred, and the temperature was raised to 120 ° C. 10 parts by weight of styrene, 85.2 parts by weight of propylene methacrylate and 66 parts by weight of a monoacrylate ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto, and 3 parts by weight 9.00 parts by weight of 2, 2'-azobis-2-methylbutyronitrile was added dropwise for 1 hour, and the stirring was continued at 90 ° C for 2 hours.

Then, the inside of the reaction vessel was changed to air, 0.7 parts by weight of ginsyl (dimethylaminomethyl) phenol and 0.12 parts by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours.

Thereafter, 56.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added, and the mixture was reacted at 100 ° C for 3.5 hours.

The polystyrene-equivalent weight average molecular weight Mw of the thus obtained adhesive resin I measured by the GPC method was about 6000, and the acid value was 90 mgKOH / g.

[Synthesis Example 10: Synthesis of Binder Resin J]

While nitrogen substitution was performed, 145 parts by weight of propylene glycol monomethyl ether acetate was stirred, and the temperature was raised to 120 ° C.

To this were added dropwise 30 parts by weight of benzyl methacrylate, 85.2 parts by weight of propylene methacrylate, and 46 parts by weight of a monoacrylate ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton. Furthermore, 7.47 parts by weight of 2, 2'-azobis-2-methylbutyronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C for 2 hours.

Then, the inside of the reaction vessel was changed to air, 0.7 parts by weight of ginsyl (dimethylaminomethyl) phenol and 0.12 parts by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 50.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added, and the mixture was reacted at 100 ° C for 3.5 hours.

The polystyrene-equivalent weight average molecular weight Mw of the thus obtained adhesive resin measured by GPC method was about 14,000, and the acid value was 80 mgKOH / g.

[Synthesis Example 11: Synthesis of Binder Resin K]

In the same manner as the resin I obtained in Synthesis Example 9, styrene, glycidyl methacrylate, and a monoacrylate ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.) were used. polymerization.

Then, the inside of the reaction vessel was changed to air, 0.7 parts by weight of ginsyl (dimethylaminomethyl) phenol and 0.12 parts by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 50.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added, and the mixture was reacted at 100 ° C for 3.5 hours.

The polystyrene-equivalent weight average molecular weight Mw of the thus obtained adhesive resin K measured by GPC method was about 8000, and the acid value was 78 mgKOH / g.

[Synthesis Example 12: Synthesis of Binder Resin L]

While nitrogen substitution was performed, 145 parts by weight of propylene glycol monomethyl ether acetate was stirred, and the temperature was raised to 120 ° C. 10 parts by weight of styrene, 115.2 parts by weight of propylene methacrylate, and 46 parts by weight of a monoacrylate ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto. Then, 7.47 parts by weight of 2,2'-azobis-2-methylbutyronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C for 2 hours.

Then, the inside of the reaction vessel was changed to air, 0.7 parts by weight of ginsyl (dimethylaminomethyl) phenol and 0.12 parts by weight of hydroquinone were added to 58.3 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 57.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7% of triethylamine were added. The reaction was performed at 100 ° C for 3.5 hours by weight.

The polystyrene-equivalent weight average molecular weight Mw of the thus obtained adhesive resin L measured by the GPC method was about 8000, and the acid value was 100 mgKOH / g.

[Synthesis Example 13: Synthesis of Binder Resin M]

In the same manner as the resin I obtained in Synthesis Example 9, styrene, glycidyl methacrylate, and a monoacrylate ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.) were used. polymerization.

Next, the inside of the reaction vessel was changed to air, 0.7 parts by weight of ginsyl (dimethylaminomethyl) phenol and 0.12 parts by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 30.1 parts by weight of succinic anhydride and 0.7 parts by weight of triethylamine were added, and the mixture was reacted at 100 ° C for 3.5 hours.

The polystyrene-equivalent weight average molecular weight Mw of the thus obtained adhesive resin M measured by GPC method was about 9,000, and the acid value was 81 mgKOH / g.

[Synthesis Example 14: Synthesis of Binder Resin N]

In the same manner as the resin I obtained in Synthesis Example 9, styrene, glycidyl methacrylate, and a monoacrylate ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were polymerized. .

Next, the inside of the reaction vessel was changed to air, 0.7 parts by weight of ginsyl (dimethylaminomethyl) phenol and 0.12 parts by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 69.2 parts by weight of trimellitic anhydride and 0.7 parts by weight of triethylamine were added. The reaction was carried out at 100 ° C for 3.5 hours.

The polystyrene-equivalent weight average molecular weight Mw of the thus obtained adhesive resin N measured by GPC method was about 7000, and the acid value was 79 mgKOH / g.

[Synthesis Example 15: Synthesis of Binder Resin P]

114.0 parts by weight of propylene glycol monomethyl ether acetate was added to a 4-necked flask, and the temperature was raised to 85 ° C. while blowing nitrogen gas. 96.8 parts by weight of benzyl methacrylate, 33.3 parts by weight of methacrylic acid, and 4.93 parts by weight of 2, 2'-azobisisobutyronitrile were dissolved in 96.5 parts by weight of propylene glycol monomethyl ether acetate dropwise over 4 hours. Participants.

After the completion of the dropwise addition, the reaction solution was kept at 85 ° C. and further stirred for 2 hours, and thereafter, nitrogen bubbling was stopped, and the temperature was raised to 100 ° C. and stirred for 1 hour.

The polystyrene-equivalent weight average molecular weight of the thus obtained adhesive resin P measured by GPC method was 15,000, and the acid value was 180 mgKOH / g.

[Synthesis Example 16: Synthesis of Binder Resin Q]

114.0 parts by weight of propylene glycol monomethyl ether acetate was added to a 4-necked flask, and the temperature was raised to 85 ° C. while blowing nitrogen gas. 96.8 parts by weight of benzyl methacrylate, 33.3 parts by weight of methacrylic acid, and 9.85 parts by weight of 2, 2'-azobisisobutyronitrile were dissolved in 96.5 parts by weight of propylene glycol monomethyl ether acetate dropwise over 4 hours. Participants.

After the completion of the dropwise addition, the reaction solution was kept at 85 ° C. and further stirred for 2 hours, and thereafter, nitrogen bubbling was stopped, and the temperature was raised to 100 ° C. and stirred for 1 hour.

Polybenzene measured by GPC method for the thus obtained adhesive resin Q The weight average molecular weight in terms of ethylene was 8000, and the acid value was 175 mgKOH / g.

[Synthesis Example 17: Synthesis of Binder Resin R]

10 parts by weight of a monoacrylate ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton, 62.0 parts by weight of benzyl methacrylate, and 28.0 parts by weight of methacrylic acid were dissolved in propylene glycol monomethyl ether ethyl In 150 parts by weight of the acid ester, 0.65 parts by weight of azobisisobutyronitrile was added in a nitrogen atmosphere, and the reaction was performed at 80 ° C. for 7 hours.

The polystyrene-equivalent weight average molecular weight Mw of the thus obtained adhesive resin R measured by the GPC method was about 17,000, and the acid value thereof measured by the neutralization titration method was 102.

[Synthesis Example 18: Synthesis of Binder Resin S]

114 parts by weight of propylene glycol monomethyl ether acetate was added to a 4-necked flask, and the temperature was raised to 85 ° C. while blowing nitrogen gas. 114 parts by weight of benzyl methacrylate, 26 parts by weight of methacrylic acid, and 9.9 parts by weight of 2, 2'-azobisisobutyronitrile were dissolved in 96 parts by weight of propylene glycol monomethyl ether acetate dropwise over 4 hours. In the adult.

After the dropwise addition, the reaction solution was further stirred for 2 hours while maintaining the temperature at 85 ° C. After that, nitrogen gas bubbling was stopped, and the temperature was raised to 100 ° C and stirred for 1 hour. 0.7 part by weight of tetraethylammonium chloride was added thereto, and the mixture was stirred and dissolved at 80 ° C. Then, 16 parts by weight of acrylic acid-3,4-epoxycyclohexyl-1-methyl ester and propylene glycol were added dropwise over 1 hour. A solution of 24 parts by weight of monomethyl ether acetate.

The reaction solution was stirred at 80 ° C for 30 hours to obtain a polystyrene-equivalent weight average molecular weight measured by GPC method of 8000, Polymer solution with an acid value of 90 mgKOH / g.

[Synthesis Example 19: Synthesis of Adhesive Resin D1]

Except that the methacrylic acid in Synthesis Example 3 (Synthesis of Adhesive Resin D) was changed to acrylic acid, synthesis was performed under the same conditions as in Synthesis Example 3, and a weight average molecular weight of 8200 and an acid value of 101 mgKOH / g of polymer solution.

[Synthesis Example 20: Synthesis of Adhesive Resin E1]

Except that the cyclohexyl methacrylate in Synthesis Example 3 (Synthesis of Adhesive Resin D) was changed to methyl methacrylate, the synthesis was performed under the same conditions as in Synthesis Example 3 to obtain a weight average molecular weight of 8000. Polymer solution with an acid value of 102 mgKOH / g.

[1] Examples 1 to 4 and Comparative Examples 1 to 2: C. I. Example of use of pigment green 36.

[Preparation of coloring composition]

CI Pigment Green 36 having an average primary particle diameter of 0.015 μm as a pigment, 6.85 parts by weight, CI Pigment Yellow 150 having an average primary particle size of 0.025 μm as an average primary particle diameter of 2.93 parts, and propylene glycol monomethyl ether acetate 60.00 as a solvent. Parts by weight, 1.96 parts by weight of various dispersants described in Table-1 as a dispersant, and 3.26 parts by weight, based on solid content, of various binder resins described in Table-1 as a dispersant. 225 parts by weight of 0.5 mm zirconia beads were filled into a stainless steel container together, and dispersed for 6 hours by a paint shaker to prepare a green pigment dispersion liquid.

Next, each component described in Table-2 was mixed with the obtained green pigment dispersion liquid to prepare a coloring composition. Furthermore, the so-called "solvent" in Table-2 The "agent" is different from the solvent contained in the "green pigment dispersion", and it is prepared separately.

In the table, the dispersant A ′ and the dispersant C are the compounds obtained in the above Synthesis Examples 2 and 3, respectively, and the dispersant B ′ is the following compound.

Dispersant B ': "Solsperse 24000GR" manufactured by Lubrizol

The adsorption group has the following structure, a polymer dispersant composed of a polyester acid amidoamine salt having an amine value of 39 mgKOH / g and an acid value of 33 mgKOH / g.

With respect to the obtained colored composition, changes in viscosity, dissolution time of the colored resin film, and contrast were measured. The measurement methods are described below, and the measurement results are shown in Table-1.

[Viscosity change of coloring composition]

Using an E-type viscosity meter "RE-80L" manufactured by Toki Sangyo Co., Ltd., the coloring compositions obtained in the above examples and comparative examples were measured separately.

‧ Viscosity (20 rpm) immediately after manufacture (preparation) and ‧ standing in a constant temperature bath at 23 ° C for 2 weeks.

Comparing the viscosity change rate during the 14th day, those who are less than 4% are marked as ○, those who are more than 4% and less than 10% are marked as △, and those who are more than 10% are marked as ×.

The results are shown in Table-1.

[Determination of dissolution time]

The coloring compositions obtained in the above Examples and Comparative Examples were each spin-coated on a glass substrate on which chromium was vapor-deposited, and pre-baked on a hot plate at 80 ° C. for 3 minutes to prepare dry coating films.

Furthermore, the rotation speed during spin coating was adjusted so that the obtained dry coating film had a film thickness with a color coordinate of y = 0.600.

After exposing the obtained dry coating film at 60 mJ / cm ² through a mask pattern using a high-pressure mercury lamp, spray development was performed using a 0.04% by weight potassium hydroxide aqueous solution (developing solution temperature of 23 ° C.) at a pressure of 0.25 MPa. The time until the dry coating film was dissolved to expose the substrate surface, that is, the "dissolution time of the colored composition" was measured.

Regarding the dissolution time of the coloring composition obtained in each of the examples and comparative examples, those with less than 100 seconds were recorded as ○, those with 100 seconds or more and less than 120 were recorded as Δ, and those having 120 or more were recorded as ×. The results are shown in Table-1.

[Measurement of contrast]

Using the colored composition obtained in each Example and Comparative Example, spin coating and pre-baking were performed on a transparent glass substrate in the same manner as in the above [Measurement of Dissolution Time]. Except that the photomask pattern is not interposed, the obtained dry coating film is exposed in the same manner as in the above [Measurement of Dissolution Time], and under the same conditions as in the above [Measurement of Dissolution Time] Development. Then, after washing with a sufficient amount of water, it was dried with clean air.

The obtained dried coating film was baked in a 230 ° C. oven for 30 minutes to prepare a colored resin film. The thickness of the obtained colored resin film was about 2.4 μm. In this way, a coloring plate having a colored resin film on a transparent glass substrate was produced.

Figures 2 (a) and (b) are schematic diagrams for explaining the method for measuring the chromaticity of parallel transmitted light and orthogonal transmitted light of a coloring plate.

First, as shown in FIG. 2 (a), polarizing plates 33 and 35 are laminated on both sides of the obtained colored plate (hereinafter referred to as "colored plate 34"), and the polarization axes of the polarizing plates 33 and 35 are parallel to each other. From the side of one side of the polarizing plate 35 The light 36 of the backlight 37 uses the "BM-5A" 32 manufactured by TOPCON TECHNOHOUSE, a color luminance meter, and measures the brightness Lp (brightness of parallel transmitted light) of the light passing through the other polarizing plate 33 under a field of view of 2 °.

Then, as shown in FIG. 2 (b), in a state where the polarization axes of the polarizing plates 33 and 35 are orthogonal to each other, the light 36 of the backlight 37 is irradiated from the side of the polarizing plate 35, and the color luminance meter 32 is used to In the same manner as the above-mentioned Lp, the brightness Lc (brightness of orthogonally transmitted light) of the light transmitted through the other polarizing plate 33 is measured.

It should be noted that the backlight 37 uses a light emission spectrum as shown in FIG. 3. The measurement of the spectrum was performed using a spectroradiometer CS-1000A manufactured by Konica Minolta, and the measurement was performed using a filter "ND Filter ND4" manufactured by Kenko Corporation in order to control the amount of light and make the measurement easy.

The polarizing plates 33 and 35 are those having the spectral characteristics shown in FIG. 4.

The contrast of the colored plates of each of the examples and comparative examples was calculated from the brightness Lp of the parallel transmitted light and the brightness Lc of the orthogonal transmitted light by using the formula Lp / Lc. In addition, the blank test value at the time of measurement using the basic glass instead of the coloring plate of each Example and the comparative example was 12,800. The results are shown in Table-1.

[2] Examples 5 to 36 and Comparative Examples 3 to 7: Examples of using zinc bromide phthalocyanine pigments.

[2-1] Examples 5 to 6 and Comparative Examples 3 to 4: Examples of using zinc bromide phthalocyanine pigments.

[Preparation of pigment dispersion]

7.24 parts by weight of zinc bromide phthalocyanine obtained in Synthesis Example 1 and 2.54 parts by weight of CI Pigment Yellow 150, 60.00 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 1.96 parts by weight of various components described in Table-3 as a dispersant in terms of solid content, and a table as a dispersion resin The binder resin described in -3 was filled into a stainless steel container with 3.26 parts by weight in terms of solid content and 225 parts by weight of zirconia beads having a diameter of 0.5 mm, and dispersed for 6 hours by a paint shaker to prepare a pigment dispersion liquid. T, U, V and W.

Among them, the dispersants A and B in Table-3 are the following compounds.

[Dispersant A: Dispersant "BYK-LPN 6919" manufactured by BYK Chemical Co., Ltd.]

It is a methacrylic AB block copolymer. The amine value is 121 mgKOH / g and the acid value is less than 1 mgKOH / g.

About 100 mole% of the repeating units having a functional group containing a nitrogen atom contained in the B block have a structure represented by the following formula (a), and the repeating unit represented by the following formula (b) is in A The proportion in the blocks was 11 mol%.

[Chemical 33]

[Dispersant B: "Disperbyk 2000" manufactured by BYK Chemical Company]

It is a methacrylic AB block copolymer composed of an A-block having a lipophilic property and a B-block having a functional group containing a nitrogen atom. The functional group (adsorbing group) containing a nitrogen atom mainly has the following structure,

A block copolymer with an amine value of about 10 mgKOH / g and a main chain of methacrylic acid.

[Viscosity change of pigment dispersion]

Regarding the pigment dispersion liquids T, U, V, and W obtained in Examples 5 to 6 and Comparative Examples 3 to 4, the E-type viscosity meter "RE-80L" manufactured by Toki Sangyo Co. was used to measure the viscosity immediately after preparation. And the viscosity after standing for 7 days in a constant temperature bath at 23 ° C (both 20 rpm). The results are shown in Table-4.

According to Table-4, the viscosity change rate after 7 days is 2% or less in the pigment dispersion liquids of Examples 5 and 6. In contrast, the pigment dispersion liquids of Comparative Examples 3 and 4 without using the dispersant of the present invention Medium is 100% or more.

[Preparation of coloring composition]

The other components were mixed into each of the above-mentioned pigment dispersions to prepare the coloring compositions shown in Table-5. In addition, "Solvent 1" and "Solvent 2" in Table-5 are different from the solvent contained in the pigment dispersion liquid, and they are formulated separately.

[Measurement of contrast]

Using a spin coater, apply the colored composition obtained in Examples 5 to 6 and Comparative Examples 3 to 4 on a 50 mm square and 0.7 mm thick glass substrate ("AN100" manufactured by Asahi Glass Co., Ltd.), It was then dried at 80 ° C for 3 minutes.

In addition, the rotation speed during spin coating is adjusted so that the obtained dry coating film has a film thickness with a color coordinate of y = 0.600.

Then, a full-surface exposure process was performed using a 2 kW high-pressure mercury lamp at an exposure amount of 300 mJ / cm ² . Thereafter, development was performed at a developing solution temperature of 23 ° C. using a 0.1% by weight sodium carbonate aqueous solution. Subsequently, a spray-washing treatment was performed at a water pressure of 3 kg / cm ² for 30 seconds, and a thermosetting treatment was performed at 230 ° C. for 30 minutes to form a colored resin film. In this way, a coloring plate having a colored resin film on a transparent glass substrate was produced.

Then, the contrast of the obtained colored plate was measured. The measurement method is the same as that described in [Measurement of Contrast] in [1] above. The measurement results are shown in Table-6.

According to the results of Table-4 and Table-6, it can be seen that the colored composition of Examples 5 to 6 using the dispersant of the present invention has better dispersion stability than the colored composition of Comparative Examples 3 to 4, and satisfies high requirements. Contrast, which is extremely useful.

[2-2] Examples 7 to 15 and Comparative Examples 5 to 6: Examples using [2-1-1] resin.

[Preparation of pigment dispersion]

A green pigment dispersion liquid X was prepared in the same manner as in the above-mentioned pigment dispersion liquid V except that the binder resin E was used as the dispersion resin. (It is used in Comparative Example 5 described later.)

[Preparation of coloring composition]

In the ratio shown in Table-7, the pigment dispersion liquid T (the pigment dispersion liquid X in Comparative Example 5 and the pigment dispersion liquid W in Comparative Example 6), a solvent, a binder resin, and a polymerizable monomer were used. The coloring compositions of Examples 7 to 15 and Comparative Examples 5 to 6 were prepared by mixing the photopolymer, the photopolymerization starting component, and the surfactant. In addition, the numerical value in Table-7 is content (weight part). In Table-7, ﹡ 1 (Comparative Example 5) is the amount (content) of pigment dispersion liquid X, and ﹡ 2 (Comparative Example 6) is the amount of pigment dispersion liquid Y used.

[Viscosity change of coloring composition]

The colored composition obtained in Examples 7 to 15 and Comparative Examples 5 to 6 was measured using an E-type viscosity meter "RE-80L" manufactured by Toki Sangyo Co., Ltd.

‧Viscosity (20 rpm) after storage at 23 ° C for 1 day, and after standing for 7 days in a 35 ° C thermostatic bath. The results are shown in Table-8.

In addition, the "viscosity change rate" in Table-8 is simply expressed as the ratio of the difference between the viscosity of "after 7 days" and the viscosity of "after 1 day of preparation" to the viscosity of "after 1 day of preparation".

According to Table-8, comparing the change rate of viscosity (viscosity increase rate) after standing at 35 ° C for 7 days, it can be seen that the viscosity of the colored composition of Examples 7 to 13 using [2-1-1] resin decreases, or Only 1% viscosity increase compared with the coloring groups of Examples 14 and 15 using other adhesive resins Compared with the product, the viscosity stability is higher.

On the other hand, it was found that Comparative Examples 4 and 5 in which the dispersant of the present invention was not used are not suitable for producing a color filter because they are rapidly cured.

[Measurement of contrast]

After the colored composition obtained in Examples 7, 14 and 15 was stored at 23 ° C for 1 day, the colored composition was prepared in the same manner as in [Measurement of Contrast] in [2-1] above. Coloring board.

In addition, the colored compositions obtained in Examples 7, 14 and 15 are prepared to be respectively

‧ Those who stored at 23 ° C for 7 days, and ‧ Those who stored at 23 ° C for 12 days, and used these to make colored plates in the same manner.

About the produced colored plates, the contrast was measured in the same manner as in [Measurement of Contrast] in [2-1] above. The results are shown in Table-9.

According to Table-9, it can be seen that the coloring composition of Example 7 using [2-1-1] resin can maintain high contrast for a longer period of time than the coloring composition of Examples 14 and 15 using other binder resins. , So better.

[Determination of dissolution time]

The coloring compositions obtained in Examples 8 to 15 were each spin-coated on a glass substrate on which chromium was vapor-deposited, and pre-baked on a hot plate at 80 ° C. for 3 minutes to prepare a dry coating film. Furthermore, the rotation speed during spin coating was adjusted so that the obtained dry coating film had a film thickness with a color coordinate of y = 0.600.

Next, the obtained dry coating film was exposed at 60 mJ / cm ² through a linear mask pattern with a width of 50 μm and a length of 3 mm using a high-pressure mercury lamp, and then a 0.04% by weight potassium hydroxide aqueous solution (developing solution temperature of 23 ° C.) was used. Spray development was performed at a pressure of 0.25 MPa.

The time taken to dissolve the colored composition in the unexposed portion in the developing solution to expose the substrate is the dissolution time of the colored composition. The results are shown in Table-10.

[Determination of Defects in Linear Patterns]

Using the colored composition obtained in Examples 8 to 15, a dry coating film was formed on the glass substrate on which chromium was vapor-deposited in the same manner as in the above-mentioned [Measurement of dissolution time], and exposed through a photomask pattern and development. The development time was set to twice the dissolution time measured in the above [Measurement of Dissolution Time].

After development, it was washed with a sufficient amount of water and then dried with clean air. After that, it was baked in an oven at 230 ° C. for 30 minutes to form a linear pattern composed of a colored resin film. The thickness of the colored resin film is about 1.8 μm.

Ten linear patterns were observed at a magnification of 10 using an optical microscope, and the recesses at the edges of the lines were counted as the number of defects. This was repeated twice to confirm reproducibility, and the average value was calculated. The results are shown in Table-10.

In addition, a microscope observation diagram of a representative example of the linear pattern is shown in FIG. 5.

According to Table-10, it is known that the dissolution time of Examples 8 to 13 using the coloring composition containing [2-1-1] resin is shorter than 60 seconds, compared to Examples 14 and 15 using other binder resins. Better developability.

It was also found that the colored composition of Example 13 containing a compound (pentaerythritol tetraacrylate. Molecular weight: 352, double bond equivalent: 88) having a molecular weight of 400 or less and a double bond equivalent of 110 or less, as a polymerizable monomer. The number of defects of the linear pattern is particularly small, so that a pattern with good linearity is obtained.

[2-3] Examples 16 to 20 and Comparative Example 7: Examples using [2-1-2] resin as a binder resin [Preparation of pigment dispersion]

A pigment dispersion liquid Y was prepared in the same manner as in the above-mentioned pigment dispersion liquid T except that the binder resin R was used as the dispersion resin. (It is used in Comparative Example 7 described later.)

[Preparation of coloring composition]

As shown in Table-11, the components were mixed to prepare a colored composition. In (wherein Pigment Dispersion Liquid T was used in Examples 16 to 20, and Pigment Dispersion Liquid Y was used in Comparative Example 7), the expressions such as "dispersion resin D" in Table-11 mean "using a binder resin D as a dispersion resin. "

In addition, the "solvent 1" and "solvent 2" in Table-11 represent solvents that are newly prepared in addition to the solvents contained in the "pigment dispersion".

[Determination of dissolution time]

Using the coloring compositions obtained in Examples 16 to 20 and Comparative Example 7, the dissolution time of the coloring composition was measured in the same manner as in the item [Measurement of Dissolution Time] of the above [2-2]. Among them, a linear mask pattern with a width of 25 μm was used, and the distance between the mask pattern and the substrate was fixed at 150 μm, and exposure was performed. The measurement results of the dissolution time are shown in Table-12.

[Determination of Defects in Linear Patterns]

Using the colored compositions obtained in Examples 16 to 20 and Comparative Example 7, the number of defects was measured in the same manner as in the above [2-2] [Measurement of Defects in Linear Patterns]. This was repeated twice to confirm reproducibility, and the average value was calculated. The results are shown in Table-12.

From the results of Table-12, it is clear that the coloring composition of Examples 16 to 20 using [2-1-2] resin has a shorter dissolution time and better developability. In addition, it was found that a pattern having fewer defects had a better linearity.

[2-4] Examples 21 to 29: Using an oxime ester compound as a photopolymerization start Examples of agents. [Preparation of coloring composition]

57.78 parts by weight of the pigment dispersion liquid T, 25.93 parts by weight of propylene glycol monomethyl ether acetate, 8.00 parts by weight of ethyl 3-ethoxypropionate, and other ingredients were mixed to prepare the colors shown in Table-13.组合 物。 Composition.

The photopolymerization starting components 5 to 8 (oxime ester-based initiators a, b, c, and d) in Table-13 are the following compounds, respectively.

(Oxime ester starter a)

(Oxime ester starter b)

(Oxime ester starter c)

(Oxime ester-based initiator d: "Irgacure OXE02" manufactured by Ciba Specialty Chemicals)

[Determination of dissolution time]

Using the coloring compositions obtained in Examples 21 to 29, the dissolution time of the coloring composition was measured in the same manner as in the item [Measurement of dissolution time] of the above [2-3]. Among them, the film thickness of the prepared dry coating film is about 2.5 μm. The measurement results of the dissolution time are shown in Table-14.

[Determination of line width]

A linear pattern obtained in the same manner as in the above [Measurement of Dissolution Time] was observed with an optical microscope, and the line width was measured. The results are shown in Table-14.

[Foreign body evaluation]

For the colored compositions obtained in Examples 21 to 29,

(iii) Those who were allowed to stand at 23 ° C for one day after preparation, and (iv) Those who were allowed to stand at 23 ° C for one day and stored in a constant temperature bath at 35 ° C for six days, were spin-coated on 5 cm square glass substrates ( "AN100" manufactured by Asahi Glass Co., Ltd. was heated at 80 ° C for 3 minutes, and exposed at 60 mJ / cm ² to form a dry coating film.

Furthermore, the rotation speed of the spin coating is adjusted so that the film thickness of the dry coating film is between 2 and 3 μm.

The entire surface of the obtained dried coating film was observed with an optical microscope at a magnification of 5 times, and the number of foreign materials was measured. The results are shown in Table-14.

In Table-14, ○ means that there are no foreign matters, ○ _△ means that there are 5 or less foreign matters, and △ means that there are 6 or more foreign matters.

[NMP resistance]

The glass substrate on which the dry coating film was formed in the same manner as in (iii) in the above [foreign substance evaluation] was set in a sample bottle containing N-methylpyrrolidone (NMP) so as to have a length Half was immersed in N-methylpyrrolidone (NMP), capped, and left to stand at 23 ° C for 30 minutes.

After the substrate is taken out, it is washed with water and dried by blowing compressed air.

Using an optical microscope, the vicinity of the boundary between the non-impregnated portion and the impregnated portion in the dry coating film on the substrate was observed at a magnification of 5 times. The results are shown in Table-14.

In addition, the surface state of the observation part was evaluated in Table-14 as follows.

○: No difference from the impregnated part impregnated with NMP, and the surface is smooth

○ _△ : A small amount of precipitates were visible on the surface. The surface of the NMP non-impregnated portion becomes rough, or although it is not obvious, the boundary between the NMP impregnated portion / non-impregnated portion can still be determined.

(Triangle | delta): Obvious deposits are visible on the surface, and the boundary line of an NMP impregnated part / non-impregnated part can be clearly discerned.

From the results in Table-14, it can be seen that Examples 21 to 25 using an oxime ester compound as a photopolymerization initiator (photopolymerization initiator) are compared with Examples 26 to 29 using other photopolymerization initiators. No foreign matter is generated and NMP resistance is excellent. In addition, Example 25, in which an oxime ester compound and an acetophenone derivative were used as the photopolymerization starting component, showed that the total content of the photopolymerization starting component was the same or less compared with other examples, but showed more High sensitivity (can obtain thicker line width patterns). [2-5] Examples 30 to 36: Examples using an aromatic carboxylic acid-based compound.

To 10.55 parts by weight of the pigment dispersion liquid T, 5.96 parts by weight of propylene glycol monomethyl ether acetate and 0.42 parts by weight of a binder resin E, and a photopolymerization initiator "Irgacure OXE02" manufactured by Ciba Refining Co., Ltd. (chemical Refer to the "oxime ester-based initiator d" in the above [2-5] for the structure and "Irgacure 907" (2-methyl-1- [4- (methylthio) phenyl) manufactured by Ciba Refining Co., Ltd. ]-2- Phenylpropane-1-one) each 0.10 parts by weight, 0.77 parts by weight of pentaerythritol tetraacrylate as a polymerizable monomer (wherein, only 0.86 parts by weight in Example 36), and the aromatics described in Table-16 0.085 parts by weight of a family carboxylic acid compound (or a compound to be compared therewith) to prepare a colored composition.

The aromatic carboxylic acid compounds (and the compounds to be compared with them) used in the examples are shown in Table 15 below.

[Evaluation of colored composition]

For the colored composition obtained in Examples 30 to 36

(v) those who are left to stand at 23 ° C for one day after preparation, and (vi) those who (v) are further left in a constant temperature bath at 35 ° C for six days, The following evaluations were performed. The results are shown in Table-16. [Viscosity change of composition]

Using the E-type viscosity meter "RE-80L" manufactured by Toki Sangyo Co., Ltd., the viscosity of the coloring composition (20) obtained in Examples 30 to 36 and left to stand by the method of (v) or (vi) above (20) rpm). In addition, the "viscosity change rate" in Table-16 refers to the difference between the viscosity of "and then 35 ° C, 6 days later" and the viscosity of "23 ° C, 1 day later" relative to "after standing at 23 ° C for 1 day" The ratio of viscosity. The measurement results are shown in Table-16.

[Determination of Defects in Linear Patterns]

The coloring compositions obtained in Examples 30 to 36 and left to stand by the method of (v) or (vi) above were respectively measured with [Measurement of Defects in Linear Patterns] described in [2-2] above. Items are measured in the same way. In addition, each coloring composition (v) and (vi) of each Example was measured twice, and the average value was calculated | required. The measurement results are shown in Table-16.

[Determination of line width]

The coloring compositions obtained in Examples 30 to 36 and left to stand by the method of (v) or (vi) above were respectively used in the same manner as the above [2-4] [Measurement of Line Width] Perform the measurement. The results are shown in Table-16.

[6-4] Measurement of dissolution time

The coloring compositions obtained in Examples 30 to 36 and left to stand in the method (v) or (vi) above were respectively used in the same manner as the above [2-3] [Measurement of dissolution time] Perform the measurement. The results are shown in Table-16.

According to Table-16, it can be seen that Examples 30 to 32 containing aromatic carboxylic acid compounds have higher viscosity stability and shorter dissolution time (excellent developability) than Examples 33 to 36 not containing the compound. Solubility decreases over time. In addition, it can be seen that the chronology of the line width is reduced (the chronology of sensitivity is decreased) is less, and the chronology of the defect is also increased less. [3] Examples 37 to 43: C. I. Pigment Red 254 and other use examples.

[Preparation of pigment dispersion] (1) Preparation of P.R. 254 pigment dispersion

Added 8.50 parts by weight of CI Pigment Red 254 as a red pigment, 6.23 parts by weight of the dispersant A based on solid content conversion, 2.83 parts by weight of the resin H obtained in Synthesis Example 8, based on solid content conversion, and propylene glycol monomethyl ether as a solvent 50.16 parts by weight of acetate was filled into a stainless steel container together with 225 parts by weight of zirconia beads having a diameter of 0.5 mm, and dispersed in a paint shaker for 6 hours to prepare a PR 254 pigment dispersion.

(2) Preparation of P. R. 177 / P. Y. 150 pigment dispersion

CI Pigment Red 177, which is 22.40 parts by weight of a red pigment, CI Pigment Yellow Y150, which is 5.60 parts by weight of a yellow pigment, and 8.48 parts by weight of a dispersant "Disperbyk 2001" manufactured by BYK Chemical Co., Ltd., Synthesis Example 18 Resin S obtained in 9.03 parts by weight based on solid content conversion and 157.66 parts by weight of propylene glycol monomethyl ether acetate as a solvent were filled into a stainless steel container together with 675 parts by weight of zirconia beads with a diameter of 0.5 mm, and the paint was vibrated The machine was dispersed for 6 hours to prepare a PR 177 / PY 150 pigment dispersion.

[Preparation of coloring composition]

To 3.87 parts by weight of the above PR 254 pigment dispersion and 4.15 parts by weight of the above PR 177 / PY 150 pigment dispersion, 5.63 parts by weight of propylene glycol monomethyl ether acetate was added, and the resin F obtained in Synthesis Example 6 was converted by solid content. 0.44 parts by weight, 0.05 parts by weight of Ciba Refining Company's photopolymerization initiator "Irgacure OXE02" (for the chemical structure, refer to "oxime ester-based initiator d" in [2-5] above), Ciba Refining The company's photopolymerization initiator "Irgacure 907" (2-methyl-1- [4- (methylthio) phenyl] -2- Phenylpropane-1-one) 0.07 parts by weight, 0.003 parts by weight of the surfactant "F475" manufactured by Dainippon Ink Co., and 0.70 parts by weight of "TO1382" manufactured by Toa Kosei Corporation as a polymerizable monomer 0.78 parts by weight in Example 43), and 0.08 parts by weight of the aromatic carboxylic acid-based compound (or a compound to be compared therewith) described in Table-17 to prepare a red colored composition.

The aromatic carboxylic acid compounds (and the compounds to be compared with them) used in the examples are shown in Table 15 above.

[Evaluation of colored composition]

For the colored compositions obtained in Examples 37 to 43

(v) Those who were allowed to stand at 23 ° C for one day after preparation, and (vi) Those who were (v) allowed to stand in a constant temperature bath at 35 ° C for 6 days were each evaluated as follows. The results are shown in Table-17.

[Viscosity change of composition]

Using an E-type viscometer "RE-80L" manufactured by Toki Sangyo Co., Ltd., the viscosity of the colored composition obtained in Examples 37 to 43 and left to stand by the method of (v) or (vi) above was used. (20 rpm). again

The "viscosity change rate" in Table-17 is the ratio of the difference between the viscosity of "further 35 ° C, 6 days later" and the viscosity of "23 ° C, 1 day later" to the viscosity of "23 ° C, 1 day later". To represent. The measurement results are shown in Table-17.

According to Table-17, it can be seen that Examples 37 to 39 containing aromatic carboxylic acid compounds had less increase in viscosity over time and higher viscosity stability than Examples 40 to 43 not containing the compound.

The present invention has been described in detail and with reference to specific embodiments, but it should be understood by those skilled in the art that various changes or modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application (Japanese Patent Application No. 2007-163914) filed on June 21, 2007, Japanese Patent Application (Japanese Patent Application No. 2007-196441) filed on July 27, 2007, and February 6, 2008 Japanese Patent Application (Japanese Patent Application No. 2008-026120) filed on January 7, 2008, Japanese Patent Application (Japanese Patent Application No. 2008-031884) filed on February 13, 2008, Japanese Patent Application (Japanese Patent Application, filed on April 7, 2008) 2008-099747) and Japanese Patent Application (Japanese Patent Application No. 2008-143372) filed on May 30, 2008, the contents of which are incorporated herein by reference.

(Industrial availability)

The present invention exerts the following useful effects and has great industrial use value.

(1) It is possible to disperse highly micronized pigments in recent years with a small amount of addition. As a result, pigment dispersions and coloring of color filters with high transmittance, high contrast, and low film thickness can be produced.组合 物。 Composition.

(2) In particular, it is possible to provide pigment dispersion liquids and color filters that achieve the problems that exist when using zinc bromide phthalocyanine green pigments for the purpose of increasing the brightness of green pixels. Coloring composition for light sheet.

(3) A color filter coloring composition having the following advantages: It has good solubility in the developer and can be developed within a specific time during the development step; no undissolved matter of the colored resin composition remains on the non-image portion of the substrate; excellent adhesion to the substrate; no hardening When the image forming ability decreases, a high transmittance can be produced. High contrast. Low film thickness color filter.

(4) By using the coloring composition for a color filter described above, a high-quality color filter can be provided.

(5) A high-quality liquid crystal display device and an organic EL display using the above color filters can be provided.

10‧‧‧ transparent support substrate

20‧‧‧ pixels

30‧‧‧ Organic protective layer

32‧‧‧Color Brightness Meter

33, 35‧‧‧ polarizing plates

34‧‧‧ coloring board

36‧‧‧light

37‧‧‧ backlight

40‧‧‧ inorganic oxide film

50‧‧‧ transparent anode

51‧‧‧ Hole injection layer

52‧‧‧ Hole Transmission Layer

53‧‧‧Light-emitting layer

54‧‧‧ Electron injection layer

55‧‧‧ cathode

100‧‧‧Organic EL element

500‧‧‧Organic luminous body

FIG. 1 is a schematic cross-sectional view showing an example of an organic EL element including a color filter of the present invention.

Figures 2 (a) and (b) are schematic diagrams illustrating the method for measuring the chromaticity of parallel transmitted light and orthogonal transmitted light of the coloring plate in the examples.

FIG. 3 is a graph showing the emission spectrum of the backlight light source used when measuring the chromaticity coordinates (x, y) of the XYZ colorimetric chromaticity diagram of the produced pixel and the contrast ratio in the embodiment.

FIG. 4 is a diagram showing a spectrum showing characteristics of a polarizing plate used in the contrast measurement in the examples.

FIG. 5 is a diagram showing a representative example of a linear pattern (pixel) used for measuring defects in the Examples by using a microscope. (a) is a pattern without defects, (b) is a pattern with 57 defects, and (c) is a pattern with 100 or more defects.

Claims (24)

A pigment dispersion, characterized in that it contains a pigment, a solvent, a dispersant, and a dispersing resin; the pigment contains zinc bromide phthalocyanine; the solvent contains propylene glycol monomethyl ether acetate; and the dispersant contains a solvent A block copolymer composed of A block and B block having a functional group containing a nitrogen atom. The amine value of the dispersant is 100 mgKOH / g or more and 140 mgKOH / g or less in terms of effective solid content (but 100 mgKOH is excluded). / g); in the above block copolymer, the B block system contains a repeating unit represented by the following formula (ii); in the above block copolymer, the A block contains 5 to 40 mol%. Part of the structure represented by formula (IV); (Wherein, R ⁴¹ and R ⁴² each independently represent a cyclic or chain alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, and R ⁴³ represents one having 1 or more carbon atoms. Alkylene, R ⁴⁴ represents a hydrogen atom or a methyl group); (In the general formula (IV), n represents any integer from 1 to 5; R ⁵⁰ represents a hydrogen atom or a methyl group). For example, the pigment dispersion liquid according to the first patent application scope further contains an aromatic carboxylic acid-based compound. For example, the pigment dispersion liquid according to the second patent application range, wherein the aromatic carboxylic acid compound is a compound represented by the following general formula (VI), (In the above general formula (VI), Z ¹ represents a methylene group or -O-, and m represents an integer of 0 to 3; wherein, when m is 2 or 3, m Z ¹ may be the same or different; X ³ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, benzyl, phenethyl, benzyloxy, or -COOX ⁴ (Wherein X ⁴ represents an alkyl group or a phenyl group having 1 to 7 carbon atoms), these groups may each have a substituent). For example, the pigment dispersion liquid according to item 3 of the patent application scope, wherein the compound represented by the general formula (VI) is a phthalic acid monoester compound. For example, in the pigment dispersion liquid of claim 1 or 2, in the above block copolymer, more than 20 mol% of the repeating units having a functional group containing a nitrogen atom are those having primary to tertiary amine groups. Repeating unit. For example, in the pigment dispersion liquid of claim 1 or 2, in the above block copolymer, the repeating unit having a functional group containing a nitrogen atom is a repeating unit having a tertiary amine group, and the repeating unit is derived from ( Dimethylaminoethyl meth) acrylate. For example, the pigment dispersion liquid of claim 1 or 2, wherein the average primary particle diameter of the pigment is 0.04 μm or less. A coloring composition for a color filter, characterized in that it contains a pigment, a solvent, a dispersant, and a binder resin; the pigment contains zinc bromide phthalocyanine; the solvent contains propylene glycol monomethyl ether acetate; and the dispersant Containing a block copolymer composed of A-block having a lipophilic property and B-block having a functional group containing a nitrogen atom, the amine value of the dispersant is 100 mgKOH / g or more and 140 mgKOH / g in terms of effective solid content. g or less (but excluding 100 mgKOH / g); in the block copolymer, the B block system contains a repeating unit represented by the following formula (ii); in the block copolymer, the A block contains 5 to 40 Moore% has a partial structure represented by the following general formula (IV); (Wherein, R ⁴¹ and R ⁴² each independently represent a cyclic or chain alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, and R ⁴³ represents one having 1 or more carbon atoms. Alkylene, R ⁴⁴ represents a hydrogen atom or a methyl group); (In the general formula (IV), n represents any integer from 1 to 5; R ⁵⁰ represents a hydrogen atom or a methyl group). For example, the coloring composition according to item 8 of the patent application scope further contains an aromatic carboxylic acid-based compound. For example, the colored composition according to item 9 of the application, wherein the aromatic carboxylic acid compound is a compound represented by the following general formula (VI) [Chem. 3] (In the above general formula (VI), Z ¹ represents a methylene group or -O-, and m represents an integer of 0 to 3; wherein, when m is 2 or 3, m Z ¹ may be the same or different; X ³ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, benzyl, phenethyl, benzyloxy, or -COOX ⁴ (Wherein X ⁴ represents an alkyl group or a phenyl group having 1 to 7 carbon atoms), these groups may each have a substituent). For example, the colored composition according to item 10 of the application, wherein the compound represented by the general formula (VI) is a phthalic acid monoester compound. For example, in the colored composition of claim 8 or 9, in the above block copolymer, more than 20 mol% of the repeating units having a functional group containing a nitrogen atom are those having primary to tertiary amine groups. Repeating unit. For example, in the colored composition of claim 8 or 9, in the above block copolymer, the repeating unit having a functional group containing a nitrogen atom is a repeating unit having a tertiary amine group, and the repeating unit is derived from ( Dimethylaminoethyl meth) acrylate. For example, the colored composition according to item 8 or 9 of the scope of patent application, wherein the average primary particle diameter of the pigment is 0.04 μm or less. For example, the coloring composition of the scope of application for patent No. 8 or 9, wherein the above-mentioned adhesive resin includes the following resins: For copolymers of epoxy-containing (meth) acrylates and other radical polymerizable monomers, Copolymer A resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy group, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of a hydroxyl group generated by the addition reaction. For example, the colored composition according to item 8 or 9 of the scope of patent application, which further contains at least one of a photopolymerization starting component and a thermal polymerization initiator. For example, the coloring composition according to claim 16 in which the photopolymerization starting component contains an oxime ester compound. For example, the colored composition according to item 17 of the application, wherein the oxime ester compound is a compound represented by the following general formula (I), [In the above general formula (I), R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms or 4 to 25 carbon atoms Heteroaralkyl, which may each have a substituent; or, R ¹ may be bonded to X or Y to form a ring; R ² represents an alkylfluorenyl group having 2 to 20 carbon atoms, and an alkenyl group having 3 to 25 carbon atoms , 4 to 8 carbon cycloalkanoyl groups, 7 to 20 carbon arylene groups, 2 to 10 carbon alkoxycarbonyl groups, 7 to 20 carbon aryloxycarbonyl groups, 2 to 20 carbon heteroaromatics Group, heteroarylfluorenyl group having 3 to 20 carbon atoms or alkylaminocarbonyl group having 2 to 20 carbon atoms, all of which may have a substituent; X represents a group which may have a substituent and is formed by condensation of two or more rings At least one of a divalent aromatic hydrocarbon group and an aromatic heterocyclic group; Y represents an aromatic group which may have a substituent]. For example, if the coloring composition of claim 18 is applied, the compound represented by the general formula (I) is a compound represented by the following structural formula (i), [In the above general formula (i), R ¹ , R ² and Y have the same meanings as in the above general formula (I); ring X ² represents a ring condensed with a benzene ring X ¹ and may be a single ring or may be a condensed ring composed of two or more of the ring configuration; and, X ² may be a ring fused with any position of the benzene ring X ^1; X ¹ and benzene ring condensed thereto of X ² may further have a substituent]. For example, the colored composition according to item 8 or 9 of the scope of patent application, which further contains a polymerizable monomer. For example, the colored composition of the scope of application for patent No. 20, wherein the polymerizable monomer is an addition polymerizable compound having at least one ethylenic double bond, the molecular weight of the compound is 650 or less and the double bond equivalent is 150 or less . A color filter is provided with a substrate and a pixel formed on the substrate, and is characterized in that a part or all of the pixel is formed using a coloring composition according to any one of claims 8 to 21 of a patent application. A liquid crystal display device having the number 22 of the scope of patent application Color filters. An organic EL display includes a color filter with the scope of patent application No. 22.