TWI688611B - Colorant dispersion liquid and manufacturing method thereof, coloring composition and manufacturing method thereof, coloring cured film, display element and solid-state imaging element - Google Patents

Abstract

The present invention provides a coloring composition that can form a coloring cured film excellent in solvent resistance, and can solve the problem of color migration when adjacent pixels are formed to form pixels of other colors or the generation of foreign matter. A coloring agent dispersion liquid, which is a coloring agent dispersion liquid containing (A) a coloring agent containing a pigment, (B) a dispersing agent, and (C) a solvent, (B) a dispersing agent contains (b1) an amine value of Y mgKOH/g And (b2) a (meth)acrylic dispersant with an amine value of X mgKOH/g (where Y>140 and 0<X<100).

Description

Colorant dispersion liquid and manufacturing method thereof, coloring composition and manufacturing method thereof, coloring cured film, display element and solid-state imaging element

The present invention relates to a coloring agent dispersion liquid, a method for manufacturing a colorant dispersion liquid, a coloring composition, a method for manufacturing a coloring composition, a coloring cured film, a display element, and a solid-state imaging element. A coloring composition used in the formation of a coloring cured film used in a reflective color liquid crystal display element, a solid-state imaging element, an organic electroluminescence (EL) display element, an electronic paper, etc., and a method of manufacturing the same A coloring cured film formed by coloring a composition, a display element and a solid-state imaging element including the coloring cured film, a coloring agent dispersion liquid used in the preparation of the coloring composition, and a manufacturing method thereof.

The following method is known: when manufacturing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is coated on a substrate and dried, and then the dried coating film is formed into a desired pattern shape A method of irradiating radiation (hereinafter referred to as "exposure") and developing, thereby arranging three primary color pixels of red, green, and blue on a substrate (so-called photolithography. For example, refer to Patent Document 1 to Patent Document 2) . Furthermore, a method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed is also known (for example, refer to Patent Document 3). In addition, a method of obtaining each color pixel by an inkjet method using a pigment-dispersed coloring resin composition is also known (for example, refer to Patent Document 4).

In recent years, the development of liquid crystal display devices has also been developed from the use of personal computers and monitors with relatively small screen areas to the use of televisions with large screens and high image quality. In TV applications, compared with existing monitor applications, higher image quality, that is, improvement in contrast and color purity is required. In order to improve the contrast, it is required that the particle size of the organic pigment used in the coloring curable composition used when forming the color filter is smaller. Furthermore, in order to improve the color purity of the display device, it is required that the content of the colorant (organic pigment, etc.) in the solid content of the colored curable composition be higher. In addition, from the viewpoint of improving the color separation of the solid-state imaging device, a higher content rate of the colorant (organic pigment, etc.) is also required.

For the above-mentioned requirements, it is necessary to make the particle size of the pigment finer and the pigment dispersion composition with higher dispersibility. For example, regarding the zinc bromide phthalocyanine pigment that has been attracting attention as a green pixel forming application due to good hue in recent years, in order to improve dispersibility, for example, the surface of the phthalocyanine pigment is usually treated with a derivative compound on the surface of the pigment Modification, using dispersants such as low molecular weight resins with polar functional groups that are easily adsorbed on the modified surface, to achieve pigment dispersibility and dispersion stability, and to obtain pigment dispersions containing pigments, surface modifiers, and dispersants . Furthermore, the obtained pigment dispersion liquid further contains a binder resin, a polymerizable compound, a photopolymerization initiator, and other components to form a photosensitive composition, which is used to form a color pattern of a color filter by photolithography, etc. Operation.

As the pigment becomes finer and the pigment content becomes higher, dispersion becomes difficult. To solve this problem, as a dispersant used in a photosensitive resin composition for color filters, it is proposed to use a solvent-soluble A pigment dispersion liquid in which an acrylic block copolymer of a block and a block having a specific amine value serves as a dispersant (for example, refer to Patent Document 5). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2-144502 [Patent Document 2] Japanese Patent Laid-Open No. 3-53201 [Patent Document 3] Japanese Patent Laid-Open No. 6-35188 [Patent Document 4] Japanese Patent JP 2000-310706 [Patent Document 5] Japanese Patent Laid-Open No. 2009-52010

[Problems to be Solved by the Invention] However, studies by the present inventors and others have found that a green pixel formed using the coloring composition described in Patent Document 5 not only has insufficient solvent resistance, but also has a difference with the green pixel. When pixels of other colors (for example, blue pixels) are formed adjacent to each other, the green pixels are contaminated by components (for example, colorants) in the coloring composition used in the formation of the pixels of other colors (hereinafter also referred to as "shifting properties") ), or a foreign object is generated at the boundary between the green pixel and pixels of other colors.

Therefore, an object of the present invention is to provide a coloring composition capable of forming a coloring cured film excellent in solvent resistance, and capable of solving the problem of color shift when adjacent pixels are formed to form pixels of other colors or the generation of foreign matter and a method for manufacturing the same. Furthermore, an object of the present invention is to provide a coloring cured film formed using the colored composition, and a display element and a solid-state imaging element including the colored cured film. In addition, an object of the present invention is to provide a coloring agent dispersion liquid suitable for the preparation of the coloring composition and a method for producing the same. [Means to solve the problem]

The inventors of the present invention conducted intensive studies and found that the above-mentioned problems can be solved by using a specific dispersant in combination.

That is, the present invention provides a coloring agent dispersion liquid, which is a coloring agent dispersion liquid containing (A) a coloring agent containing a pigment, (B) a dispersing agent, and (C) a solvent, and (B) a dispersing agent contains (b1) an amine A dispersant with a value of Y mgKOH/g and a (meth)acrylic dispersant with an amine value of X mgKOH/g (where Y>140 and 0<X<100).

The present invention also provides methods for manufacturing the coloring agent dispersion liquids (i) and (ii) described below. (I) A method for manufacturing a coloring agent dispersion liquid, which includes the step of mixing/dispersing (A) a pigment-containing coloring agent in (C) a solvent in the presence of (B) a dispersing agent For the manufacturing method, (B) the dispersant uses a first dispersant containing (b1) a dispersant with an amine value of Y mgKOH/g (where Y>140) and a (A) containing (b2) an amine value of X mgKOH/g (A Base) a second dispersant of acrylic dispersant (wherein 0<X<100). (Ii) A method for manufacturing a coloring agent dispersion liquid, which is a method for manufacturing a coloring agent dispersion liquid including a step of mixing a first dispersion liquid and a second dispersion liquid, the first dispersion liquid containing at least (b1) The first dispersant (where Y>140) and (C) solvent of the dispersant with an amine value of Y mgKOH/g, and the second dispersion contains at least (b2) (A) with an amine value of X mgKOH/g (2) The second dispersant and (C) solvent of the acrylic dispersant (wherein 0<X<100), and at least one of the first dispersion liquid and the second dispersion liquid contains (A) a coloring agent containing a pigment.

Furthermore, the present invention provides a coloring composition comprising (A) a coloring agent containing a pigment, (B) a dispersing agent, (C) a solvent, (D) a binding resin, and (E) a polymerizable compound, (B) The dispersant contains (b1) a dispersant with an amine value of Y mgKOH/g and (b2) a (meth)acrylic dispersant with an amine value of X mgKOH/g (where Y>140 and 0<X< 100).

The present invention further provides a method for manufacturing a coloring composition, which includes a step of mixing a coloring agent dispersion liquid obtained by the manufacturing method with at least (E) a polymerizable compound.

In addition, the present invention provides a colored cured film formed using the colored composition, and a display element and a solid-state imaging element including the colored cured film. It is also suitable that the display element and the solid-state imaging element of the present invention include a coloring cured film including a first colored cured film and a second cured film, and the first colored cured film is a colored cured film formed using the coloring composition, The second cured film is a coloring cured film containing an acid dye. Here, the "colored cured film" refers to pixels of various colors, a protective film, a black matrix, a spacer, an insulating film, and the like used in a display element or a solid-state imaging element. [Effect of invention]

According to the present invention, it is possible to provide a coloring composition that can form a coloring cured film excellent in solvent resistance, and can solve the problem of color shift when forming adjacent pixels to form pixels of other colors or the generation of foreign matter. Therefore, the coloring composition of the present invention can be used in various color filters including color filters for color separation of color liquid crystal display elements, solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper It is extremely suitable for the production of optical sheets.

Hereinafter, the present invention will be described in detail.

Colorant dispersion liquid Hereinafter, the constituent components of the colorant dispersion liquid of the present invention will be described in detail. -(A) Colorant-The coloring composition of the present invention contains a pigment as (A) colorant. The pigment can be used without particular limitation as long as it has colorability, and the color or material can be appropriately selected according to the use of the coloring composition. When the coloring composition of the present invention is used for forming the pixels of each color constituting the color filter, high color purity, brightness, contrast, etc. are required for the color filter, so organic pigments are preferred.

Organic pigments can be exemplified by compounds classified as pigments in the Colour Index (CI; issued by The Society of Dyers and Colourists), specifically the dye index (CI ) Name compound. CI Pigment Red 57: 1, CI Pigment Red 166, CI Pigment Red 170, CI Pigment Red 177, CI Pigment Red 179, CI Pigment Red 208, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 264 and other red pigments; CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Green 59 and other green pigments; CI Pigment Blue 15: 6, CI Pigment Blue 16, CI Pigment Blue 79, CI Pigment Blue 80, etc. Blue pigment; CI Pigment Yellow 14, CI Pigment Yellow 74, CI Pigment Yellow 83, CI Pigment Yellow 109, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 179, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 211, CI Pigment Yellow 215 and other yellow pigments; CI Pigment Orange 38 and other orange pigments; CI Pigment Violet 19, CI Pigment Violet 23 and other purple pigments.

In addition to this, the following formula can also be used:

[Chemical 1]

The indicated pigments are used as red pigments. In addition, lake pigments can also be used as pigments. Examples of the lake pigments include triarylmethane-based dyes or xanthene-based dyes that are laked with homopolyacid or heteropolyacid. The triarylmethane-based lake pigment is disclosed in, for example, Japanese Patent Laid-Open No. 2011-186043 and the like. Xanthene-based lake pigments are disclosed in, for example, Japanese Patent Laid-Open No. 2010-191304.

In the present invention, the pigment can also be purified and used by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or a combination of these methods. Moreover, the pigment can also be used by modifying the surface of the particles with resin as necessary. Furthermore, organic pigments can be used by so-called salt milling to refine primary particles. For the method of salt grinding, for example, the method disclosed in Japanese Patent Laid-Open No. 08-179111 can be used.

Among them, the coloring agent dispersion liquid of the present invention preferably contains a halogenated metal phthalocyanine pigment as a pigment. Examples of the halogenated metal phthalocyanine pigments include halogenated copper phthalocyanine pigments and halogenated zinc phthalocyanine pigments, and it is particularly preferable to contain halogenated zinc phthalocyanine pigments such as C.I. Pigment Green 58 and C.I. Pigment Green 59.

Moreover, the (A) colorant may further contain a dye. Dyes include xanthene dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, azo dyes, squarylium dyes, dipyrromethene dyes, phthalocyanine dyes, quinone imine dyes, quinoline Organic dyes such as dyes, porphyrin dyes, coumarin dyes, etc. More specifically, Japanese Patent Laid-Open No. 2010-32999, Japanese Patent Laid-Open No. 2010-254964, Japanese Patent Laid-Open No. 2011-138094, International Publication No. 2010/123071, Japanese Patent Laid-Open Organic dyes described in 2011-116803, JP 2011-117995, JP 2011-133844, JP 2011-174987, etc.

In the present invention, the pigment and the dye may be used alone or in combination of two or more.

In the present invention, from the viewpoint of making a colorant dispersion liquid having excellent dispersion stability and storage stability, (A) the content ratio of the colorant is preferably 10% by mass to 90% of all solid components of the colorant dispersion liquid % By mass, more preferably 20% by mass to 85% by mass, and from the viewpoint of forming a pixel having excellent transparency and color purity, or a black matrix having excellent light-shielding properties, it is preferably in all solid components of the coloring composition described later as 5 to 70% by mass, more preferably 10 to 60% by mass. Here, the "solid content" is a component other than the solvent (C) described later.

In the coloring agent dispersion liquid of the present invention, the content ratio of the pigment may be 20% by mass or more, further 50% by mass or more, and further 80% by mass or more relative to the total content of the (A) colorant. Make it a coloring agent dispersion liquid with excellent dispersion stability and storage stability.

-(B) Dispersant-The coloring agent dispersion liquid of the present invention contains (b1) a dispersant with an amine value of Y mgKOH/g (hereinafter also referred to as "dispersant (b1)") and (b2) an amine value of X mgKOH (g) (meth)acrylic dispersant (hereinafter also referred to as "dispersant (b2)") (where Y>140 and 0<X<100) is used as component (B). In addition, the “amine value” in the present invention means the number of mg of KOH equivalent to the acid equivalent required to neutralize 1 g of the solid content of the dispersant.

The dispersant (b1) is not particularly limited if it has an amine value greater than 140 mgKOH/g, and a urethane-based dispersant, polyethyleneimine-based dispersant, polyester-based dispersant, ( Known dispersants such as meth)acrylic dispersants. Among these dispersants, (meth)acrylic dispersants are preferred.

As the dispersant (b1) and the dispersant (b2) as the (meth)acrylic dispersant, commercially available dispersants can be used, and a dispersant synthesized by using a monomer having an amine group by a known method can also be used . Examples of commercially available (meth)acrylic dispersants include Disperbyk Dispersant (Disperbyk)-2000 (non-volatile content = 40% by mass, amine value 4 mgKOH/g), Dispersibi Gram dispersant-2001 (non-volatile component = 46% by mass, amine value 29 mgKOH/g), BYK-LPN21116 (non-volatile component = 40% by mass, amine value 29 mgKOH/g), BYK-LPN22102 (non-volatile component = 40% by mass, amine value 29 mgKOH/g) [above manufactured by BYK Corporation] etc. as a dispersant (b2).

The dispersant (b1) and the dispersant (b2) can be used alone or in combination of two or more.

From the viewpoint of forming a colored cured film having excellent solvent resistance, the amine value Y (mgKOH/g) of the dispersant (b1) is preferably Y>150, and more preferably Y>160. Moreover, from the viewpoint of preparing a coloring agent dispersion liquid having excellent storage stability, Y≦230 is preferable, and Y≦200 is more preferable.

From the viewpoint of forming a colored cured film excellent in heat resistance, the amine value X (mgKOH/g) of the dispersant (b2) is preferably X<80, and more preferably X<60.

Moreover, from the viewpoint of preparing a coloring composition excellent in storage stability, the sum of the amine value Y (mgKOH/g) of the dispersant (b1) and the amine value X (mgKOH/g) of the dispersant (b2) (Y+ X) is preferably Y+X≦400, and more preferably Y+X≦300. In addition, in the calculation of "Y+X" when using two or more dispersants (b1) with different amine values and when using two or more dispersants (b2) with different amine values, the most applied content The amine value of the dispersant (b1) and the amine value of the dispersant (b2) with the highest content.

Coloring composition of the present invention may be suitably selected dispersing agent (b1) with a dispersing agent (b2) content ratio, the content of w dispersion agent (b1) ₁ with a dispersing agent (b2) content w ratio w ₂ is ₁ / w ₂ The mass ratio is preferably 10/90 to 90/10, more preferably 15/85 to 75/25, and still more preferably 20/80 to 60/40.

The component (B) may use other dispersants other than the dispersant (b1) and the dispersant (b2). Examples of such other dispersants include carbamate-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene alkyl phenyl ether-based dispersants, and polyethylene glycols. Diester-based dispersant, sorbitan fatty acid ester-based dispersant, polyester-based dispersant, (meth)acrylic-based dispersant, etc. Commercially available products such as BYK-LPN6919 (nonvolatile content = 60% by mass) , Amine value 72 mgKOH/g, manufactured by BYK (BYK) Co., Ltd. (meth)acrylic dispersant, Dispapic dispersant-161, Dispapic dispersant-162, Dispap BYK dispersant-165, DISPABIC dispersant-167, DISPABIC dispersant-170, DISPABIC dispersant-182 (above are manufactured by BYK), Urethane-based dispersants such as Solsperse 76500 (manufactured by Lubrizol Corporation), and polyethyleneimine-based dispersants such as Solsperse 24000 (manufactured by Lubrizol Corporation), Ajisper (Ajisper) PB821, Aquisper PB822, Aquisper PB880, Aquisper PB881 (above manufactured by Ajinomoto Fine Chemical Co., Ltd.) and other polyester-based dispersants, in addition to BYK-LPN21324 (manufactured by BYK Corporation) can be used.

In the case of using a dispersant other than the dispersant (b1) and the dispersant (b2) together, the content of the other dispersant is preferably 50% by mass or less relative to the total content of the (B) dispersant, more preferably 20% by mass or less.

In the present invention, the content of (B) dispersant is preferably 5 parts by mass to 300 parts by mass, more preferably 10 parts by mass to 200 parts by mass, and even more preferably 100 parts by mass of (A) the colorant. 20 parts by mass to 100 parts by mass. By setting it as such a form, it becomes easy to obtain the desired effect of this application. In particular, by using a specific dispersant in combination with the coloring composition of the present invention, a coloring agent dispersion liquid and a coloring composition having excellent storage stability can be prepared even if the content of the dispersing agent is reduced compared to the conventional coloring composition. Therefore, it has the advantage of being able to increase the amount of other components constituting the coloring composition by the amount reduced by the dispersant. For example, the content ratio of the colorant can be increased, so that the color purity of the display element can be improved, or the color separation of the solid-state imaging element can be improved. Alternatively, the content ratio of the polymerizable compound can be increased, so that the solvent resistance of the colored cured film can be improved.

-(C) solvent-As the (C) solvent in the present invention, as long as it can disperse or dissolve the components (A) to (B) or other components constituting the coloring agent dispersion liquid, and does not react with these components Moderately volatile solvents can be selected and used appropriately.

Examples of such organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Alcohol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether (Poly)alkanediols such as ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether Monoalkyl ether; alkyl lactate such as methyl lactate and ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tert-butanol, octanol, 2-ethylhexanol, (Cyclic) alkyl alcohols such as cyclohexanol; ketone alcohols such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol mono (Poly)alkanediol monoalkyl such as diethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate Ether acetate; glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether; cyclic ethers such as tetrahydrofuran; methyl ethyl ketone, cyclohexanone, Ketones such as 2-heptanone and 3-heptanone; diacetates such as propylene glycol diacetate, 1,3-butanediol diacetate and 1,6-hexanediol diacetate;

Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl Alkoxycarboxylic acid esters such as ethyl-3-methoxybutyl propionate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, acetic acid Isoamyl ester, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, ethyl Fatty acid alkyl esters such as methyl acetate, ethyl acetate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N,N-dimethylformamide, N,N-di Acetylamine such as methylacetamide and N-methylpyrrolidone, or internal amide etc.

Among these organic solvents, from the viewpoints of solubility, pigment dispersibility, and applicability, it is preferably one or more selected from (poly)alkanediol monoalkyl ether acetate, ketol, and ketone.

In the present invention, one type of solvent may be used alone or two or more types may be used in combination.

(C) The content of the solvent is not particularly limited, but the total concentration of the components of the colorant dispersion liquid from which the solvent is removed is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, and It is preferable that the total concentration of the components of the color removal composition to be described later be 5 to 50% by mass, and more preferably 10 to 40% by mass. By setting it as such a form, dispersibility and stability can be improved, and the coloring composition excellent in coating property can be obtained.

The coloring agent dispersion liquid of the present invention may further contain other components than the components (A) to (C) as necessary. Specifically, (D) a binder resin, an additive, etc. disclosed below are mentioned, and the detail is mentioned later.

Manufacturing method of colorant dispersion liquid The colorant dispersion liquid of the present invention can be prepared by an appropriate method, for example, manufactured by (C) in a solvent, (B) in the presence of a dispersing agent, using, for example, a bead mill , Roller mills, etc., (A) the coloring agent containing the pigment is optionally crushed with (D) a part of the binding resin or other components, mixed and dispersed. In the present invention, the first dispersant containing at least the dispersant (b1) and the second dispersant containing at least the dispersant (b2) may be used as the (B) dispersant. That is, if the first dispersant contains at least the dispersant (b1), it may contain other dispersants. Furthermore, if the second dispersant contains at least a dispersant (b2), it may contain other dispersants.

Furthermore, in the present invention, the first dispersant and the second dispersant can be used in the form of separately prepared dispersion liquids. More specifically, for example, it is a method of manufacturing a coloring agent dispersion liquid in which a first dispersion liquid and a second dispersion liquid are mixed, and the first dispersion liquid contains a first dispersant and (C) containing at least a dispersant (b1) ) A solvent, the second dispersion liquid contains at least a second dispersant (b2) and a solvent (C). (A) The coloring agent containing the pigment may be contained in at least one of the first dispersion liquid and the second dispersion liquid, and may be contained in both the first dispersion liquid and the second dispersion liquid. Among them, from the viewpoint that the effects of the present invention can be more enjoyed, a method for producing a coloring agent dispersion liquid using the first dispersant and the second dispersant in the form of a separately prepared dispersion liquid is preferred.

Coloring composition The coloring composition of the present invention contains (A) a coloring agent containing a pigment, (B) a dispersing agent, (C) a solvent, (D) a binding resin, and (E) a polymerizable compound, and (B) a dispersing agent contains ( b1) A dispersant with an amine value of Y mgKOH/g and (b2) a (meth)acrylic dispersant with an amine value of X mgKOH/g (where Y>140 and 0<X<100). The coloring composition of the present invention can be prepared using the coloring agent dispersion liquid of the present invention. Specifically, the coloring agent dispersion liquid of the present invention can be prepared by containing (D) a binder resin and (E) a polymerizable compound.

-(D) Adhesive resin-The (D) adhesive resin in the present invention is not particularly limited, but it is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as "carboxyl group-containing polymer") is preferred, and for example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter also referred to as "unsaturated monomer (d1) ") A copolymer with other copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as "unsaturated monomer (d2)").

Examples of the unsaturated monomer (d1) include (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono[2-(meth)acryloyloxyethyl]ester, ω-carboxy polyhexyl Lactone mono(meth)acrylate, p-vinyl benzoic acid, etc.

One type of these unsaturated monomers (d1) may be used alone or two or more types may be used in combination.

Furthermore, the unsaturated monomer (d2) may, for example, include N-position-substituted maleimide such as N-phenylmaleimide, N-cyclohexylmaleimide; styrene, Aromatic vinyl compounds such as α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, acenaphthene; methyl (meth)acrylate, ( N-butyl meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, Polyethylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) Mono(meth)acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono(meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, (meth) Tricyclo[5.2.1.0 ^2,6 ]decane-8-yl ester, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxybenzene (meth)acrylate Ester, p-cumylphenol ethylene oxide modified (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylic acid-3,4-epoxycyclohexyl methyl ester, 3-[( (Meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethyloxetane (meth)acrylate;

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3-(vinyloxymethyl)- Vinyl ethers such as 3-ethyloxetane; polystyrene, polymethyl (meth)acrylate, poly-n-butyl (meth)acrylate, polysiloxanes, etc. in the polymer molecular chain Macromonomers having a single (meth)acryloyl group at the end.

One type of these unsaturated monomers (d2) may be used alone or two or more types may be used in combination.

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

Specific examples of the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2) include, for example, Japanese Patent Laid-Open No. 7-140654, Japanese Patent Laid-Open No. 8-259876, and Japanese Patent Laid-Open No. 10-31308, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-174224, Japanese Patent Laid-Open No. 11-258415, Japanese Patent Laid-Open No. 2000-56118, Japanese Patent Laid-Open The copolymer disclosed in 2004-101728 and the like.

Furthermore, in the present invention, for example, Japanese Patent Laid-Open No. 5-19467, Japanese Patent Laid-Open No. 6-230212, Japanese Patent Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 9-325494 , Japanese Patent Laid-Open No. 11-140144, Japanese Patent Laid-Open No. 2008-181095, etc., disclose the use of a carboxyl group-containing polymer having a polymerizable unsaturated bond such as (meth)acryloyl group in the side chain. As a binder resin.

The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as "GPC") (elution solvent: tetrahydrofuran) of the binder resin in the present invention is usually 1,000 to 100,000, preferably 3,000～50,000. By adopting such a form, the balance of coloring power and brightness, the residual film ratio of the coating, the pattern shape, the heat resistance, the electrical characteristics, and the resolution can be further improved, and the precipitation or foreign matter of the coating film can be suppressed to a high level produce.

Moreover, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, and more preferably 1.0 to 3.0. In addition, the "Mn" here means the polystyrene conversion number average molecular weight measured by GPC (elution solvent: tetrahydrofuran).

The adhesive resin in the present invention can be manufactured by a known method, for example, it can be disclosed in Japanese Patent Laid-Open No. 2003-222717, Japanese Patent Laid-Open No. 2006-259680, International Publication No. 2007/029871 manual, etc. Method to control its structure or Mw, Mw/Mn.

In the present invention, one type of adhesive resin may be used or two or more types may be used in combination.

In the present invention, the content of the (D) binder resin is usually 10 parts by mass to 1,000 parts by mass, preferably 20 parts by mass to 500 parts by mass, and more preferably 50 parts by mass relative to 100 parts by mass of the (A) colorant. Parts to 200 parts by mass. By adopting such a form, the balance of the coloring power and brightness, the developability of the coloring, the storage stability of the coloring composition, the pattern shape, and the chromaticity characteristics can be further improved, and the generation of precipitates or foreign matters in the coating film can be suppressed.

-(E) Polymerizable compound- In the present invention, the "polymerizable compound" refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include ethylenically unsaturated groups, oxetanyl groups, oxetanyl groups, and N-alkoxymethylamine groups. In the present invention, the polymerizable compound is preferably a compound having two or more (meth)acryloyl groups or a compound having two or more N-alkoxymethylamine groups.

Specific examples of the compound having two or more (meth)acryloyl groups include a polyfunctional (meth)acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, modified with caprolactone Polyfunctional (meth)acrylate, polyfunctional (meth)acrylate modified with alkylene oxide, polyfunctional (meth)acrylic acid obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate Carbamate, polyfunctional (meth)acrylate having a carboxyl group obtained by reacting a (meth)acrylate having a hydroxyl group with an acid anhydride, and the like.

Here, the aliphatic polyhydroxy compound includes, for example, divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. The aliphatic polyhydroxy compound of 3 yuan or more. Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta( Meth)acrylate, glycerol dimethacrylate, etc. Examples of the multifunctional isocyanate include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride. Pyromellitic anhydride and biphenyl tetracarboxylic anhydride Tetracarboxylic acid dianhydride such as carboxylic dianhydride and benzophenone tetracarboxylic dianhydride.

Furthermore, examples of the polyfunctional (meth)acrylate modified with caprolactone include the compounds described in paragraphs [0015] to [0018] of Japanese Patent Laid-Open No. 11-44955. The polyfunctional (meth)acrylate modified with alkylene oxide may be exemplified by bisphenol A di(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide. Isocyanuric acid tri(meth)acrylate modified with at least one of ethylene oxide and propylene oxide, trimethylol modified with at least one selected from ethylene oxide and propylene oxide Propane tri(meth)acrylate, pentaerythritol tri(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide, at least one selected from ethylene oxide and propylene oxide A modified pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide, selected from ethylene oxide and cyclic Dipentaerythritol hexa(meth)acrylate modified by at least one of oxypropane and the like.

In addition, the compound having two or more N-alkoxymethylamine groups includes, for example, a compound having a melamine structure, a benzoguanamine structure, and a urea structure. In addition, the melamine structure and benzoguanamine structure refer to a chemical structure having more than one triazine ring or triphenyl ring substituted with phenyl groups as the basic skeleton, and further include melamine, benzoguanamine, or condensates of these concept. Specific examples of compounds having two or more N-alkoxymethylamine groups include N,N,N',N',N'',N''-hexa(alkoxymethyl)melamine, N ,N,N',N'-tetra(alkoxymethyl)benzoguanamine, N,N,N',N'-tetra(alkoxymethyl) glycoluril, etc.

Among these polymerizable compounds, polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid and caprolactone-modified polyfunctional (meth) are preferred Acrylate, polyfunctional (meth)acrylate carbamate, polyfunctional (meth)acrylate with carboxyl group, N,N,N',N',N'',N''-hexa(alkoxy) Methyl) melamine, N,N,N',N'-tetra(alkoxymethyl)benzoguanamine. The polyfunctional (methyl) obtained by reacting an aliphatic polyhydroxy compound of 3 or more with (meth)acrylic acid in order to achieve a well-balanced and higher level of heat resistance, solvent resistance and developability ) Among acrylates, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are particularly preferred. Among polyfunctional (meth)acrylates having a carboxyl group, it is particularly preferred to use A compound obtained by reacting pentaerythritol triacrylate and succinic anhydride, and a compound obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride.

In the present invention, (E) a polymerizable compound may be used alone or in combination of two or more.

The content of the (E) polymerizable compound is preferably 10 parts by mass to 1,000 parts by mass, more preferably 20 parts by mass to 500 parts by mass, and even more preferably 40 parts by mass relative to 100 parts by mass of the colorant (A). 150 parts by mass. By adopting such a form, heat resistance, solvent resistance, and developability can be achieved at a higher level in a well-balanced manner.

-(F) Photopolymerization initiator-The coloring composition of the present invention may contain a photopolymerization initiator. Thus, it is possible to impart radioactivity to the colored composition. The photopolymerization initiator used in the present invention is a compound that generates an active species capable of initiating polymerization of a polymerizable compound by exposure to radiation such as visible rays, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays.

Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyl oxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, and α-bis Ketone compounds, polynuclear quinone compounds, diazo compounds, amide imine sulfonate compounds, etc.

In the present invention, one type of photopolymerization initiator may be used or two or more types may be used in combination. The photopolymerization initiator is preferably at least one selected from the group of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyl oxime compounds.

Among the preferred photopolymerization initiators in the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Tons of ketones, etc.

Further, specific examples of the acetophenone compound include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethyl Amino-1-(4-morpholinophenyl)butane-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholine Substituted phenyl) butane-1-one and so on.

Moreover, specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2' -Bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichloro Phenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, etc.

In addition, when a biimidazole compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor together in terms of improving sensitivity. Here, the "hydrogen donor" refers to a compound that can supply a hydrogen atom to a radical generated from a biimidazole compound due to exposure. Examples of hydrogen donors include thiol hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 4,4'-bis(dimethylamino)benzophenone, 4,4'- Amine hydrogen donors such as bis(diethylamino)benzophenone. In the present invention, one type of hydrogen donor may be used or two or more types may be used in combination. In terms of further improving sensitivity, it is preferable to use one or more thiol hydrogen donors in combination with one or more amine hydrogen donors.

Furthermore, specific examples of the triazine compound include 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)vinyl ]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(tri Chloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4 -Methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-all Triazine compounds having a halomethyl group such as triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine.

Furthermore, specific examples of the O-acyl oxime compound include: 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyl oxime), and ethyl ketone ,1-[9-ethyl-6-(2-methylbenzyl)-9H-oxazol-3-yl]-,1-(O-acetamide oxime), ethyl ketone, 1-[9 -Ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzyl)-9H-oxazol-3-yl)-,1-(O-acetoxime), ethyl ketone, 1 -[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolyl)methoxybenzyl}}-9H-oxo Oxazol-3-yl]-,1-(O-acetyl oxime), etc. Commercial products of O-acyl oxime compounds can also be used NCI-831, NCI-930 (above manufactured by ADEKA Co., Ltd.), OXE-03, OXE-04 (above by BASF) Manufacturing) etc.

In the present invention, when a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound is used, a sensitizer may be used in combination. Examples of such sensitizers include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-diethylamine Acetophenone, 4-dimethylaminobenzeneacetone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis( 4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzyl) coumarin, 4-(diethylamino) ) Chalcone etc.

In the present invention, the content of the (F) photopolymerization initiator is preferably 0.01 to 120 parts by mass, more preferably 1 to 100 parts by mass, and more preferably 100 parts by mass relative to 100 parts by mass of the (E) polymerizable compound. More preferably, it is 5-50 mass parts. By adopting such a form, heat resistance, solvent resistance, and developability can be achieved at a higher level in a well-balanced manner. Therefore, the curability and film characteristics can be further improved.

-Additives- The coloring composition of the present invention may optionally contain various additives. Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly(fluoroalkyl acrylate); surfactants such as fluorine-based surfactants and silicone surfactants; vinyl groups Trimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Silane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3- Adhesion promoters such as chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis(4-methyl-6 -Tert-butylphenol), 2,6-di-tert-butylphenol, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis [2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10- Antioxidants such as tetraoxa-spiro[5·5]undecane, thiodiethylidene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, alkoxybenzophenones and other ultraviolet absorbers; sodium polyacrylate and other anticoagulants; propane di Acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3- Amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and other residue improvers; succinic acid mono[2-(meth)acryloyloxygen Development improver such as ethyl ethyl] ester, phthalic acid mono[2-(meth)acryloyloxyethyl] ester, ω-carboxy polycaprolactone mono(meth)acrylate, etc.

Manufacturing method of the coloring composition The coloring composition of the present invention can be prepared by an appropriate method, and it is preferable to add (E) a polymerizable compound and optionally (D) a binding resin to the coloring agent dispersion liquid manufactured by the method , (F) Photopolymerization initiator, further added (C) solvent or other components, and the method of mixing and preparing.

Colored cured film and method of forming the same The colored cured film of the present invention is formed using the colored composition of the present invention, and specifically refers to each color pixel, black matrix, black spacer, etc. used in a color filter.

Hereinafter, the coloring cured film used in the color filter and its forming method will be described.

As a method of forming the coloring cured film constituting the color filter, first, the following method may be mentioned. First, a light-shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, after applying, for example, a green liquid composition of the radiation-sensitive coloring composition of the present invention to the substrate, pre-baking is performed to evaporate the solvent to form a coating film. Next, after exposing this coating film through a photomask, it develops using an alkaline developing solution, and the unexposed part of the coating film is dissolved and removed. Thereafter, a pixel array is formed by performing post-baking, and the pixel array arranges green pixel patterns (colored cured films) in a predetermined arrangement.

Next, using each of the radioactive coloring compositions of red or blue, coating, pre-baking, exposing, developing, and post-baking each radioactive coloring composition in the same manner as described above, in order on the same substrate A red pixel array and a blue pixel array are formed. Thus, a color filter in which pixel arrays of three primary colors of red, green, and blue are arranged on the substrate. However, in the present invention, the order of forming the pixels of each color is not limited to the order.

Furthermore, the black matrix can be formed by using photolithography to form a metal thin film of chromium or the like formed by sputtering or evaporation into a desired pattern, but it is also possible to use a radiation-sensitive coloring composition in which black pigment is dispersed The object is formed in the same manner as the pixel is formed.

Examples of the substrate used when forming the color curing film include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamide imide, polyimide, and the like.

Furthermore, on these substrates, appropriate pretreatments such as chemical treatment using a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum evaporation, etc. may be performed in advance as necessary.

When coating the radiation-sensitive coloring composition on the substrate, spray coating, roll coating method, spin coating method (spin coating method), slot die coating method (slit coating method), bar coating method, etc. can be used. In particular, the spin coating method and the slit die coating method are preferably used.

The heating and drying conditions in the pre-baking are usually 70 to 110° C. for about 1 to 10 minutes.

In the case of forming a cured film of a color filter used in a display element, the coating thickness is usually 0.6 μm to 8 μm, preferably 1.2 μm to 5 μm in terms of the film thickness after drying. In addition, when a cured film of a color filter used in a solid-state imaging device is formed, the coating thickness is generally 0.3 μm to 5 μm, preferably 0.5 μm to 2 μm in terms of the film thickness after drying.

Examples of the light source used when forming at least one selected from the group consisting of pixels and black matrices include xenon lamps, halogen lamps, tungsten filament lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, and low-pressure mercury lamps. Lamp sources such as argon ion laser, yttrium aluminum garnet laser (YAG laser, Yttrium-Aluminum-Garnet Laser), XeCl excimer laser, nitrogen laser, etc. The exposure light source can also use an ultraviolet light emitting diode (Light Emitting Diode, LED). Radiation with a wavelength in the range of 190 nm to 450 nm is preferred.

The exposure amount of radiation is generally preferably 10 J/m ² to 10,000 J/m ² .

Furthermore, the alkaline developer is preferably, for example, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7 -Aqueous solutions of undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene, etc.

A water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can also be added to the alkaline developer in an appropriate amount. In addition, it is usually washed with water after development.

As the development treatment method, a shower development method, a spray development method, a dip (dip) development method, a puddle (coating liquid) development method, etc. can be applied. The developing conditions are preferably 5 seconds to 300 seconds at normal temperature.

The post-baking conditions are usually about 180 to 280°C for about 10 to 60 minutes.

The film thickness of the pixel formed as described above is 0.5 μm to 8 μm, preferably 1 μm to 4 μm when the coloring cured film of the color filter used in the display element is formed. In addition, when a coloring cured film of a color filter used in a solid-state imaging device is formed, it is usually 0.3 μm to 4 μm, preferably 0.5 μm to 2 μm.

Furthermore, as a second method of forming a color-cured film constituting a color filter, it can be obtained by an inkjet method disclosed in Japanese Patent Laid-Open No. 7-318723, Japanese Patent Laid-Open No. 2000-310706, etc. The method of each color pixel. In this method, first, a spacer having a light-shielding function is formed on the surface of the substrate. Next, in the formed separator, a liquid composition such as a green thermosetting coloring composition of the present invention is ejected by an inkjet device, and then pre-baking is performed to evaporate the solvent. Secondly, after exposing this coating film as needed, post-baking is performed to cure it to form a green pixel pattern.

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

In addition, the separator not only functions as a light-shielding device, but also functions to prevent the thermosetting coloring composition of each color ejected into the partition from mixing colors. Therefore, compared with the black matrix used in the first method, In other words, the film thickness is thicker. Therefore, the separator is usually formed using a black radiation-sensitive composition.

The substrate and the radiation light source used when forming the color curing film, and the pre-baking and post-baking methods and conditions are the same as the first method. As described above, the film thickness of the pixel formed by the inkjet method is equal to the height of the separator.

After forming a protective film as needed on the pixel pattern obtained as described above, a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed to make a color filter. Usually, a radiation-sensitive composition is used to form the spacer, but a spacer (black spacer) having light-shielding properties can also be made. In this case, a coloring radioactive composition in which a black colorant is dispersed is used.

The color filter including the color curing film of the present invention formed as described above is excellent in solvent resistance, and can solve the problem of color shift when the adjacent pixels are formed to form pixels of other colors or the generation of foreign materials. Display elements, color camera elements, color sensors, organic EL display elements, electronic paper, solid-state imaging elements, etc. are extremely useful.

Display Element The display element of the present invention includes the color curing film of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.

The color liquid crystal display element including the color curing film of the present invention may be a transmissive type or a reflective type, and an appropriate structure may be adopted. For example, a structure in which a color filter is formed on a substrate different from a driving substrate on which a thin film transistor (Thin Film Transistor, TFT) is arranged, and a structure in which the driving substrate and the substrate on which the color filter are formed are opposed via a liquid crystal layer It is also possible to use a substrate in which a color filter is formed on the surface of a driving substrate provided with a thin-film transistor (TFT) and a substrate in which an electrode of ITO (indium tin oxide doped with tin) is formed Opposite structure of the liquid crystal layer. The latter structure has the advantage that the aperture ratio can be significantly improved to obtain a bright, high-definition liquid crystal display element. In addition, in the case of adopting the latter structure, the black matrix or the black spacer may be formed on either side of the substrate on which the color filter is formed and the substrate on which the ITO electrode is formed.

In particular, the display device of the present invention is preferably a display device including the color curing film of the present invention and a color curing film containing an acid dye. More preferably, the display element of the present invention includes a first colored cured film, a second colored cured film, and a third colored cured film. The first colored cured film is formed using the coloring composition of the present invention, and the second colored cured film contains It is formed by the coloring composition of acid dye. Even more preferably, it is a display element comprising a first colored cured film formed using the coloring composition of the present invention, a second colored cured film containing an acid dye adjacent to the first colored cured film, and a third colored cured film . From the viewpoint of making a display element having excellent chromaticity characteristics, such a form is preferable. In addition, the "acid dye" in the present invention refers to an ionic dye in which an anion portion becomes a chromophore, and is a compound in which an anion portion constituting a chromophore forms a salt with a counter cation.

The reason for this is uncertain, but the inventors of the present invention speculate as follows. For example, when the first colored composition is applied to a substrate containing a second colored cured film formed using the second colored composition, the first colored composition penetrates from the outermost surface of the second colored cured film, and there is a second colored cured film The components such as the coloring agent or the dispersing agent contained in the first coloring composition may interact with the components such as the coloring agent or the dispersing agent included in the first coloring composition. More specifically, when the second coloring cured film contains an acid dye and the first coloring composition contains a pigment and an amine group-containing dispersant, the acid dye and the amine group-containing dispersant are present Possibility of salt exchange. The dispersing agent having an amine group is originally a component that contributes to the dispersion of the pigment contained in the first coloring composition, but contributes to the dispersion of the pigment due to salt exchange with the acid dye The amount of dispersant is reduced, and there is a possibility that the dispersion stability of the pigment is impaired. As a result, the pigment is precipitated as a foreign substance, and there is a possibility that the chromaticity characteristic of the display element is lowered.

It is considered that among the dispersant (b1) and the dispersant (b2) contained in the coloring composition of the present invention, the dispersant (b1) having a high amine value has strong interaction with the pigment. Therefore, in the case of using the coloring composition of the present invention as the first coloring composition, the dispersant (b2), which has a weaker interaction with the pigment, preferentially performs salt exchange with the acid dye, and is ensured by the dispersant (b1) The dispersion stability of the pigment makes it difficult for the pigment to precipitate as a foreign substance. It is preferable that the amine value Y (mgKOH/g) of the dispersant (b1) and the amine value X (mgKOH/g) of the dispersant (b2) satisfy the following relationship. From the viewpoint of forming a coloring cured film excellent in dye transferability, Y+X≧190 is preferable. From the viewpoint of reducing the generation of foreign matter at the borders of pixels of adjacent colors, it is preferable that Y-X≧50. In addition, in the calculation of "Y+X" and "YX" when two or more dispersants (b1) having different amine values are used and when two or more dispersants (b2) having different amine values are used, The amine value of the dispersant (b1) with the highest content and the amine value of the dispersant (b2) with the highest content are used. The first colored cured film, the second colored cured film, and the third colored cured film may be a combination of red, green, and blue, or may be a combination of yellow, cyan, and magenta. Moreover, for example, the first colored cured film may be a red cured film, the second colored cured film may be a green cured film, the third colored cured film may be a blue cured film, or the first colored cured film may be a blue cured film, The second colored cured film is a red cured film, and the third colored cured film is a green cured film. Among them, a display element including a green cured film formed using the coloring composition of the present invention containing a halogenated metal phthalocyanine pigment, and a red cured film or a blue cured film containing an acid dye is preferable.

The acid dye is preferably a compound having an anionic chromophore and an onium cation, and more preferably a compound having an anionic chromophore and an ammonium cation. Examples of the anionic chromophore include anionic azo chromophore, anionic triarylmethane chromophore, anionic anthraquinone chromophore, anionic xanthene chromophore, anionic quinoline chromophore, and anionic Cyanine chromophore, anionic dipyrromethene chromophore, etc. Specifically, a compound classified as a dye in the Color Index (C.I.; issued by The Society of Dyers and Colourists) can be cited, and a coloring portion of an acid dye classified as C.I. acid is particularly preferable. Among them, it is preferably at least one anionic chromophore selected from the group consisting of an anionic xanthene chromophore, an anionic cyanine chromophore, and an anionic dipyrromethene chromophore, and more preferably contains A red cured film or a blue cured film of a compound having a compound selected from the group consisting of anionic xanthene chromophore, anionic cyanine chromophore and anionic dipyrromethene chromophore Of at least one anionic chromophore and ammonium cation.

The color liquid crystal display element including the color curing film of the present invention may include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL: Cold Cathode Fluorescent Lamp). Examples of white LEDs include white LEDs that combine red LEDs, green LEDs, and blue LEDs to obtain white light by mixing colors; and white LEDs that combine blue LEDs, red LEDs, and green phosphors to obtain white light by mixing colors; A blue LED, a red light-emitting phosphor, and a green light-emitting phosphor are combined to obtain a white LED of white light by mixing colors; a white LED of white light is obtained by mixing a blue LED and a YAG-based phosphor; a blue LED, A combination of orange light-emitting phosphors and green light-emitting phosphors, a white LED that obtains white light by mixing colors; a combination of ultraviolet LEDs, red light-emitting phosphors, green light-emitting phosphors, and blue light-emitting phosphors to obtain white light by mixing colors LED etc.

The twisted nematic (TN) type, super twisted nematic (STN) type, and in-plane switching (IPS) type can be applied to the color liquid crystal display element including the color curing film of the present invention , Vertical Alignment (VA) type, Optically Compensated Birefringence (OCB) type and other suitable liquid crystal modes.

Further, the organic EL display element including the color curing film of the present invention can adopt an appropriate structure, and for example, the structure disclosed in Japanese Patent Laid-Open No. 11-307242 can be cited.

Moreover, the electronic paper including the coloring cured film of the present invention can adopt an appropriate structure, and for example, the structure disclosed in Japanese Patent Laid-Open No. 2007-41169 can be cited.

Solid-state imaging element The solid-state imaging element of the present invention includes the coloring cured film of the present invention. Furthermore, the solid-state imaging element of the present invention can adopt an appropriate structure. For example, as an embodiment, using the coloring composition of the present invention, a coloring pixel (colored cured film) is formed on the semiconductor substrate such as a complementary metal oxide semiconductor (CMOS) substrate by the same operation as described above ), a solid-state imaging element with particularly excellent color separation properties can be produced.

In particular, the solid-state imaging element of the present invention is preferably a solid-state imaging element including the color curing film of the present invention and a color curing film containing an acid dye. More preferably, the solid-state imaging element of the present invention includes a first colored cured film, a second colored cured film, and a third colored cured film. The first colored cured film is formed using the coloring composition of the present invention, and the second colored cured film is used It is formed by a coloring composition containing acid dyes. More preferably, a solid-state imaging element including a first colored cured film formed using the coloring composition of the present invention, a second colored cured film adjacent to the first colored cured film and containing an acid dye, and a third colored cured film. From the viewpoint of the self-made solid-state imaging element excellent in chromaticity, such a form is preferable.

The preferred form in this case is the same as the preferred form described in the display element. [Example]

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

<Synthesis of Dispersant> Dispersant Synthesis Example 1 In a flask with a stirring bar, 30.0 g of methyl methacrylate, 86.2 g of n-butyl methacrylate, and 1.5 g of azodiisobutyronitrile (AIBN) And 4.0 g of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester was dissolved in 150 mL of toluene, and nitrogen foaming was performed for 30 minutes. Thereafter, stirring was gradually performed to raise the temperature of the reaction solution to 60°C, and the temperature was maintained for 24 hours to carry out living radical polymerization.

Next, a solution in which 364 mg of AIBN and 14.8 g of dimethylaminoethyl methacrylate were dissolved in 50 mL of toluene and replaced with nitrogen for 30 minutes was added to the reaction solution, and the solution was performed at 60°C for 24 hours Living radical polymerization. Thereafter, it was adjusted to a 40% by mass solution of propylene glycol monomethyl ether by concentration under reduced pressure. As described above, A block containing a repeating unit derived from dimethylaminoethyl methacrylate and B having a repeating unit derived from methyl methacrylate and n-butyl methacrylate were obtained. Block copolymer dispersant (b2-1). Let this be a "dispersant (b2-1) solution".

Dispersant Synthesis Example 2 to Dispersant Synthesis Example 9 In Dispersant Synthesis Example 1, the amount of monomers used was changed as shown in Table 1, except that Dispersant Synthesis Example 1 was used to synthesize a dispersant. . In addition, Table 1 describes the molar ratio of the monomers constituting the dispersant. Dispersant (b1-1) to dispersant (b1-5) correspond to dispersant (b1). Dispersant (b2-1) to dispersant (b2-3) correspond to dispersant (b2). Dispersant (b3) is another dispersant.

<Measurement of Amine Value> The amine value of the dispersant obtained in each of the above synthesis examples was measured according to the following procedure.

Weigh 0.5 g of dispersant solution in units of precision to 1 mg and divide into glass containers. Add 20 mL of acetic anhydride/acetic acid = 9/1 (volume ratio) to dissolve, and leave at room temperature for 3 hours. Thereafter, after further adding 30 mL of acetic acid, titration was performed with a 0.1 mol/L perchloric acid·acetic acid solution using a potential difference measuring device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.). Carry out the blank test in the same way. The amine value (unit: mgKOH/g) was calculated based on the drop amount of the 0.1 mol/L perchloric acid·acetic acid solution of the dispersant and blank test. Table 1 shows the measurement results.

[Table 1]

In Table 1, each component is shown below. MMA: methyl methacrylate nBMA: n-butyl methacrylate DMMA: dimethylaminoethyl methacrylate

<Synthesis of Adhesive Resin> Synthesis Example 1 of Adhesive Resin 1 A flask equipped with a condenser and a stirrer was charged with 29 parts by mass of propylene glycol monomethyl ether acetate and subjected to nitrogen substitution. Heated to 80°C, 30.85 parts by mass of propylene glycol monomethyl ether acetate, 6.06 parts by mass (70.4 mmol) of methacrylic acid, 16.67 parts by mass (166.5 mmol) of methyl methacrylate, 15.15 were added dropwise at the same temperature for 1 hour A mixed solution of mass parts (93.4 mmol) of phenyl methacrylate and 2.27 mass parts of 2,2′-azobis(2,4-dimethylvaleronitrile) was maintained at this temperature for 2 hours of polymerization. Thereafter, the temperature of the reaction solution was increased to 100° C., and polymerization was further carried out for 1 hour, thereby obtaining a solution (solid content concentration of 40% by mass) containing the binder resin (D1). Use this as the "adhesive resin (D1) solution". The Mw of the obtained adhesive resin (D1) was 9,700, and Mn was 4,800.

Binder Resin Synthesis Example 2 A flask equipped with a condenser and a stirrer was charged with 86.4 parts by mass of cyclohexanone and replaced with nitrogen. Heat to 80°C, add 18.0 parts by mass of cyclohexanone, 21.6 parts by mass of methacrylic acid, and 27.0 parts by mass of (meth)acrylic acid tricyclo-[5.2.1.0 ^2,6 ]-dec 13.5 parts by mass of 2-ethylhexyl EO modified acrylate (manufactured by East Asia Synthetic Co., Ltd., trade name M-120) and 31.0 parts by mass of glycerol methacrylate mixed solution and 64 parts by mass of cyclohexanone and 7.2 parts by mass of a mixed solution of 2,2'-azobisbutyronitrile was polymerized while maintaining this temperature for 1 hour. Thereafter, the temperature of the reaction solution was increased to 90°C, and the superposition was further performed for 1 hour. Next, under air bubbling conditions, 25.72 parts by mass of 2-methacryloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd. under the trade name karenz MOI) was added dropwise over 15 minutes (as opposed to The molar number of glycerol methacrylate is 95 mol%) and a mixed solution of 0.36 parts by mass of 4-methoxyphenol, and the temperature is maintained to perform an addition reaction for 1.5 hours. Thereafter, the solution was cooled to room temperature, and cyclohexanone was added so that the nonvolatile content became 40% by mass, thereby obtaining a solution (solid content concentration of 40% by mass) containing the binder resin (D2). Use it as a "adhesive resin (D2) solution". The obtained adhesive resin (D2) had Mw=8,600 and Mn=3,600.

<Preparation and Evaluation of Colorant Dispersion Liquid> Preparation Example 1 Using 12 parts by mass of CI Pigment Green 58 and 3 parts by mass of CI Pigment Yellow 138 as colorants; 6.5 parts by mass as a dispersant with a solid content concentration of 40% by mass Method, a solution obtained by diluting LPN6919 (manufactured by BYK) with propylene glycol monomethyl ether acetate (PGMEA), 6.0 parts by mass of dispersant (b3) solution (solid content concentration 40% by mass) ; 12.5 parts by mass of a binder resin (D1) solution (solid content concentration of 40% by mass); as a solvent, 60 parts by mass of propylene glycol monomethyl ether acetate is processed by a bead mill to prepare colorant dispersion 1. In addition, the amine value of LPN6919 (manufactured by BYK) measured by the above method was 121 mgKOH/g.

Evaluation of the storage stability of the colorant dispersion liquid The viscosity of the colorant dispersion liquid 1 immediately after preparation was measured using an E-type viscometer (manufactured by Tokyo Keiki). Next, the colorant dispersion liquid 1 was filled in a light-shielding glass container, and after being allowed to stand in a sealed state at 23° C. for 14 days, the viscosity was measured again using an E-type viscometer (manufactured by Tokyo Instruments). Next, the increase rate of the viscosity after 14 days of storage relative to the viscosity immediately after preparation was calculated, and the case where the increase rate was less than 3% was evaluated as "AA", and the case where 3% or more and less than 5% was evaluated as "A", and 5 % Or more and less than 10% are evaluated as "B", and 10% or more are evaluated as "C". The results are shown in Table 2.

Preparation Example 2 to Preparation Example 40 In Preparation Example 1, the type and amount of each component were changed as shown in Tables 2 to 3 to obtain Colorant Dispersion Liquid 2 to Colorant Dispersion Liquid 40. In addition, in the evaluation of the storage stability of the colorant dispersion liquid, except that the colorant dispersion liquid 2 to the colorant dispersion liquid 40 were used instead of the colorant dispersion liquid 1, the evaluation was carried out in the same manner as in Preparation Example 1. The results are shown in Tables 2 to 3.

[Table 2]

[table 3]

In Tables 2 to 3, each component is shown below. G58: CI Pigment Green 58 G59: CI Pigment Green 59 Y138: CI Pigment Yellow 138 Y139: CI Pigment Yellow 139 LPN6919: The solid content concentration becomes 40% by mass, using PGMEA to manufacture LPN6919 (BYK) ) The diluted solution

<Preparation and Evaluation of Coloring Composition> Comparative Example 1 100.0 parts by mass of colorant dispersion 1 were used as a binder resin, a 12.0 parts by mass adhesive resin (D1) solution (solid content concentration of 40% by mass) and 10.3 parts by mass adhesive resin ( D2) A solution (solid content concentration of 40% by mass), as a polymerizable compound, a mixture of 9.1 parts by mass of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name Kayarad ( KAYARAD) DPHA), 3.0 parts by mass of a mixture of dipentaerythritol pentaacrylate and succinic acid monoester, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by East Asia Synthetic Co., Ltd., trade name TO-1382), 2.5 parts by mass of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one (Ciba specialty chemicals) company as a photopolymerization initiator Manufactured under the trade name of Irgacure 369) and 1.4 parts by mass of NCI-831 (made by Adicco), 0.1 parts by mass of Megafac F-554 (Di Aisheng Co., Ltd.), and 116.0 parts by mass of propylene glycol monomethyl ether acetate and 40.0 parts by mass of ethyl 3-ethoxypropionate as a solvent were mixed to prepare a green colored composition (GS-1).

Evaluation of solvent resistance: Using a spin coater, apply a coloring composition (GS-1) on a soda glass substrate on the surface of which a SiO ₂ film that prevents elution of sodium ions is formed, and then perform 2 minutes on a 90°C hot plate Pre-baked to form a coating film with a thickness of 2.5 μm. Next, after cooling the substrate to room temperature, the coating film was exposed to radiation at a wavelength of 365 nm, 405 nm, and 436 nm using a high-pressure mercury lamp and a photomask at an exposure of 400 J/m ² . Thereafter, on these substrates, a developing solution containing a 0.04% by mass potassium hydroxide aqueous solution at 23° C. was sprayed at a developing pressure of 1 kgf/cm ² (nozzle diameter 1 mm), and shower development was performed for 60 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 230° C. for 20 minutes, thereby forming a short stripe pattern on the substrate. For this short stripe pattern, a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) was used to measure the chromaticity coordinate values (x, y) and stimulus values (Y) in the CIE color system with a C light source and a 2-degree field of view ). Next, the substrate was immersed in N-methylpyrrolidone at 25°C for 3 minutes. For the short stripe pattern after dipping, use a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) to measure the chromaticity coordinate values (x, y) and stimulus values in the CIE color system with a C light source and a 2-degree field of view (Y). Calculate the color change before and after dipping, that is, ΔE ^* ab, and evaluate the case where the value of ΔE ^* ab is 1.0 or less as “AA”, and the case where it is greater than 1.0 and less than 2.0 as “A”, and it is greater than 2.0 and be A case of 3.0 or less is evaluated as "B", and a case of more than 3.0 is evaluated as "C". The results are shown in Tables 4 to 5. In addition, the smaller the ΔE ^* ab value, the better the solvent resistance.

Evaluation of heat resistance Using a spin coater, the coloring composition (GS-1) was applied to a soda glass substrate on the surface of which a SiO ₂ film was formed to prevent elution of sodium ions, and then preheated on a hot plate at 90°C for 2 minutes. Bake to form a coating film with a thickness of 2.5 μm. Next, after cooling the substrate to room temperature, the coating film was exposed to radiation at a wavelength of 365 nm, 405 nm, and 436 nm using a high-pressure mercury lamp and a photomask at an exposure of 400 J/m ² . Thereafter, for these substrates, a developer solution containing 0.04% by mass of potassium hydroxide aqueous solution at 23° C. was sprayed at a development pressure of 1 kgf/cm ² (nozzle diameter 1 mm), thereby performing shower development for 60 seconds. After that, the substrate was washed with ultrapure water, air-dried, and then post-baked in a dust-free oven at 230° C. for 20 minutes, thereby forming a colored cured film on the substrate. Using the color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) to obtain the color-cured film, the chromaticity coordinate values (x, y) and stimulus values (Y) in the CIE color system were measured with a C light source and a 2-degree field of view ). Next, the substrate was additionally baked at 230°C for 20 minutes twice. For the substrate after two additional bakings, the chromaticity coordinate values (x, y) and stimulation values (Y) were measured, and the color change before and after the two additional bakings, that is, ΔE ^* ab was evaluated. As a result, the case where the value of ΔE ^* ab is 1.5 or less is evaluated as “A”, the case where it is greater than 1.5 and 3.0 or less is evaluated as “B”, and the case where it is greater than 3.0 is evaluated as “C”. The results are shown in Tables 4 to 5. In addition, the smaller the ΔE ^* ab value, the better the heat resistance.

Evaluation of the storage stability of the coloring composition In the evaluation of the storage stability of the coloring agent dispersion, the coloring composition (GS-1) was used instead of the coloring agent dispersion 1, and the coloring composition ( GS-1) The viscosity immediately after preparation and the viscosity after storage at 23°C for 14 days, the rate of increase after storage at 23°C for 14 days was calculated. The case where the increase rate is less than 3% is evaluated as "AA", the case where 3% or more and less than 5% is evaluated as "A", and the case where 5% or more and less than 10% is evaluated as "B", and 10% or more Is evaluated as "C", and the results are shown in Tables 4 to 5.

Evaluation of foreign matter at the border with adjacent pixels Using a spin coater, the coloring composition (GS-1) was applied to a soda glass substrate on the surface of which a SiO ₂ film that prevents elution of sodium ions was formed, and then on a 90°C hot plate Pre-bake for 2 minutes to form a coating film with a thickness of 2.4 μm. Secondly, after cooling the substrate to room temperature, using a high-pressure mercury lamp without a photomask, the entire surface of the coating film was exposed to a wavelength of 365 nm, 405 nm, and 436 nm at an exposure of 400 J/m ² . radiation. Thereafter, these substrates were sprayed at a development pressure of 1 kgf/cm ² (nozzle diameter 1 mm) at 23° C., containing a 0.04% by mass potassium hydroxide aqueous solution, thereby performing spray development for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and further post-baked in a dust-free oven at 230° C. for 30 minutes, thereby forming a green cured film (T-1) on the substrate. Next, the blue coloring composition (BS-1) prepared by the method disclosed below is applied on the green cured film (T-1) using a spin coater, and then is performed on a hot plate at 90°C for 2 minutes Pre-baked to form a coating film with a thickness of 2.5 μm. Next, after cooling the substrate to room temperature, the coating film was exposed to radiation at a wavelength of 365 nm, 405 nm, and 436 nm using a high-pressure mercury lamp and a photomask at an exposure of 400 J/m ² . Thereafter, these substrates were sprayed at a development pressure of 1 kgf/cm ² (nozzle diameter 1 mm) at 23° C., containing a 0.04% by mass potassium hydroxide aqueous solution, thereby performing spray development for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and further baked in a dust-free oven at 230°C for 30 minutes, thereby forming a blue dot pattern on the green cured film (T-1) Color cured film (T-2). The obtained substrate was observed with a scanning electron microscope (Scanning Electron Microscope, SEM) at a magnification of 20,000 times to confirm the foreign matter near the boundary between the green cured film (T-1) and the blue cured film (T-2) The state of occurrence. In a region where the blue cured film (T-2) is formed obliquely with respect to the green cured film (T-1), the number of foreign objects observed in one field of view is 10 or less is evaluated as "A", 11 or more cases were evaluated as "B", and 51 or more cases were evaluated as "C". The results are shown in Tables 4 to 5.

The preparation method of the blue coloring composition (BS-1) is shown below. 15 parts by mass of CI Pigment Blue 15:6 as a coloring agent, 12.5 parts by mass of BYK-LPN21116 (manufactured by BYK) as a dispersant (solid content concentration of 40% by mass), and 72.5 parts by mass of a solvent Propylene glycol monomethyl ether acetate is processed with a bead mill to prepare a pigment dispersion (X-1). Furthermore, 10 parts by mass of the dye represented by the following formula (a) was dissolved in 90 parts by mass of methyl lactate to prepare a dye solution (X-2). 15.6 parts by mass of pigment dispersion liquid (X-1), 5.8 parts by mass of dye solution (X-2), 5.1 parts by mass of binder resin (D1) solution (solid content concentration of 40% by mass), 7.7 parts by mass of dipentaerythritol hexaacrylic acid A mixture of ester and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd. under the trade name of DPHA), 2.1 parts by mass of NCI-831 (manufactured by Adicco Co., Ltd.), 0.4 parts by mass of Mega Method F -554 (manufactured by Dickson Co., Ltd.), 0.14 parts by mass of the compound represented by the following formula (b), and 63.1 parts by mass of propylene glycol monomethyl ether acetate were mixed to prepare a blue colored composition (BS-1).

[Chem 2]

Evaluation of transference property The spin coating machine was used to apply a coloring composition (GS-1) on a soda glass substrate on the surface of which a SiO ₂ film was formed to prevent elution of sodium ions. Pre-bake to form a coating film with a thickness of 2.4 μm. Secondly, after cooling the substrate to room temperature, using a high-pressure mercury lamp without a photomask, the entire surface of the coating film was exposed to a wavelength of 365 nm, 405 nm, and 436 nm at an exposure of 400 J/m ² . radiation. Thereafter, these substrates were sprayed at a development pressure of 1 kgf/cm ² (nozzle diameter 1 mm) at 23° C., containing a 0.04% by mass potassium hydroxide aqueous solution, thereby performing spray development for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and further baked in a dust-free oven at 230° C. for 30 minutes, thereby forming a green cured film (T-3) on the substrate. For this green cured film (T-3), a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) was used to measure the chromaticity coordinate values (x, y) in the CIE color system with a C light source and a 2-degree field of view. The stimulus value (Y ₁ ). Next, apply the blue colored composition (BS-1) on the green cured film (T-3) using a spin coater, and then pre-bake on a hot plate at 90°C for 2 minutes to form A coating film with a thickness of 2.5 μm. Next, after cooling the substrate to room temperature, the developing solution containing 0.04% by mass of potassium hydroxide aqueous solution at 23° C. was sprayed on the substrate at a developing pressure of 1 kgf/cm ² (nozzle diameter 1 mm). Spray development in seconds. After that, the substrate was washed with ultrapure water and air-dried. For this green cured film (T-3), a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) was used to measure the chromaticity coordinate values (x, y) in the CIE color system with a C light source and a 2-degree field of view. Stimulus value (Y ₂ ). ΔY=Y ₁ -Y _{2 is} calculated, and a value of ΔY of less than 0.2 is evaluated as “A”, a value of 0.2 or more and less than 0.7 is evaluated as “B”, and a value of 0.7 or more is evaluated as “C”. The results are shown in Tables 4 to 5. In addition, the smaller the ΔY value, the more it can be said that the migration resistance is suppressed, which is preferable.

Evaluation of average surface roughness Using a spin coater, the coloring composition (GS-1) was applied to a soda glass substrate on the surface of which a SiO ₂ film was formed to prevent elution of sodium ions, and then it was performed on a hot plate at 90°C for 100 seconds. Pre-baked to form a coating film with a thickness of 2.5 μm. Next, after cooling the substrate to room temperature, the coating film was exposed to radiation at a wavelength of 365 nm, 405 nm, and 436 nm using a high-pressure mercury lamp and a photomask at an exposure of 400 J/m ² . Thereafter, for these substrates, a developer solution containing 0.04% by mass of potassium hydroxide aqueous solution at 23° C. was sprayed at a development pressure of 1 kgf/cm ² (nozzle diameter 1 mm), thereby performing shower development for 60 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and further baked in a dust-free oven at 220° C. for 30 minutes to form a pixel array of green striped pixel patterns arranged on the substrate. The average surface roughness (smoothness of the surface of the pattern) of the upper part of the obtained pixel pattern was measured using an atomic force microscope manufactured by Digital Instruments, and the average surface roughness of 30 Å or less was evaluated as "A". A case of more than 30 Å and 50 Å or less is evaluated as "B", and a case of more than 50 Å is evaluated as "C". The results are shown in Tables 4 to 5.

Example 1 to Example 31 and Comparative Example 2 to Comparative Example 12 In Comparative Example 1, the type and amount of each component were changed as shown in Tables 4 to 5 to obtain a green coloring composition (GS-2) to Coloring composition (GS-43). Next, the coloring composition (GS-2) to the coloring composition (GS-43) were used instead of the coloring composition (GS-1), and the evaluation was performed in the same manner as in Comparative Example 1. The results are shown in Tables 4 to 5. Among them, in Examples 25 to 31 and Comparative Examples 11 to 12 in which two coloring agent dispersion liquids are used, first, the two coloring agent dispersion liquids are mixed, and a binder resin and polymerizability are mixed in the mixed liquid Compounds, photopolymerization initiators, additives, and solvents, thereby preparing colored compositions (GS-35) to colored compositions (GS-43).

[Table 4]

[table 5]

In Tables 4 to 5, each component is shown below. E1: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name Kayarad DPHA) E2: monoester of dipentaerythritol pentaacrylate and succinic acid, dipentaerythritol Mixture of hexaacrylate and dipentaerythritol pentaacrylate (manufactured by East Asia Synthetic Co., Ltd., trade name TO-1382) F1: 2-benzyl-2-dimethylamino-1-(4-morpholinobenzene Base) butane-1-one (manufactured by Ciba Chemical Co., Ltd. under the trade name Yanjiagu 369) F2: NCI-831 (manufactured by Adicco Co., Ltd.) G1: Meijiafa F-554 (Di Aisheng Co., Ltd. Manufactured by the company) C1: propylene glycol monomethyl ether acetate C2: ethyl 3-ethoxypropionate

no

no

no.

Claims (20)

A coloring agent dispersion liquid, characterized in that it is a coloring agent dispersion liquid containing (A) a coloring agent containing a pigment, (B) a dispersing agent and (C) a solvent, (B) a dispersing agent contains (b1) an amine value Dispersant of Y mgKOH/g and (b2) (meth)acrylic dispersant with amine value of X mgKOH/g (where Y>140 and 0<X<100). The coloring agent dispersion liquid as described in Item 1 of the patent application scope, wherein Y>150 and Y≦230. The coloring agent dispersion liquid as described in item 1 or item 2 of the patent application scope, wherein X<80. The coloring agent dispersion liquid as described in Item 1 or Item 2 of the patent application scope, wherein Y+X≧190 and Y+X≦400. The coloring agent dispersion liquid as described in Item 1 or Item 2 of the patent application, wherein Y-X≧50. The coloring agent dispersion liquid as described in item 1 or item 2 of the patent application range, wherein the pigment contains a halogenated metal phthalocyanine pigment. A method for manufacturing a coloring agent dispersion liquid, characterized in that it includes the steps of mixing/dispersing (A) a coloring agent containing a pigment in (C) a solvent in the presence of (B) a dispersing agent, (B) a dispersing agent Use a first dispersant containing (b1) an amine value of Y mgKOH/g (where Y>140) and a (meth)acrylic dispersant containing (b2) an amine value of X mgKOH/g (where , 0<X<100) second dispersant. A method for manufacturing a coloring agent dispersion liquid, characterized in that it is a method for manufacturing a coloring agent dispersion liquid including the step of mixing a first dispersion liquid and a second dispersion liquid, the first dispersion liquid containing at least (b1 ) A dispersant with an amine value of Y mgKOH/g (where Y>140) the first dispersant and (C) solvent, the second dispersion contains at least (b2) an amine value of X mgKOH/g ( The second dispersant and (C) solvent of the meth)acrylic dispersant (where 0<X<100), at least one of the first dispersion liquid and the second dispersion liquid contains (A) a coloring agent containing a pigment. A coloring composition, characterized in that it is a coloring composition containing (A) a coloring agent containing a pigment, (B) a dispersing agent, (C) a solvent, (D) a binding resin, and (E) a polymerizable compound, ( B) The dispersant contains (b1) a dispersant with an amine value of Y mgKOH/g and (b2) a (meth)acrylic dispersant with an amine value of X mgKOH/g (where Y>140 and 0<X<100 ). The coloring composition as described in item 9 of the patent application scope, wherein Y>150 and Y≦230. The coloring composition as described in item 9 or item 10 of the patent application scope, where X<80. The coloring composition as described in item 9 or item 10 of the patent application, where Y+X≧190 and Y+X≦400. The coloring composition as described in item 9 or item 10 of the patent application, where Y-X≧50. The coloring composition as described in item 9 or 10 of the patent application, wherein the pigment includes a halogenated metal phthalocyanine pigment. A method for manufacturing a coloring composition, characterized by comprising the step of mixing a coloring agent dispersion liquid obtained by the manufacturing method described in item 7 or 8 of the patent application scope with at least (E) a polymerizable compound. A coloring cured film characterized by being formed using the coloring composition as described in any one of claims 9 to 14. A display element characterized by comprising a coloring cured film as described in item 16 of the patent application. A display element characterized in that it is a display element including a colored cured film, the colored cured film containing a first colored cured film and a second cured film, the first colored cured film is as described in item 16 of the patent application The second cured film is a colored cured film containing acid dyes. A solid-state imaging element, characterized by comprising a color-curing film as described in item 16 of the patent application. A solid-state imaging element, characterized in that it is a solid-state imaging element including a colored cured film, the colored cured film containing a first colored cured film and a second cured film, the first colored cured film is as claimed in the patent scope item 16 The said color curing film, the second cured film is a color curing film containing acid dye.