JP2016210973A - Coloring agent dispersion and manufacturing method therefor, coloring composition and manufacturing method therefor, colored cured film, display element and solid state image sensor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition capable of forming a colored cured film excellent in solvent resistance and capable of solving a problem of color migration or generation of debris in forming the same with neighboring other color pixels.SOLUTION: There is provided coloring agent dispersion containing (A) a coloring agent containing a pigment, (B) a dispersion and (C) a solvent, where the (B) dispersion contains (b1) a dispersion with amine value of Y mgKOH/g and (b2) a (meth)acrylic dispersion with amine value of X mgKOH/g, where Y>140 and 0<X<100.SELECTED DRAWING: None

Description

  The present invention relates to a colorant dispersion, a method for producing a colorant dispersion, a color composition, a method for producing a color composition, a colored cured film, a display element, and a solid-state image sensor. -Type color liquid crystal display element, solid-state imaging element, organic EL display element, colored composition used for forming a colored cured film used for electronic paper and the like, a method for producing the same, and colored curing formed using the colored composition The present invention relates to a film, a display device and a solid-state imaging device including the colored cured film, a colorant dispersion used for preparing the coloring composition, and a method for manufacturing the same.

  In producing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape. A method (so-called photolithography method, for example, see Patent Documents 1 and 2) in which pixels of three primary colors of red, green, and blue are arranged on a substrate by irradiation (hereinafter referred to as “exposure”) and development. Are known. In addition, a method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (see, for example, Patent Document 3) is also known. Furthermore, a method for obtaining pixels of each color by an ink jet method using a pigment-dispersed colored resin composition is also known (for example, see Patent Document 4).

In recent years, the development of liquid crystal display devices has been expanded from the use of personal computers and monitors having a relatively small screen to the use of televisions requiring a large screen and high image quality.
In television applications, higher image quality, that is, improvement in contrast and color purity is required compared to conventional monitor applications. In order to improve the contrast, the particle size of the organic pigment used in the colored curable composition used for forming the color filter is required to be finer. Moreover, in order to improve the color purity of the display device, a higher content of colorant (organic pigment or the like) in the solid content of the colored curable composition is required. Furthermore, from the viewpoint of improving the color separation property of the solid-state imaging device, a material having a higher content of a colorant (such as an organic pigment) is required.

In response to the above requirements, a pigment dispersion composition having a finer particle diameter and higher dispersibility is required.
For example, for brominated zinc phthalocyanine pigments that have recently attracted attention for the formation of green pixels due to their good hue, for example, the surface of the phthalocyanine pigment is usually modified with its derivative compound to improve the dispersibility. The pigment, the surface modifier, and the dispersant, while using a dispersant such as a low molecular weight resin having a polar functional group that is easily adsorbed on the modified surface and improving the dispersibility and dispersion stability of the pigment A pigment dispersion containing is obtained. The resulting pigment dispersion 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 filter coloring pattern by a photolithography method or the like. To be done.

  Dispersion becomes difficult as the pigment becomes finer and the pigment content increases, but in order to solve this problem, it has solvophilicity as a dispersant used in the photosensitive resin composition for color filters. A pigment dispersion using a block and a block acrylic block copolymer having a specific amine value as a dispersant has been proposed (see, for example, Patent Document 5).

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP 2009-52010 A

  However, the green pixel formed using the coloring composition described in Patent Document 5 is not only insufficient in solvent resistance, but is also adjacent to the green pixel in another color pixel (for example, a blue pixel). When forming a green pixel, a component (for example, a colorant) in a coloring composition used for forming a pixel of another color contaminates the green pixel (hereinafter also referred to as “transferability”), or the green pixel. It has been found by the present inventors that foreign matter is generated at the boundary between the pixel and other color pixels.

  Accordingly, an object of the present invention is to provide a colored composition capable of forming a colored cured film having excellent solvent resistance and eliminating the problem of transferability and the generation of foreign matters when pixels of other colors are formed adjacent to each other. It is in providing a thing and its manufacturing method. Moreover, the subject of this invention is providing the display element and solid-state image sensor which comprise the colored cured film formed using the said colored composition, and the said colored cured film. Furthermore, the subject of this invention is providing the coloring agent dispersion suitable for preparation of the said coloring composition, and its manufacturing method.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by using a specific dispersant in combination.

  That is, the present invention is a colorant dispersion containing (A) a colorant containing a pigment, (B) a dispersant and (C) a solvent, wherein (B) the dispersant is (b1) the amine value is YmgKOH. A colorant dispersion comprising: (b2) a dispersant having a / g and (b2) a (meth) acrylic dispersant having an amine value of X mgKOH / g (where Y> 140 and 0 <X <100). To do.

The present invention also provides a method for producing a colorant dispersion of the following (i) and (ii).
(I) A method for producing a colorant dispersion comprising the step of mixing and dispersing (A) a colorant containing a pigment in (C) a solvent in the presence of (B) a dispersant,
(B) As a dispersant, (b1) a first dispersant containing a dispersant having an amine value of YmgKOH / g (provided that Y> 140), and (b2) an amine value of XmgKOH / g (meth) A method for producing a colorant dispersion using a second dispersant containing an acrylic dispersant (however, 0 <X <100).
(Ii) at least (b1) a first dispersant containing a dispersant having an amine number of YmgKOH / g (where Y> 140) and (C) a first dispersion containing a solvent;
At least (b2) a second dispersant containing a (meth) acrylic dispersant (where 0 <X <100) having an amine value of X mgKOH / g, and (C) a second dispersion containing a solvent. A method for producing a colorant dispersion comprising the step of mixing
A manufacturing method in which at least one of the first dispersion and the second dispersion contains (A) a colorant containing a pigment.

  The present invention also provides a colored composition comprising (A) a colorant containing a pigment, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a polymerizable compound, And (b1) a dispersant having an amine value of YmgKOH / g and (b2) a (meth) acrylic dispersant having an amine value of XmgKOH / g (provided that Y> 140 and 0 <X <100 A coloring composition containing the same).

  The present invention further provides a method for producing a colored composition, comprising the step of mixing the colorant dispersion obtained by the above production method and at least (E) a polymerizable compound.

  Furthermore, the present invention provides a colored cured film formed using the above colored composition, and a display element and a solid-state imaging device including the colored cured film. The display device and the solid-state imaging device of the present invention include a colored cured film having a first colored cured film and a second cured film, and the first colored cured film is formed using the colored composition. It is also preferable that the second cured film is a colored cured film containing an acid dye. Here, the “colored cured film” means each color pixel, protective film, black matrix, spacer, insulating film, and the like used for a display element or a solid-state imaging element.

  According to the present invention, a colored composition capable of forming a colored cured film having excellent solvent resistance and eliminating the problem of transferability and the generation of foreign matters when pixels of other colors are adjacently formed. Can be provided. Therefore, the colored composition of the present invention is extremely useful for producing various color filters including color liquid crystal display elements, color separation color filters for solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. It can be preferably used.

  Hereinafter, the present invention will be described in detail.

The following colorant dispersion will be described in detail components of the colorant dispersion of the present invention.
-(A) Colorant-
The coloring composition of the present invention includes a pigment as the colorant (A). The pigment can be used without particular limitation as long as it has colorability, and the color and material can be appropriately selected according to the use of the colored composition. When the colored composition of the present invention is used for forming each color pixel constituting the color filter, an organic pigment is preferred because the color filter is required to have high color purity, luminance, contrast, and the like.

Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (CI). Names can be mentioned.
C. I. Pigment red 57: 1, C.I. I. Pigment red 166, C.I. I. Pigment red 170, C.I. I. Pigment red 177, C.I. I. Pigment red 179, C.I. I. Pigment red 208, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Red pigments such as CI Pigment Red 264;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Green pigments such as CI Pigment Green 59;
C. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Pigment blue 79, C.I. I. Blue pigments such as CI Pigment Blue 80;
C. I. Pigment yellow 14, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 179, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 211, C.I. I. Yellow pigments such as CI Pigment Yellow 215;
C. I. Orange pigments such as CI Pigment Orange 38;
C. I. Pigment violet 19, C.I. I. Purple pigment such as CI Pigment Violet 23.

  In addition, the following formula:

Can also be used as a red pigment. Furthermore, lake pigments can also be used as pigments. Examples of lake pigments include triarylmethane dyes and xanthene dyes laked with isopolyacids or heteropolysanacids. Triarylmethane-based lake pigments are disclosed in, for example, Japanese Patent Application Laid-Open No. 2011-186043. Xanthene-based lake pigments are disclosed in, for example, JP 2010-191304 A.

  In the present invention, the pigment can be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Moreover, the pigment surface may be used by modifying the particle surface with a resin if desired. Further, the organic pigment can be used by refining primary particles by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be employed.

  Among these, the colorant dispersion of the present invention preferably contains a metal halide phthalocyanine pigment as a pigment. Examples of the halogenated metal phthalocyanine pigment include a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment. I. Pigment green 58, C.I. I. It preferably contains a halogenated zinc phthalocyanine pigment such as CI Pigment Green 59.

  Further, (A) a colorant may further contain a dye. Examples of the dye include organic dyes such as xanthene dye, triarylmethane dye, cyanine dye, anthraquinone dye, azo dye, squarylium dye, dipyrromethene dye, phthalocyanine dye, quinoneimine dye, quinoline dye, porphyrin dye, and coumarin dye. . More specifically, JP 2010-32999 A, JP 2010-254964 A, JP 2011-138094 A, International Publication No. 2010/123071, Pamphlet 2011-116803, JP 2011. Organic dyes described in JP-A No. 117995, JP-A No. 2011-133844, JP-A No. 2011-174987, and the like.

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

  In the present invention, the content ratio of (A) the colorant is 10 to 90% by mass in the total solid content of the colorant dispersion from the viewpoint of making the colorant dispersion excellent in dispersion stability and storage stability. Preferably, it is more preferably 20 to 85% by mass, and from the point of forming a pixel having excellent transparency and color purity or a black matrix having excellent light shielding properties, It is preferable that it is 70 mass%, and it is more preferable that it is 10-60 mass%. Here, solid content is components other than the (C) solvent mentioned later.

  In the colorant dispersion 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 based on the total content in (A) the colorant. Thus, a colorant dispersion having excellent dispersion stability and storage stability can be obtained.

-(B) Dispersant-
In the colorant dispersion of the present invention, as component (B), (b1) a dispersant having an amine value of YmgKOH / g (hereinafter also referred to as “dispersant (b1)”) and (b2) an amine value of XmgKOH. / G (meth) acrylic dispersant (hereinafter also referred to as “dispersant (b2)”) (where Y> 140 and 0 <X <100). The “amine value” in the present invention represents the number of mg of KOH equivalent to the acid required to neutralize 1 g of the solid content of the dispersant.

  The dispersant (b1) is not particularly limited as long as the amine value is a dispersant greater than 140 mgKOH / g, such as urethane dispersant, polyethyleneimine dispersant, polyester dispersant, (meth) acrylic dispersant, and the like. A well-known dispersing agent can be used. Among these, (meth) acrylic dispersants are preferable.

  As the dispersant (b1) and the dispersant (b2) which are (meth) acrylic dispersants, commercially available ones can be used, and a known method using a monomer having an amino group It is also possible to use those synthesized by the above. As commercially available (meth) acrylic dispersants, Disperbyk-2000 (nonvolatile component = 40% by mass, amine value 4 mgKOH / g), Disperbyk-2001 (nonvolatile component = 46% by mass, amine value 29 mgKOH / g) BYK-LPN21116 (nonvolatile component = 40% by mass, amine value 29 mgKOH / g), BYK-LPN22102 (nonvolatile component = 40% by mass, amine value 29 mgKOH / g) [above, manufactured by BYK (BYK) Co., Ltd.] (B2).

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

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

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

  Further, from the viewpoint of preparing a coloring composition having excellent 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 the calculation of “Y + X” 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, Applies the amine value of the dispersant (b1) with the highest content and the amine value of the dispersant (b2) with the highest content.

In the coloring composition of the present invention, the content ratio of the dispersant (b1) and the dispersant (b2) can be appropriately selected. The content w ₁ of the dispersant (b1) and the dispersant (b2) the ratio w ₁ / w ₂ between the content w ₂ is preferably 10 / 90-90 / 10 in mass ratio, more preferably 15 / 85-75 / 25, more preferably 20/80 to 60/40.

  (B) As a component, other dispersing agents other than the said dispersing agent (b1) and a dispersing agent (b2) can also be used together. Examples of such other dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid esters. System dispersants, polyester dispersants, (meth) acrylic dispersants, and the like. Commercially available products include, for example, BYK-LPN6919 (nonvolatile component = 60 mass%, amine value 72 mgKOH / g, manufactured by BYK Corporation (BYK)). (Meth) acrylic dispersants such as Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)) Urethane dispersants such as Solsperse 76500 (manufactured by Lubrizol Corp.), polyethyleneimine dispersants such as Solsperse 24000 (manufactured by Lubrizol Corp.), Ajisper PB821, Azisper PB822, Azisper PB880, Azisper PB881 (and above) In addition to polyester-based dispersants such as Ajinomoto Fine Techno Co., Ltd., BYK-LPN21324 (manufactured by BYK Corporation (BYK)) can be used.

  When other dispersants other than the dispersant (b1) and the dispersant (b2) are used in combination, the content ratio of the other dispersant is preferably 50% by mass or less with respect to the total content of the (B) dispersant, 20 mass% or less is more preferable.

In this invention, 5-300 mass parts is preferable with respect to 100 mass parts of (A) colorants, and, as for content of (B) dispersing agent, 10-200 mass parts is more preferable, and 20-100 mass parts is further. preferable. By setting it as such an aspect, it becomes easy to obtain the desired effect of this application.
In particular, the coloring composition of the present invention is a coloring agent dispersion that is excellent in storage stability even if the content of the dispersing agent is reduced as compared with the conventional coloring composition by using a specific dispersing agent in combination. And coloring compositions can be prepared. Therefore, there is an advantage that the amount of the other components constituting the coloring composition can be increased by the amount of the dispersant reduced. For example, since the content ratio of the colorant can be increased, the color purity of the display element can be improved, and the color separation property of the solid-state imaging element can be improved. Or since the content rate of a polymeric compound can be increased, the solvent resistance of a colored cured film can be improved.

-(C) Solvent-
As the solvent (C) in the present invention, the components (A) to (B) constituting the colorant dispersion and other components are dispersed or dissolved, and do not react with these components and have appropriate volatility. As long as it is a thing, it can select and use suitably.

Among such organic solvents, for example,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, (poly) alkylene glycol monoalkyl ethers such as tripropylene glycol monoethyl ether;
Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol;
Keto alcohols such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether;
Cyclic ethers such as tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;

Alkoxycarboxylates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyrate Fatty acid alkyl esters such as propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone, and lactams.

  Of these organic solvents, one or more selected from (poly) alkylene glycol monoalkyl ether acetate, ketoalcohol and ketone are preferred from the viewpoints of solubility, pigment dispersibility, coatability and the like.

  In this invention, a solvent can be used 1 type or in mixture of 2 or more types.

  (C) Although content of a solvent is not specifically limited, The quantity from which the total density | concentration of each component except the solvent of the colorant dispersion liquid becomes 5-80 mass% is preferable, and it is 10-60 mass%. The amount in which the total concentration of each component excluding the solvent of the coloring composition described below is 5 to 50% by mass is preferable, and the amount to be 10 to 40% by mass is more preferable. By setting it as such an aspect, the dispersibility and stability are improved and the coloring composition which is excellent in applicability | paintability can be obtained.

  The colorant dispersion of the present invention may contain other components other than the components (A) to (C) as necessary. Specific examples include (D) binder resins and additives which will be described later, and details thereof will be described later.

Method for Producing Colorant Dispersion The colorant dispersion of the present invention can be prepared by an appropriate method. For example, (A) a colorant containing a pigment is contained in (C) a solvent, and (B) in the presence of the dispersant. In some cases, (D) it can be produced by a method of mixing and dispersing together with a part of the binder resin and other components, for example, using a bead mill, a roll mill or the like.
In the present invention, as the dispersant (B), a first dispersant containing at least the dispersant (b1) and a second dispersant containing at least the dispersant (b2) may be used. That is, the first dispersant may contain other dispersant as long as it contains at least the dispersant (b1). Moreover, the 2nd dispersing agent may contain the other dispersing agent, if the dispersing agent (b2) is contained at least.

  In the present invention, the first dispersant and the second dispersant may be used in the form of a dispersion prepared separately. More specifically, for example, a first dispersant containing at least a dispersant (b1) and a (C) first dispersion containing a solvent, a second dispersant containing at least a dispersant (b2), and ( C) A method for producing a colorant dispersion in which a second dispersion containing a solvent is mixed. (A) The colorant containing the pigment may be contained in at least one of the first dispersion and the second dispersion, and is contained in both the first dispersion and the second dispersion. It doesn't matter. Among these, from the viewpoint of further enjoying the effects of the present invention, a method for producing a colorant dispersion using the first dispersant and the second dispersant in the form of a dispersion prepared separately is preferable.

Coloring composition The coloring composition of the present invention comprises (A) a colorant containing a pigment, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a polymerizable compound. The dispersant is (b1) a dispersant having an amine value of YmgKOH / g, and (b2) a (meth) acrylic dispersant having an amine value of XmgKOH / g (provided that Y> 140 and 0 <X <100. .)including. The coloring composition of the present invention can be prepared using the colorant dispersion of the present invention. Specifically, the (D) binder resin and the (E) polymerizable compound are added to the colorant dispersion of the present invention. It can contain and prepare.

-(D) Binder resin-
The binder resin (D) in the present invention is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). And a copolymer of another 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], ω-carboxypolycaprolactone mono (meta ) Acrylate, p-vinylbenzoic acid and the like.

  These unsaturated monomers (d1) can be used alone or in combination of two or more.

Examples of the unsaturated monomer (d2) include:
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;
Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (polymerization degree 2 10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate Glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[( (Meth) acrylic acid esters such as (meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.

  These unsaturated monomers (d2) can be used alone or in combination of two or more.

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

  Specific examples of the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. No. 10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Coalescence can be mentioned.

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

  The binder resin in the present invention has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran), usually 1,000 to 100,000, preferably Is 3,000 to 50,000. By adopting such an embodiment, the balance between coloring power and luminance, the remaining film ratio of the coating, the pattern shape, heat resistance, electrical characteristics, and resolution can be further enhanced, and the occurrence of precipitates and coating foreign matter can be increased. Can be suppressed at a level.

  Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3. .0. In addition, Mn here says the number average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran).

  The binder resin in the present invention can be produced by a known method. For example, it is disclosed in JP2003-222717A, JP2006-259680A, International Publication No. 2007/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

  In this invention, binder resin can be used 1 type or in combination of 2 or more types.

  In this invention, content of (D) binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts, More preferably, it is 50-200 mass. Part. By adopting such an embodiment, the balance between coloring power and luminance, alkali developability, storage stability of the colored composition, pattern shape, and chromaticity characteristics can be further enhanced, and the occurrence of precipitates and coating film foreign matter 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 an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. 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-alkoxymethylamino groups.

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

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and 3 such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of aliphatic polyhydroxy compounds having a valence higher than that. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol dimethacrylate. Etc. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

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

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

  Among these polymerizable compounds, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional urethanes (Meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N ′ -Tetra (alkoxymethyl) benzoguanamine is preferred. Among the polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Among polyfunctional (meth) acrylates having a carboxyl group, erythritol hexaacrylate is obtained by reacting pentaerythritol triacrylate and succinic anhydride, and reacting dipentaerythritol pentaacrylate and succinic anhydride. The compound is particularly preferable in that heat resistance, solvent resistance and developability can be achieved in a balanced manner at a higher level.

  In this invention, (E) polymeric compound can be used 1 type or in mixture of 2 or more types.

  (E) As for content of a polymeric compound, 10-1,000 mass parts is preferable with respect to 100 mass parts of (A) coloring agents, 20-500 mass parts is more preferable, 40-150 mass parts is still more preferable. . By setting it as such an aspect, heat resistance, solvent resistance, and developability can be achieved in a well-balanced and higher level.

-(F) Photopolymerization initiator-
The coloring composition of the present invention can contain a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The photopolymerization initiator used in the present invention is a compound that generates active species capable of initiating polymerization of a polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray.

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

  In this invention, a photoinitiator can be used 1 type or in mixture of 2 or more types. The photopolymerization initiator is preferably at least one selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, and an O-acyloxime compound.

  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 and the like can be mentioned.

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

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and 2,2′-bis. (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′ , 5,5′-tetraphenyl-1,2′-biimidazole and the like.

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

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

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) ) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3- And dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime). As commercial products of O-acyloxime compounds, NCI-831, NCI-930 (above, manufactured by ADEKA Corporation), OXE-03, OXE-04 (above, manufactured by BASF Corporation) and the like can also be used.

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

  In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (E) polymeric compounds, and, as for content of (F) photoinitiator, 1-100 mass parts is more preferable, 50 parts by mass is more preferable. By setting it as such an aspect, since heat resistance, solvent resistance, and developability are achieved in a well-balanced and higher level, sclerosis | hardenability and a film characteristic can be improved more.

-Additives-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicone surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropro Adhesion promoters such as rutrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- t-butylphenol, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- [3- (3-t-butyl-4-hydroxy) -5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxa-spiro [5 · 5] undecane, thiodiethylenebis [3- (3,5-di- antioxidants such as t-butyl-4-hydroxyphenyl) propionate]; 2- (3-t-butyl-5-methyl-2-hydroxy) Phenyl) -5-chlorobenzotriazole, alkoxybenzophenones and other ultraviolet absorbers; aggregation inhibitors such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol Residue improving agents such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. An improving agent etc. can be mentioned.

Method for Producing Colored Composition The colored composition of the present invention can be prepared by an appropriate method. In the colorant dispersion produced by the above-described method, (E) a polymerizable compound, and if necessary, (D) A binder resin, (F) a photopolymerization initiator, and an additional (C) solvent and other components are preferably added and mixed.

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

  Hereinafter, a colored cured film used for a color filter and a method for forming the same will be described.

  As a method for forming the colored cured film constituting the color filter, the following method is first exemplified. 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, for example, after applying a green liquid composition of the radiation-sensitive colored composition of the present invention on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which green pixel patterns (colored cured films) are arranged in a predetermined arrangement.

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

  A black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithographic method. It can also be formed in the same manner as in the case of forming the above-mentioned pixel using a sexually colored composition.

  Examples of the substrate used when forming the colored cured film include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.

  In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  When applying the radiation-sensitive coloring composition to the substrate, an appropriate coating method such as spraying, roll coating, spin coating (spin coating), slit die coating (slit coating), bar coating, etc. In particular, it is preferable to employ a spin coating method or a slit die coating method.

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

  The coating thickness in the case of forming a cured film of the color filter used for the display element is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, as the film thickness after drying. Moreover, the coating thickness in the case of setting it as the cured film of the color filter used for a solid-state image sensor is 0.3-5 micrometers normally as a film thickness after drying, Preferably it is 0.5-2 micrometers.

  Examples of the radiation light source used when forming at least one selected from the pixel and the black matrix include, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, and a low pressure. Examples thereof include a lamp light source such as a mercury lamp, and a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. An ultraviolet LED can also be used as the exposure light source. The wavelength is preferably radiation in the range of 190 to 450 nm.

In general, the exposure dose of radiation is preferably 10 to 10,000 J / m ² .

  Examples of the alkali developer include sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, and 1,8-diazabicyclo- [5.4.0] -7-undecene. An aqueous solution of 1,5-diazabicyclo- [4.3.0] -5-nonene is preferable.

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

  As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

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

  The film thickness of the pixels formed in this manner is 0.5 to 8 μm, preferably 1 to 4 μm, when a colored cured film of a color filter used for a display element is used. Moreover, when setting it as the colored cured film of the color filter used for a solid-state image sensor, it is 0.3-4 micrometers normally, Preferably it is 0.5-2 micrometers.

  Further, as a second method for forming a colored cured film constituting a color filter, a method for obtaining pixels of each color by an ink jet method disclosed in JP-A-7-318723, JP-A-2000-310706, etc. Can be adopted. In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, for example, a green liquid composition of the thermosetting coloring composition of the present invention is discharged into the formed partition wall by an inkjet apparatus, and then prebaked to evaporate the solvent. Next, this coating film is exposed as necessary and then cured by post-baking to form a green pixel pattern.

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

  In addition, since the partition plays not only a light shielding function but also a function for preventing the color mixing of the thermosetting coloring compositions discharged in the respective sections, it is compared with the black matrix used in the first method described above. The film thickness is thick. Therefore, a partition is normally formed using a black radiation sensitive composition.

  The substrate used for forming the colored cured film, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. In this way, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the partition wall.

  A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer). In this case, a colored radiation-sensitive composition in which a black colorant is dispersed is used.

  The color filter including the colored cured film of the present invention formed in this way has excellent solvent resistance and can eliminate the problem of dye transfer and the generation of foreign matters when pixels of other colors are formed adjacent to each other. Therefore, it is extremely useful for a color liquid crystal display element, a color image pickup tube element, a color sensor, an organic EL display element, electronic paper, a solid-state image pickup element and the like.

Display element The display element of the present invention comprises the colored cured 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 provided with the colored cured film of the present invention may be a transmissive type or a reflective type, and can take an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. Further, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (tin-doped indium oxide) electrode is formed are a liquid crystal layer. It is also possible to adopt a structure that is opposed to each other. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained. When the latter structure is adopted, the black matrix and the black spacer may be formed on either the substrate side on which the color filter is formed or the substrate side on which the ITO electrode is formed.

  In particular, the display element of the present invention is preferably a display element comprising the colored cured film of the present invention and a colored cured film containing an acid dye. More preferably, the display element of the present invention comprises a first colored cured film, a second colored cured film, and a third colored cured film, and the first colored cured film uses the colored composition of the present invention. It is preferably formed and the second colored cured film is formed using a colored composition containing an acid dye. More preferably, a first colored cured film formed using the colored 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 A display element including a colored cured film is preferable. Such an embodiment is preferable from the viewpoint of creating a display element having excellent chromaticity characteristics. In the present invention, the “acidic dye” is an ionic dye in which the anion portion becomes a chromophore, and the anion portion constituting the chromophore and a counter cation form a salt.

The reason for this is not clear, but the present inventors presume as follows. For example, when the first colored composition is applied to a substrate having a second colored cured film formed using the second colored composition, the first colored composition is the last of the second colored cured film. There is a possibility that the components such as the colorant and the dispersant contained in the second colored cured film soak in from the surface and the component such as the colorant and the dispersant contained in the first colored composition may interact with each other. . More specifically, in the case where the second colored cured film contains an acidic dye and the first colored composition contains a pigment and a dispersant having an amino group, the acidic dye and the amino group The possibility of salt exchange with the dispersant having The dispersant having an amino group is originally a component that contributes to the dispersion of the pigment contained in the first coloring composition, but the amount of the dispersant that contributes to the dispersion of the pigment by salt exchange with the acidic dye. May decrease, and the dispersion stability of the pigment may be impaired. As a result, there is a possibility that the pigment is deposited as a foreign substance and the chromaticity characteristics of the display element are lowered.
Of the dispersant (b1) and dispersant (b2) contained in the colored composition of the present invention, the dispersant (b1) having a higher amine value is considered to have a stronger interaction with the pigment. Therefore, when the colored composition of the present invention is used as the first colored composition, the dispersant (b2) having a weaker interaction with the pigment preferentially salt-exchanges with the acid dye to disperse the pigment. Since the stability is ensured by the dispersant (b1), it is considered that the pigment is less likely 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 colored cured film having excellent dye transfer properties, it is preferable that Y + X ≧ 190. From the viewpoint of reducing the occurrence of foreign matter at the boundary between adjacent pixels of other colors, it is preferable that Y−X ≧ 50. “Y + X” and “Y” 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. In the calculation of “−X”, the amine value of the dispersant (b1) having the highest content and the amine value of the dispersant (b2) having the highest content are applied.
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 a combination of yellow, cyan, and magenta. . Further, 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, The colored cured film may be a blue cured film, the second colored cured film may be a red cured film, and the third colored cured film may be a green cured film. Especially, the display element which comprises the green cured film formed using the coloring composition of this invention containing a halogenated metal phthalocyanine pigment, and the red cured film or blue cured film containing an acidic dye is preferable.

  As the acidic dye, a compound having an anionic chromophore and an onium cation is preferable, and a compound having an anionic chromophore and an ammonium cation is more preferable. Anionic chromophores include anionic azo chromophore, anionic triarylmethane chromophore, anionic anthraquinone chromophore, anionic xanthene chromophore, anionic quinoline chromophore, anionic cyanine chromophore, anionic dipyrromethene chromophore. Etc. Specific examples include compounds classified as dies in the color index (CI; issued by The Society of Dyeres and Colorists). I. Color developing parts of acid dyes classified as acid are preferred. Among these, at least one anionic chromophore selected from the group consisting of an anionic xanthene chromophore, an anionic cyanine chromophore, and an anionic dipyrromethene chromophore is preferred, and an anionic xanthene chromophore, an anionic cyanine chromophore, and an anionic dipyrromethene A red cured film or a blue cured film containing at least one anionic chromophore selected from the group consisting of chromophores and a compound having an ammonium cation is more preferred.

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

  The color liquid crystal display element having the colored cured film of the present invention includes TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In-Plane Switching) type, VA (Vertical Alignment) type, OCB (Optical). An appropriate liquid crystal mode such as a Compensated Birefringence type is applicable.

  Moreover, the organic EL display element provided with the colored cured film of the present invention can take an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242.

  Moreover, the electronic paper provided with the colored cured film of the present invention can take an appropriate structure, and examples thereof include a structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169.

Solid-state image sensor The solid-state image sensor of the present invention comprises the colored cured film of the present invention. In addition, the solid-state imaging device of the present invention can take an appropriate structure. For example, as one embodiment, by using the colored composition of the present invention to form a colored pixel (colored cured film) on a semiconductor substrate such as a CMOS substrate by the same operation as described above, particularly color separation is performed. It is possible to manufacture a solid-state imaging device having excellent properties.

  In particular, the solid-state imaging device of the present invention is preferably a solid-state imaging device comprising the colored cured film of the present invention and a colored cured film containing an acid dye. More preferably, the solid-state imaging device of the present invention includes a first colored cured film, a second colored cured film, and a third colored cured film, and the first colored cured film uses the colored composition of the present invention. The second colored cured film is preferably formed using a colored composition containing an acid dye. More preferably, a first colored cured film formed using the colored 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 A solid-state imaging device having a colored cured film is preferable. Such an aspect is preferable from the viewpoint of creating a solid-state imaging device having excellent color separation.

  A preferable embodiment in this case is the same as that described in the display element.

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

<Synthesis of dispersant>
Dispersant synthesis example 1
In a flask equipped with a stir bar, 30.0 g of methyl methacrylate, 86.2 g of n-butyl methacrylate, 1.5 g of AIBN and 4.0 g of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved in 150 mL of toluene. Nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 60 ° C., and this temperature was maintained for 24 hours to perform living radical polymerization.

  Next, a solution obtained by dissolving 364 mg of AIBN and 14.8 g of dimethylaminoethyl methacrylate in 50 mL of toluene and replacing with nitrogen for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 60 ° C. for 24 hours. Then, it adjusted to the 40 mass% solution of propylene glycol monomethyl ether by vacuum concentration. In this way, a block copolymer dispersant (b2-1) comprising an A block having a repeating unit derived from dimethylaminoethyl methacrylate and a B block having a repeating unit derived from methyl methacrylate and n-butyl methacrylate was obtained. . This is referred to as “dispersant (b2-1) solution”.

Dispersant synthesis examples 2 to 9
In Dispersant Synthesis Example 1, a dispersant was synthesized in the same manner as Dispersant Synthesis Example 1 except that the amount of monomer used was changed as shown in Table 1. Table 1 shows the molar ratio of monomers constituting the dispersant.
Dispersants (b1-1) to (b1-5) correspond to the dispersant (b1). Dispersants (b2-1) to (b2-3) correspond to the dispersant (b2). The 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 as follows.

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

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

<Synthesis of binder resin>
Binder resin synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 29 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 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 of methyl methacrylate (166.5 mmol), phenyl methacrylate A mixed solution of 15.15 parts by mass (93.4 mmol) and 2.27 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was added dropwise over 1 hour, and this temperature was maintained at 2 Polymerized for hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and further polymerized for 1 hour to obtain a solution (solid content concentration: 40% by mass) containing the binder resin (D1). This is referred to as “binder resin (D1) solution”. The obtained binder resin (D1) had an Mw of 9,700 and an Mn of 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 purged with nitrogen. Heating to 80 ° C., at the same temperature, 18.0 parts by mass of cyclohexanone, 21.6 parts by mass of methacrylic acid, 27.0 parts by mass of tricyclo- [5.2.1.0 ^2,6 ] -decanyl (meth) acrylate Part, 2-ethylhexyl EO-modified acrylate (manufactured by Toagosei Co., Ltd., trade name: M-120) 13.5 parts by mass and glycerol methacrylate 31.0 parts by mass, cyclohexanone 64 parts by mass and 2,2′-azo A mixed solution of 7.2 parts by mass of bisbutyronitrile was added dropwise over 2 hours, and polymerization was performed for 1 hour while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 90 ° C., and polymerization was further performed for 1 hour. Next, 25.72 parts by mass of 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK, trade name Karenz MOI) (95 mol% with respect to the number of moles of glycerol methacrylate) and 0.36 parts by mass of 4-methoxyphenol The mixed solution was added dropwise over 15 minutes under air bubbling conditions, and the addition reaction was performed for 1.5 hours while maintaining this temperature. Thereafter, this solution was cooled to room temperature, and cyclohexanone was added so that the nonvolatile content was 40% by mass, thereby obtaining a solution (solid content concentration 40% by mass) containing the binder resin (D2). This is referred to as “binder resin (D2) solution”. The obtained binder resin (D2) was Mw = 8,600 and Mn = 3,600.

<Preparation and Evaluation of Colorant Dispersion>
Preparation Example 1
As a coloring agent, C.I. I. Pigment Green 58 and 12 parts by mass of C.I. I. 3 parts by weight of Pigment Yellow 138, 6.5 parts by weight of a solution obtained by diluting LPN6919 (manufactured by BYK) as a dispersant with propylene glycol monomethyl ether acetate (PGMEA) to a solid content concentration of 40% by weight, dispersion Agent (b3) solution 6.0 parts by mass (solid content concentration 40% by mass), binder resin (B1) solution 12.5 parts by mass (solid content concentration 40% by mass), and propylene glycol monomethyl ether acetate 60 parts by mass as a solvent. Using and processing with a bead mill, a colorant dispersion 1 was prepared. The amine value of LPN6919 (manufactured by BYK Corporation) measured by the above method was 121 mgKOH / g.

Evaluation of Storage Stability of Colorant Dispersion The viscosity immediately after preparation of the colorant dispersion 1 was measured using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). Next, the colorant dispersion 1 was filled in a light-shielding glass container and allowed to stand at 23 ° C. for 14 days in a sealed state, and then the viscosity was measured again using an E-type viscometer (manufactured by Tokyo Keiki). Then, the increase rate of the viscosity after storage for 14 days with respect to the viscosity immediately after preparation is calculated. When the increase rate is less than 3%, “AA”, when it is 3% or more and less than 5%, “A”, 5% or more The case of less than 10% was evaluated as “B”, and the case of 10% or more was evaluated as “C”. The results are shown in Table 2.

Preparation Examples 2-40
In Preparation Example 1, the type and amount of each component were changed as shown in Tables 2 to 3, and colorant dispersions 2 to 40 were obtained. Then, in the evaluation of the storage stability of the colorant dispersion, evaluation was performed in the same manner as in Preparation Example 1 except that the colorant dispersions 2 to 40 were used instead of the colorant dispersion 1. The results are shown in Tables 2-3.

In Tables 2-3, each component is as follows.
G58: C.I. I. Pigment Green 58
G59: C.I. I. Pigment Green 59
Y138: C.I. I. Pigment Yellow 138
Y139: C.I. I. Pigment Yellow 139
LPN6919: A solution obtained by diluting LPN6919 (manufactured by BYK) with PGMEA so as to have a solid content concentration of 40% by mass.

<Preparation and evaluation of coloring composition>
Comparative Example 1
100.0 parts by mass of the colorant dispersion 1, 12.0 parts by mass (solid content concentration 40% by mass) of the binder resin (D1) solution as a binder resin, and 10.3 parts by mass (solid content concentration) of the binder resin (D2) solution 40 mass%), a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as a polymerizable compound, 9.1 parts by mass, dipentaerythritol pentaacrylate and succinic acid Monoesterified product, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Toagosei Co., Ltd., trade name TO-1382), 3.0 parts by mass, 2-benzyl-2-dimethylamino- as a photopolymerization initiator 1- (4-morpholinofeni Le) Butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.5 parts by mass and NCI-831 (produced by ADEKA Co., Ltd.) 1.4 parts by mass, mega as a fluorosurfactant Fax F-554 (manufactured by DIC Corporation) 0.1 parts by mass, and as a solvent, 116.0 parts by mass of propylene glycol monomethyl ether acetate and 40.0 parts by mass of ethyl 3-ethoxypropionate are mixed to give a green color. A composition (GS-1) was prepared.

Evaluation of solvent resistance A colored composition (GS-1) was applied on a soda glass substrate having a SiO ₂ film formed on the surface thereof to prevent elution of sodium ions, using a spin coater, and then heated at 90 ° C. The plate was pre-baked for 2 minutes to form a coating film having a thickness of 2.5 μm.
Subsequently, after cooling this board | substrate to room temperature, the radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was exposed with the exposure amount of 400 J / m < ² > to the coating film through the photomask using the high pressure mercury lamp. Then, shower development was performed for 60 seconds by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 230 ° C. for 20 minutes to form a strip pattern on the substrate. About this strip-like pattern, using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinate value (x, y) and the stimulus value (Y) in the CIE color system with a C light source and a 2-degree field of view. It was measured.
Next, the substrate was immersed in N-methylpyrrolidone at 25 ° C. for 3 minutes. About the strip pattern after immersion, using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), C light source, 2 degree visual field, chromaticity coordinate value (x, y) and stimulus value (Y ) Was measured. 1. Color change before and after immersion, that is, ΔE ^* ab is calculated, “AA” when the value of ΔE ^* ab is 1.0 or less, “A” when greater than 1.0 and 2.0 or less. The case where it was larger than 0 and 3.0 or less was evaluated as “B”, and the case where it was larger than 3.0 was evaluated as “C”. The results are shown in Tables 4-5. It can be said that the smaller the ΔE ^* ab value, the better the solvent resistance.

Evaluation of heat resistance The colored composition (GS-1) was applied on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed using a spin coater, and then a hot plate at 90 ° C. Was pre-baked for 2 minutes to form a coating film having a thickness of 2.5 μm.
Subsequently, after cooling this board | substrate to room temperature, the radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was exposed with the exposure amount of 400 J / m < ² > to the coating film through the photomask using the high pressure mercury lamp. Then, shower development was performed for 60 seconds by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 230 ° C. for 20 minutes to form a colored cured film on the substrate. About the obtained colored cured film, using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), a chromaticity coordinate value (x, y) and a stimulus value (Y ) Was measured.
Next, the substrate was further baked twice at 230 ° C. for 20 minutes. The chromaticity coordinate values (x, y) and stimulus values (Y) of the substrate after the additional baking were measured twice, and the color change before and after the additional baking, ie, ΔE ^* ab was evaluated. As a result, the case where the value of ΔE ^* ab was 1.5 or less was evaluated as “A”, the case where it was larger than 1.5 and 3.0 or less was evaluated as “B”, and the case where it was larger than 3.0 was evaluated as “C”. The results are shown in Tables 4-5. In addition, it can be said that heat resistance is so favorable that (DELTA ⁾ E ^* ab value is small.

Evaluation of Storage Stability of Colored Composition In the evaluation of storage stability of the colorant dispersion, the color composition (GS-1) was used in the same manner except that the color composition (GS-1) was used instead of the colorant dispersion 1. The viscosity immediately after preparation of GS-1) and the viscosity after storage for 14 days at 23 ° C. were measured, and the increase rate after storage for 14 days at 23 ° C. was calculated. “AA” when the increase rate is less than 3%, “A” when it is 3% or more and less than 5%, “B” when it is 5% or more and less than 10%, and “B” when it is 10% or more. The results are shown in Tables 4-5 as "C".

Evaluation of foreign matter at the boundary with adjacent pixels After applying the colored composition (GS-1) on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions is formed using a spin coater, Pre-baking was performed for 2 minutes on a hot plate at 90 ° C. to form a coating film having a thickness of 2.4 μm.
Next, after cooling this substrate to room temperature, the entire surface was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at a dose of 400 J / m ² without using a photomask using a high-pressure mercury lamp. . Then, shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 230 ° C. for 30 minutes to form a green cured film (T-1) on the substrate.
Next, after applying the blue coloring composition (BS-1) prepared by the method described later on the green cured film (T-1) using a spin coater, pre-baking is performed for 2 minutes on a hot plate at 90 ° C. And a coating film having a thickness of 2.5 μm was formed. Subsequently, after cooling this board | substrate to room temperature, the radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was exposed to the coating film through the photomask using the high pressure mercury lamp with the exposure amount of 400 J / m < ² >. Then, shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, the substrate is washed with ultrapure water, air-dried, and further post-baked in a clean oven at 230 ° C. for 30 minutes, thereby forming a dot-patterned blue cured film on the green cured film (T-1). (T-2) was formed.
About the obtained board | substrate, it observed at a magnification of 20,000 times using a scanning electron microscope (SEM), and the generation | occurrence | production state of the foreign material in the boundary vicinity of a green cured film (T-1) and a blue cured film (T-2) is shown. confirmed. In a region where the blue cured film (T-2) is formed in a slope shape with respect to the green cured film (T-1), the case where the number of foreign matters observed in one field of view is 10 or less is “A”, 11 The case of not less than 50 and not more than 50 was evaluated as “B”, and the case of 51 or more was evaluated as “C”. The results are shown in Tables 4-5.

The preparation method of a blue coloring composition (BS-1) is as follows.
As a coloring agent, C.I. I. 15 parts by weight of CI Pigment Blue 15: 6, 12.5 parts by weight of BYK-LPN21116 (produced by BYK) as a dispersant (solid content concentration 40% by weight), and 72.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent The pigment dispersion (X-1) was prepared by processing with a bead mill.
Moreover, 10 mass parts of dyes represented by the following formula (a) were dissolved in 90 mass parts of methyl lactate to prepare a dye solution (X-2).
15.6 parts by mass of pigment dispersion (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 40% by mass), dipentaerythritol Mixture of hexaacrylate and dipentaerythritol pentaacrylate (Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) 7.7 parts by mass, NCI-831 (made by ADEKA Co., Ltd.) 2.1 parts by mass, MegaFuck F-554 0.4 parts by mass (manufactured by DIC Corporation), 0.14 parts by mass of a compound represented by the following formula (b), and 63.1 parts by mass of propylene glycol monomethyl ether acetate are mixed to give a blue colored composition ( BS-1) was prepared.

Evaluation of dye transfer property A colored composition (GS-1) was applied on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed using a spin coater, and then heated at 90 ° C. The plate was pre-baked for 2 minutes to form a coating film having a thickness of 2.4 μm.
Next, after cooling this substrate to room temperature, the entire surface was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at a dose of 400 J / m ² without using a photomask using a high-pressure mercury lamp. . Then, shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, the substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 230 ° C. for 30 minutes to form a green cured film (T-3) on the substrate. About this green cured film (T-3), using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), C light source, chromaticity coordinate value (x, y) and stimulus in the CIE color system in a 2 degree visual field The value (Y ₁ ) was measured.
Next, after coating the blue coloring composition (BS-1) on the green cured film (T-3) using a spin coater, prebaking was performed for 2 minutes on a hot plate at 90 ° C. to obtain a film thickness of 2 A 5 μm coating film was formed. Next, after cooling the substrate to room temperature, a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. is discharged to the substrate at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm). For 90 seconds. Thereafter, the substrate was washed with ultrapure water and air-dried. About this green cured film (T-3), using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), C light source, chromaticity coordinate value (x, y) and stimulus in the CIE color system in a 2 degree visual field The value (Y ₂ ) was measured.
ΔY = Y ₁ −Y ₂ is calculated, “A” when the value of ΔY is less than 0.2, “B” when the value is 0.2 or more and 0.7, and “C” when 0.7 or more. ". The results are shown in Tables 4-5. In addition, it can be said that the dye transfer property is suppressed, so that the ΔY value is small.

Evaluation of average surface roughness Colored composition (GS-1) was applied on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed on the surface by using a spin coater, and then at 90 ° C. Pre-baking was performed for 100 seconds with a hot plate to form a coating film having a thickness of 2.5 μm.
Next, after cooling the substrate to room temperature, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 400 J / m ² through a photomask. Thereafter, a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. was discharged onto these substrates at a developing 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 then post-baked in a clean oven at 220 ° C. for 30 minutes to form a pixel array in which green stripe pixel patterns were arranged on the substrate. .
The average surface roughness (smoothness of the pattern surface) at the top of the obtained pixel pattern was measured using an atomic force microscope manufactured by Digital Instruments, and the case where the average surface roughness was 30 mm or less was “A”. The case of more than 30 Å and 50 Å or less was evaluated as “B”, and the case of more than 50 と し て was evaluated as “C”. The results are shown in Tables 4-5.

Examples 1-31 and Comparative Examples 2-12
In Comparative Example 1, the types and amounts of the respective components were changed as shown in Tables 4 to 5 to obtain green colored compositions (GS-2) to (GS-43). And it evaluated similarly to the comparative example 1 except having replaced with the coloring composition (GS-1) and having used the coloring compositions (GS-2)-(GS-43). The results are shown in Tables 4-5.
However, in Examples 25-31 and Comparative Examples 11-12 using two kinds of colorant dispersions, first, two kinds of colorant dispersions are mixed, and this mixture is mixed with a binder resin, a polymerizable compound, and light. Colored compositions (GS-35) to (GS-43) were prepared by mixing a polymerization initiator, an additive, and a solvent.

In Tables 4-5, each component is as follows.
E1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA)
E2: monoesterified product of dipentaerythritol pentaacrylate and succinic acid, mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name TO-1382, manufactured by Toagosei Co., Ltd.)
F1: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name: Irgacure 369, manufactured by Ciba Specialty Chemicals)
F2: NCI-831 (manufactured by ADEKA Corporation)
G1: MegaFuck F-554 (manufactured by DIC Corporation)
C1: Propylene glycol monomethyl ether acetate C2: Ethyl 3-ethoxypropionate

Claims (20)

(A) a colorant dispersion containing a pigment, (B) a dispersant, and (C) a colorant dispersion containing a solvent,
(B) A dispersant is (b1) a dispersant having an amine value of YmgKOH / g and (b2) a (meth) acrylic dispersant having an amine value of XmgKOH / g (provided that Y> 140 and 0 <X < 100)).   The colorant dispersion according to claim 1, wherein Y> 150 and Y ≦ 230.   The colorant dispersion according to claim 1 or 2, wherein X <80.   The colorant dispersion according to claim 1, wherein Y + X ≧ 190 and Y + X ≦ 400.   The colorant dispersion according to claim 1, wherein YX ≧ 50.   The colorant dispersion according to any one of claims 1 to 5, wherein the pigment comprises a halogenated metal phthalocyanine pigment. (A) A method for producing a colorant dispersion comprising a step of mixing and dispersing a colorant containing a pigment in (C) a solvent in the presence of (B) a dispersant,
(B) As a dispersant, (b1) a first dispersant containing a dispersant having an amine value of YmgKOH / g (provided that Y> 140), and (b2) an amine value of XmgKOH / g (meth) A method for producing a colorant dispersion using a second dispersant containing an acrylic dispersant (however, 0 <X <100). A first dispersant containing at least (b1) a dispersant having an amine number of YmgKOH / g (where Y> 140) and (C) a first dispersion containing a solvent;
At least (b2) a second dispersant containing a (meth) acrylic dispersant (where 0 <X <100) having an amine value of X mg KOH / g, and (C) a second dispersion containing a solvent. A method for producing a colorant dispersion comprising the step of mixing
A manufacturing method in which at least one of the first dispersion and the second dispersion contains (A) a colorant containing a pigment. (A) A coloring composition containing a pigment, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a polymerizable compound,
(B) A dispersant is (b1) a dispersant having an amine value of YmgKOH / g and (b2) a (meth) acrylic dispersant having an amine value of XmgKOH / g (provided that Y> 140 and 0 <X < 100)).   The coloring composition according to claim 9, wherein Y> 150 and Y ≦ 230.   The coloring composition according to claim 9 or 10, wherein X <80.   The coloring composition according to any one of claims 9 to 11, wherein Y + X ≧ 190 and Y + X ≦ 400.   The coloring composition of any one of Claims 9-12 which is YX> = 50.   The coloring composition according to any one of claims 9 to 13, wherein the pigment contains a metal halide phthalocyanine pigment.   The manufacturing method of a coloring composition including the process of mixing the coloring agent dispersion obtained by the manufacturing method of Claim 7 or 8 and at least (E) polymeric compound.   The colored cured film formed using the coloring composition of any one of Claims 9-14.   A display device comprising the colored cured film according to claim 16. A display element comprising a colored cured film having a first colored cured film and a second cured film,
The first colored cured film is the colored cured film according to claim 16,
The second cured film is a colored cured film containing an acid dye,
Display element.   A solid-state imaging device comprising the colored cured film according to claim 16. A solid-state imaging device comprising a colored cured film having a first colored cured film and a second cured film,
The first colored cured film is the colored cured film according to claim 16,
The second cured film is a colored cured film containing an acid dye,
Solid-state image sensor.