JP5678411B2 - Red coloring composition and color filter - Google Patents

Description

  The present invention relates to a red coloring composition containing a dye and a pigment, and particularly relates to a red coloring composition suitable for producing a color filter having high contrast and high transmittance, and a color filter using the same.

  In recent years, liquid crystal display devices have been evaluated for space saving, light weight, power saving, and the like due to their thinness, and recently they have been rapidly spread to television applications. For television applications, it is required to further improve performance such as luminance and contrast, and further enhancement of brightness and contrast is desired for color filters that are members of liquid crystal display devices.

Conventionally, the red filter segment constituting the color filter includes C.I., which is an anthraquinone red pigment. I. PigmentRed 177 has been used. This pigment can be easily miniaturized by a mechanical treatment, and the finer pigment can be dispersed relatively easily, which is useful for increasing the contrast (for example, Patent Documents). 1). However, there is a limit to the brightness improvement in terms of spectral characteristics.
C. I. PigmentRed 254 is often used. This pigment is C.I. I. Since the transmission spectrum in the vicinity of 600 nm is closer to the short wavelength side than PigmentRed 177, the absorption of the red bright line of the backlight is less, and thus the brightness can be improved. However, miniaturization by mechanical processing is easy, but since the cohesive force is strong, it becomes difficult to disperse as the degree of miniaturization progresses, and it is not easy to improve contrast (see, for example, Patent Document 1).

  Recently, it contains a diketopyrrolopyrrole red pigment, an anthraquinone red pigment, and an azo yellow pigment, and by reducing the average primary particle size of each pigment, it has a high transmittance and a high contrast red coloring composition. Has been attempted (see, for example, Patent Document 1). However, the diketopyrrolopyrrole pigment becomes difficult to disperse as the degree of fineness proceeds as described above, and further, in the post-baking step in the step of forming the red colored layer by curing the red colored composition, the diketopyrrolopyrrole pigment is used. The pigment precipitates. The precipitated crystal causes a decrease in contrast by scattering and depolarizing light in the liquid crystal display device, and further causes a decrease in reliability such as liquid crystal contamination. Therefore, there is a limit to improving the contrast by miniaturization, and it has been difficult to obtain a red colored layer having high transmittance, high contrast, and high reliability (for example, see Patent Document 2).

  On the other hand, an attempt has been made to achieve high contrast and high transmittance by using a dye instead of a depolarizing pigment. There are many types of dyes, unlike pigments, and high transmittance can be achieved by using dyes with optimal spectral characteristics, and depolarization is virtually zero and high contrast can be obtained. A liquid crystal display device having favorable visual characteristics can be manufactured by using it for manufacturing a color filter.

However, dyes have poor heat resistance and light resistance, and have problems such as extreme fading when subjected to baking at a high temperature in the production process. Also, when used as a negative resist using radical polymerization, it is difficult to obtain sufficient sensitivity because the dye acts as a so-called “radical eater” that deactivates radicals. In order to solve this problem, attempts have been made to obtain a highly sensitive resist by adding a polyfunctional thiol to a dye resist and using an ene-thiol reaction. Low,
It was insufficient for use in a color filter for liquid crystal display devices (see, for example, Patent Documents 3 and 4).

JP 2008-209804 A JP 2007-133131 A JP 2006-71890 A JP 2006-78602 A

  An object of the present invention is to provide a color filter having high contrast and high transmittance and good visual characteristics, and a red coloring composition containing a dye and a pigment capable of providing the color filter with high productivity.

The present invention is a red coloring composition containing A) a coloring material, B) a binder resin, C) a radical polymerizable monomer, D) a photo radical generator, and E) a polyfunctional thiol, wherein the A) coloring material , Containing at least one pigment and one dye, and E) the polyfunctional thiol is 1% by mass to 10% by mass in the total solid content,
As the dye, C.I. containing a dye having an azo skeleton or a metal complex of a dye having an azo skeleton . I. Solvent Red 124, or C.I. I. A red coloring composition characterized by being Solvent Red 89 .

Further, the present invention provides the red coloring composition according to the above invention, wherein A) the coloring material is 10% by mass to 60% by mass in the total solid content, and A) the dye is 30% by mass in the total mass of the coloring material. It is a red coloring composition characterized by being within .

  Further, the present invention provides the red coloring composition according to the above invention, wherein the pigment is at least one selected from diketopyrrolopyrrole red pigments, anthraquinone red pigments, azo yellow pigments, and isoindoline yellow pigments. It is a red coloring composition characterized by containing the pigment of this.

  Further, the present invention provides the red coloring composition according to the above invention, wherein the diketopyrrolopyrrole pigment is C.I. I. Pigment Red 254, an anthraquinone red pigment is C.I. I. Pigment 177, an azo yellow pigment, C.I. I. Pigment Yellow 150, an isoindoline-based yellow pigment is C.I. I. Pigment Yellow 139, which is a red coloring composition.

Moreover, this invention is manufactured using the red coloring composition of any one of Claims 1-4 , The color filter characterized by the above-mentioned.

In the present invention, by using a dye and a pigment in combination as a coloring material, high contrast and high brightness that cannot be achieved by a pigment alone can be obtained. Furthermore, by containing a polyfunctional thiol, the reduction in sensitivity due to the dye is compensated and a highly sensitive red coloring composition is obtained.
Further, the content of the coloring material is suitably 10% to 60%. If it is 10 % or less, the film thickness becomes too thick in order to obtain a practical color strength, so that the film formation becomes difficult and the productivity also deteriorates. On the other hand, if it is 60% or more, other components necessary as a resist are insufficient, sensitivity cannot be obtained, and the film shape deteriorates.

As the dye, a dye having an azo skeleton or a cobalt complex thereof is preferable. I. Solvent Red 124, C.I. I. Solvent Red 89 is good. As the pigment, a red pigment and a yellow pigment are preferably used. I. Pigment Red 254, and C.I. I. Pigment 177, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 139 is good.

It is a structural example of the color filter for liquid crystal display devices. It is sectional drawing of the liquid crystal display device provided with the color filter of this invention.

Hereinafter, embodiments of the present invention will be described in detail.
The red coloring composition according to the present invention is a red coloring composition containing a coloring material, a binder resin, a radical polymerizable monomer, a photo radical generator, and a polyfunctional thiol. As the coloring material, at least one pigment and one kind are used. Containing a dye. In addition, it contains a dispersion aid, a photopolymerization initiator, a sensitizer, a leveling agent and the like as necessary.

  The aforementioned polyfunctional thiol compensates for a decrease in sensitivity due to inhibition of dye polymerization by a chain transfer reaction, and may be any compound having two or more thiol groups, such as hexanedithiol, decanedithiol, 1,4-butane. Diol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, Trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, Examples thereof include 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine. These polyfunctional thiols can be used alone or in combination. The content is 1% by mass to 10% by mass in the total solid content. If the amount is less than 1% by mass, the sensitivity cannot be sufficiently compensated. If the amount is 10% by mass or more, the amount of the transparent solid component such as a monomer or a binder resin is decreased, which causes a decrease in transmittance.

The content of the coloring material is preferably 10% by mass to 60% by mass, and more preferably 20% by mass to 50% by mass in the total solid content. If it is 10% by mass or less, the film thickness becomes too thick to obtain a practical color strength, so that film formation becomes difficult and productivity is also deteriorated. On the other hand, when the amount is 60% by mass or more, other components such as a monomer, a binder resin, and a polymerization initiator that are necessary as a resist are insufficient, so that the sensitivity cannot be obtained and the film shape is deteriorated and the sensitivity is lowered. Among the color materials, the dye content is preferably within 50% by mass of the total color material amount. More preferably, it is 30 mass% or less. If it is 50% by mass or more, the sensitivity is remarkably lowered due to inhibition of dye polymerization, making it difficult to use.

  The organic solvent-soluble dye in the present invention can be used without particular limitation, and examples thereof include conventionally known dyes for color filters. Examples of the known dyes include, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, Patent 2592207, US Pat. No. 4,808,501, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, Examples thereof include dyes described in Kaihei 6-51115 and JP-A-6-194828.

The chemical structure of the dye that can be used as the organic solvent-soluble dye in the present invention includes triphenylmethane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, A benzopyran type, an indigo type, etc. are mentioned. Particularly preferred as the organic solvent-soluble dye in the present invention are pyrazole azo dyes, anilinoazo dyes, pyrazolotriazole azo dyes, pyridone azo dyes, anthraquinone dyes, and anthrapyridone dyes. Among them, dyes having an azo skeleton and metal complexes of dyes having an azo skeleton are excellent in terms of coloring power and solubility. I. Solvent Red 124, C.I. I. Solvent Red 89 is a good dye for red coloring compositions.

  In the case of a resist system that performs water or alkali development, an acid dye and / or a derivative thereof can be preferably used as the organic solvent-soluble dye in the present invention from the viewpoint of completely removing the binder and / or dye by development. There is. In addition, as the organic solvent-soluble dye in the present invention, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof are also preferably used. can do.

(Acid dyes)
The acid dye will be described. The acidic dye is not particularly limited as long as it is a dye having an acidic group such as sulfonic acid, carboxylic acid, phenolic hydroxyl group, etc., but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, curability. It is selected in consideration of all required performance such as interaction with other components in the composition, light resistance, heat resistance and the like.

Hereinafter, specific examples of the acid dye will be given. However, the present invention is not limited to these. For example,
Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
Acid Yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251;
Direct Yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129, 136, 138, 141;
Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
Food Yellow 3; and derivatives of these dyes.

Among the above acid dyes,
Acid Orange 8, 51, 56, 74, 63, 74;
Acid Red 1, 4, 8, 34, 37, 42, 52, 57, 80, 97, 114, 143, 145, 151, 183, 217, 249;
Acid Yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 134, 155, 169, 172, 184, 220, 228, 230, 232, 243; Derivatives of these dyes are preferred.

  Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Orange 45; Rhodamine B; Rhodamine 110; 2,7-Naphthalendisulfonic acid; 3-[(5-chloro-2-phenoxyphenyl) hydrazono] -3,4-dihydro-4-oxo-5- [minyl]-[ulphonyl] , Etc. and derivatives of these dyes can also be suitably used.

Examples of the derivative of the acid dye include inorganic salts of acid dyes having an acid group such as sulfonic acid and carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and the like, and curable compositions. It is not particularly limited as long as it can be dissolved as a solution, but it needs solubility, absorbance, interaction with other components in the curable composition, light resistance, heat resistance, etc. in an organic solvent or developer. It is selected in consideration of all the performance to be performed.
The salt of the said acid dye and a nitrogen-containing compound is demonstrated. The method of forming a salt of an acid dye and a nitrogen-containing compound may be effective for improving the solubility of the acid dye (providing solubility in an organic solvent) and improving heat resistance and light resistance.

  The nitrogen-containing compound that forms a salt with the acid dye and the nitrogen-containing compound that forms an amide bond with the acid dye will be described. Nitrogen-containing compounds are the solubility of salts or amide compounds in organic solvents and developers, salt-forming properties, dye absorbance / color value, interaction with other components in the curable composition, and heat resistance as a colorant. In addition, it is selected in consideration of all of light resistance and the like. When selecting only from the viewpoint of absorbance and color value, the nitrogen-containing compound is preferably as low as possible in molecular weight, more preferably having a molecular weight of 300 or less, more preferably having a molecular weight of 280 or less, and a molecular weight of 250 or less. Those are particularly preferred.

The molar ratio (hereinafter referred to as “n”) of the nitrogen-containing compound / acid dye in the salt of the acid dye and the nitrogen-containing compound will be described. The above n is a value that determines the molar ratio between the acid dye molecule and the amine compound that is a counter ion, and can be freely selected according to the salt forming conditions of the acid dye-amine compound. Specifically, a number between 0 <n ≦ 5 of the number of functional groups of the acid in the acid dye is practically used, and the solubility in organic solvents and developers, salt formation, absorbance, and curable composition It is selected in consideration of all necessary performance such as interaction with other components, light resistance, heat resistance and the like. When selecting from the standpoint of absorbance only, n is preferably a value between 0 <n ≦ 4.5, more preferably a value between 0 <n ≦ 4, and 0 <n. It is particularly preferable to take a numerical value between ≦ 3.5.
Since the acidic dye shown above has become an acidic dye by introducing an acidic group in its structure, it can be made a non-acidic dye by changing its substituent.

In some cases, the acid dye works favorably during alkali development, but on the other hand, it may become over-developed, and a non-acid dye may be preferably used. As the non-acidic dye, dyes having no acidic group of the acidic dyes exemplified above are preferably used.
As a pigment constituting the red coloring composition for a color filter according to this embodiment, an anthraquinone red pigment, an azo yellow pigment, or the like can be contained as necessary. Examples of the anthraquinone red pigment include C.I. I. PigmentRed 177, and is preferably used because of its excellent light resistance, heat resistance, transparency, and coloring power. Examples of the azo yellow pigment include C.I. I. Pigment Yellow 1, 3, 10, 12, 13, 14, 17, 55, 81, 83, 93, 94, 95, 97, 150, 154, 166, 167, 180 and the like. Among them, C.I. I. Pigment Yellow 150 is particularly preferably used because of its excellent light resistance, heat resistance, transparency, and coloring power.

Note that azo yellow pigments are used for toning, but in general for color filter applications, C.I. I. Pigment Yellow 139, isoindoline pigments such as C.I. I. In many cases, a quinophthalone pigment such as Pigment Yellow 138 is used. However, when only these pigments are used, the depolarization attributed to the particle shape or molecular structure of the pigments appears, which is disadvantageous for increasing the contrast.
The content of these two pigments is preferably 60% by weight or less of an anthraquinone red pigment and 30% by weight or less of an azo yellow pigment based on the total weight of the pigment (100% by weight), more preferably The anthraquinone red pigment is preferably 50% by weight or less and the azo yellow pigment is 25% by weight or less. When the anthraquinone red pigment exceeds 60% by weight, it is difficult to obtain sufficient brightness. On the other hand, when the content of the azo yellow pigment exceeds 30% by weight, the color reproducibility tends to be deteriorated because the hue is excessively shifted to yellow.

  Examples of the diketopyrrolopyrrole red pigment include C.I. I. Pigment Orange 71, C.I. I. Pigment Red 254, 255, 264 and the like. Among them, C.I. I. PigmentRed 254 is particularly preferably used because of its excellent light resistance, transparency, and coloring power.

  As a means for reducing the primary particle size of the pigment, a method of mechanically pulverizing the pigment (referred to as a grinding method), a solution dissolved in a good solvent is introduced into a poor solvent, and a pigment having a desired primary particle size is precipitated. And a method of producing a pigment having a desired primary particle size at the time of synthesis (referred to as a synthetic precipitation method). Depending on the synthesis method and chemical properties of the pigment used, an appropriate method can be selected for each pigment. Each method will be described below.

  In the grinding method, the pigment is mechanically kneaded with a grinding agent such as water-soluble inorganic salt such as salt and a water-soluble organic solvent that does not dissolve it using a ball mill, sand mill, or kneader (hereinafter, this process is salted). In this method, the inorganic salt and the organic solvent are washed away with water and dried to obtain a pigment having a desired specific surface area. However, since the pigment may crystallize due to the salt milling treatment, a method of preventing crystal growth by adding a solid resin that is at least partially dissolved in the water-soluble organic solvent or a dispersion aid described later during the treatment is effective. It is.

  As for the ratio of the pigment to the inorganic salt, if the ratio of the inorganic salt is increased, the efficiency of refining the pigment is improved. In general, the inorganic salt is used in an amount of 1 to 30 parts by weight, preferably 2 to 20 parts by weight, based on 1 part by weight of the pigment. Further, the water-soluble organic solvent is added so that the pigment and the inorganic salt are uniformly hardened, and usually depends on the blending ratio of the pigment and the inorganic salt, but the amount of the pigment is usually 50 to 300% by weight. Used.

  The grinding method will be explained in more detail. A small amount of a water-soluble organic solvent is added as a wetting agent to a mixture of a pigment and a water-soluble inorganic salt, and after kneading with a kneader or the like, the mixture is put into water and high-speed. Agitate with a mixer to make a slurry. Next, a pigment having a desired primary particle size can be obtained by filtering, washing, and drying the slurry.

  The precipitation method is a method in which a pigment is dissolved in an appropriate good solvent and then mixed with a poor solvent to precipitate a pigment having a desired primary particle size. The primary method depends on the type and amount of the solvent, the precipitation temperature, the precipitation rate, etc. The particle size can be controlled. In general, pigments are difficult to dissolve in a solvent, so the solvents that can be used are limited. For example, strongly acidic solvents such as concentrated sulfuric acid, polyphosphoric acid, and chlorosulfonic acid, or bases such as dimethylformamide solution of liquid ammonia and sodium methylate Solvents and the like are known.

  As a typical example of the precipitation method, there is an acid pasting method in which a solution in which a pigment is dissolved in an acidic solvent is poured into another solvent and reprecipitated to obtain fine particles. Industrially, a method of injecting a sulfuric acid solution into water is generally used from the viewpoint of cost. The sulfuric acid concentration is not particularly limited, but is preferably 95 to 100% by weight. The amount of sulfuric acid used with respect to the pigment is not particularly limited. However, if the amount is too small, the solution viscosity is high and handling becomes poor. Conversely, if the amount is too large, the treatment efficiency of the pigment decreases. It is preferable to use sulfuric acid. The pigment need not be completely dissolved. The temperature at the time of dissolution is preferably 0 to 50 ° C., and if it is lower than 0 ° C., the sulfuric acid may be frozen and the solubility is also lowered. If the temperature is too high, side reactions tend to occur. The temperature of the water to be injected is preferably 1 to 60 ° C., and if the injection is started at a temperature higher than this temperature, it boils with the heat of dissolution of sulfuric acid, and the operation is dangerous. It will freeze at temperatures below this. The injection time is preferably 0.1 to 30 minutes with respect to 1 part by weight of the pigment.

  The primary particle size of the pigment can be controlled while taking into consideration the degree of sizing of the pigment by selecting a method that combines a precipitation method such as the acid pasting method and a grinding method such as the salt milling method. Is more preferable because the fluidity as a dispersion can be secured at this time. At the time of salt milling or acid pasting, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant described later can be used in combination in order to prevent pigment aggregation associated with primary particle size control. In addition, by controlling the primary particle size in the form of coexistence of two or more pigments, even a pigment that is difficult to disperse alone can be finished as a stable dispersion.

The synthetic precipitation method is a method of synthesizing a pigment and simultaneously depositing a pigment having a desired primary particle size. However, when the produced fine pigment is taken out from the solvent, if the pigment particles are not aggregated into large secondary particles, filtration, which is a general separation method, becomes difficult. It is applied to azo pigments that are easily synthesized in water.
Furthermore, as a means for controlling the primary particle diameter of the pigment, the primary particle diameter of the pigment is reduced and dispersed simultaneously by dispersing the pigment for a long time with a high-speed sand mill or the like (so-called dry milling method in which the pigment is dry-pulverized). It is also possible.

  The binder resin and radical polymerizable monomer contained in the red coloring composition for a color filter according to the present embodiment are for dispersing or dissolving the pigment and the dye, and the binder resin, the precursor monomer, or a mixture thereof. Consists of. The binder resin is preferably a resin having a transmittance of 80% or more, preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Binder resins include thermoplastic resins, thermosetting resins, and active energy ray curable resins, and precursors thereof include monomers or oligomers that cure upon irradiation with active energy rays to form transparent resins. These can be used alone or in admixture of two or more.

  The binder resin and the radical polymerizable monomer can be used in an amount of 30 to 700 parts by weight, preferably 60 to 450 parts by weight, with respect to 100 parts by weight of the total color material in the red coloring composition. Moreover, when using the mixture of binder resin and its precursor, binder resin is 20-400 weight part with respect to a total of 100 weight part of the coloring material in a red coloring composition, Preferably it is 50-250 weight. It can be used in parts. The precursor of the binder resin can be used in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, with respect to 100 parts by weight of the total color material in the red coloring composition.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Active energy ray-curable resins include (meth) acrylic having a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group. A resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer by reacting a compound or cinnamic acid is used. In addition, linear polymers containing acid anhydrides such as styrene-maleic anhydride copolymer and α-olefin-maleic anhydride copolymer can be converted to (meth) acrylic compounds having hydroxyl groups such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  Monomers and oligomers that are cured by irradiation with active energy rays to form a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A di Ricidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylic Various acrylic acid esters and methacrylic acid esters such as acid esters, epoxy (meth) acrylates, urethane acrylates, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) Examples include acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like. These can be used alone or in admixture of two or more.

  When the composition is cured by ultraviolet irradiation, a photo radical generator or the like is added to the red colored composition for a color filter according to the present embodiment. As photo radical generators, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone compounds such as hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl Benzoin compounds such as dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenylsulfur Id, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone and other benzophenone compounds, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, Thioxanthone compounds such as 2,4-diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4 -Bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl)- Triazine compounds such as 6-triazine and 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyl) Oxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine, and the like, bis (2,4,6- Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 9,10-phenanthrenequinone, camphor Examples include quinone compounds such as non-ethyl anthraquinone, borate compounds, carbazole compounds, imidazole compounds, and titanocene compounds. These photo radical generators can be used alone or in combination. The photo radical generator can be used in an amount of 5 to 200 parts by weight, preferably 10 to 150 parts by weight, with respect to 100 parts by weight of the total color material in the red coloring composition.

The photo radical generator may be used alone or in admixture of two or more. As a sensitizer, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, Isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4 ′ Amine compounds such as -bis (diethylamino) benzophenone and 4,4'-bis (ethylmethylamino) benzophenone can also be used in combination. These sensitizers can be used alone or in combination. The sensitizer can be used in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photoradical generator in the red coloring composition.

  In the red coloring composition for a color filter according to this embodiment, the coloring material is sufficiently dispersed and dissolved in the binder resin and the radical polymerizable monomer so that the dry film thickness is 0.2 to 5 μm on the glass substrate. A solvent can be used for application to the substrate. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone. , Ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent and the like, and these are used alone or in combination. A solvent can be used in the quantity of 800-4000 weight part with respect to a total of 100 weight part of the coloring material in a red coloring composition, Preferably it is 1000-2500 weight part.

  The red coloring composition for a color filter according to this embodiment is produced by finely dispersing a pigment in a pigment carrier using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor. be able to. Moreover, in order to make these dispersion | distribution favorable, dispersion | distribution adjuvants, such as a pigment derivative, a resin-type pigment dispersant, and surfactant, can be contained suitably. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion, a red coloring composition in which the pigment is dispersed in a pigment carrier and a solvent using the dispersion aid is used. If so, a color filter excellent in transparency can be obtained. The dispersion aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the total pigment in the red coloring composition.

In addition to being a dispersion aid, the dye derivative has an effect of suppressing pigment crystal growth or aggregation in the filter segment. A pigment derivative is a compound in which a substituent is introduced into an organic pigment. Examples of the organic dye include azo series such as diketopyrrolopyrrole, azo, disazo, polyazo, phthalocyanine, anthraquinone, quinacridone, dioxazine, perinone, perylene, thioindigo, isoindoline, and isoindoline. Examples thereof include linone-based dyes, quinophthalone-based dyes, selenium-based dyes, and metal complex-based dyes. The organic dye constituting the dye derivative includes light yellow compounds such as naphthalene and triazine which are not generally called dyes.
Moreover, as a substituent, the substituent represented by the following general formula (1)-(4) is mentioned.

In the general formulas (1) to (4), X represents —SO ₂ —, —CO—, —CH ₂ NHCOCH _2.
-, -CH ₂ -or a direct bond is represented. v represents an integer of 1 to 10.
R4 and R5 are each independently an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, an optionally substituted phenyl group, or R4. And R5 together represent an optionally substituted heterocyclic residue containing an additional nitrogen, oxygen or sulfur atom.
R6 represents an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group.
R7, R8, R9, and R10 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or a substituted group. Represents a good phenyl group.
Y represents -NR11-Z-NR12- or a direct bond.
R11 and R12 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group. Represents.
Z represents an alkylene group having 1 to 36 carbon atoms which may be substituted, an alkenylene group having 2 to 36 carbon atoms which may be substituted, or a phenylene group which may be substituted.
P represents a substituent represented by the following formula (5) or a substituent represented by the formula (3).
Q represents a hydroxyl group, an alkoxyl group, a substituent represented by the formula (5) or a substituent represented by the formula (3). In the formulas (5) and (3), X, R4 to R10, and v are the same as X, R4 to R10, and v in the formulas (1) to (3).

  These pigment derivatives are used alone or in admixture of two or more, and are preferably used in an amount of 5 to 40 parts by weight, preferably 10 to 30 parts by weight, based on a total of 100 parts by weight of the pigment. Below this lower limit, the effect of suppressing the crystal growth or aggregation of the pigment is reduced, and when this upper limit is exceeded, the fluidity of the resulting red colored composition tends not to be maintained.

  Examples of resin-type pigment dispersants include condensates of ricinoleic acid and 1,2-hydroxystearic acid, basic polymer compounds, copolymers containing acid groups, fatty acid esters, aliphatic polyamine / polyester graft polymers, polyethylene / Polypropylene addition polymer can be used.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and diethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylaminoacetic acid Examples include amphoteric surfactants such as alkylbetaines such as betaine and alkylimidazolines, which can be used alone or in admixture of two or more.

  In order to stabilize the viscosity with time of the composition, the red coloring composition for the color filter according to the present embodiment can contain a storage stabilizer, and to improve the adhesion to the transparent substrate. An adhesion improver such as a silane coupling agent can also be contained. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned.

  Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4- Epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and other epoxysilanes, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N- β (aminoethyl) γ-aminopropyltri Ethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- Examples include aminosilanes such as phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

The color material according to the present embodiment can be prepared in the form of gravure offset printing ink, waterless offset printing ink, silk screen printing ink, solvent development type or alkali development type colored resist. The colored resist is obtained by dispersing the dye and the pigment in a composition containing a thermoplastic resin, a thermosetting resin or an active energy ray curable resin, a monomer, a photopolymerization initiator, and a solvent. is there. The dye and the pigment are preferably contained in a proportion of 10 to 60% by mass in total, based on the total solid content of the red coloring composition (100% by mass). More preferably, it is contained in a proportion of 20 to 50% by mass, and the remainder consists essentially of a resinous binder.
The red coloring composition is coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, more preferably 0, by means such as centrifugation, sintered filter, membrane filter, or the like. It is preferable to remove particles of 2 μm or more and mixed dust.

  FIG. 1 shows a configuration example of a color filter for a liquid crystal display device in which pixels are formed using the red coloring composition described above. A black matrix 2 is provided on a transparent substrate 1 and is partitioned by the black matrix 2. Three color filter segments of a red pixel 3R, a green pixel 3G, and a blue pixel 3B are formed in the region. The red pixel 3R is formed using the red coloring composition described above, and is formed using the known green and blue-red coloring compositions of the green pixel 3G and the blue pixel 3B.

  As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. Further, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate for driving the liquid crystal after the liquid crystal panel is formed.

Each color filter segment can be formed by, for example, a printing method, a photolithography method, or the like.
The formation of each color filter segment by the printing method can be patterned simply by repeating the printing and drying of the red coloring composition prepared as the above-mentioned various printing inks. Are better. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When forming each color filter segment by photolithography, the red coloring composition prepared as the solvent developing type or alkali developing type coloring resist is applied on a transparent substrate, such as spray coating, spin coating, slit coating, roll coating, etc. By a coating method, coating is performed so that the dry film thickness is 0.2 to 10 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Thereafter, the uncured portion is removed by dipping in a solvent or an alkali developer or spraying the developer with a spray or the like to form a desired pattern. Then, a color filter can be manufactured by repeating the same operation for other colors. Furthermore, in order to accelerate the polymerization of the colored resist, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

  In developing the red coloring composition, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. 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. In order to increase the UV exposure sensitivity, the colored resist is applied and dried, and then a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to inhibit polymerization inhibition by oxygen. Ultraviolet exposure can also be performed after the film to be prevented is formed.

The color filter according to the present embodiment can be manufactured by an electrodeposition method, a transfer method, or the like in addition to the above method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a transparent substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. is there.
The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet or transfer cylinder, and this filter segment is transferred to a desired transparent substrate.

  If a black matrix is formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate, the contrast of the liquid crystal display panel can be further increased. As the black matrix, a multilayer film of chromium, chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed can be used. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

On the color filter according to the present embodiment, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed as necessary.
FIG. 2 is a schematic cross-sectional view of a liquid crystal display device including a color filter according to an embodiment of the present invention. A liquid crystal display device 4 shown in FIG. 2 is a typical example of a TFT drive type liquid crystal display device for a liquid crystal TV, and includes a pair of transparent substrates 5 and 6 disposed so as to be opposed to each other. Liquid crystal (LC) is enclosed.
The liquid crystal (LC) is aligned according to a liquid crystal alignment mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), OCB (Optically Compensated Birefringence). .

A TFT (thin film transistor) array 7 is formed on the inner surface of the first transparent substrate 5, and a transparent electrode layer 8 made of, for example, ITO is formed thereon. An alignment layer 9 is provided on the transparent electrode layer 8. Further, on the outer surface of the transparent substrate 5, a polarizing plate 10 including a retardation film is formed.
On the other hand, the color filter 11 of the present invention is formed on the inner surface of the second transparent substrate 6. The red, green and blue filter segments constituting the color filter 11 are separated by a black matrix (not shown).
A transparent protective film (not shown) is formed so as to cover the color filter 11, and further, a transparent electrode layer 12 made of, for example, ITO is formed on the color filter 11, and the alignment layer 13 covers the transparent electrode layer 12. Is provided. A polarizing plate 14 is formed on the outer surface of the transparent substrate 6. A backlight unit 16 including a three-wavelength lamp 15 is provided below the polarizing plate 10.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. The symbol of the pigment indicates a color index number. For example, “PR254” represents “CI PigmentRed 254” and “PY150” represents “CI Pigment Yellow 150”.

[Chromaticity and contrast]
The red coloring composition is applied to a glass substrate by spin coating so that the chromaticity x after curing is 0.64 (F10 light source), dried at 70 ° C. for 20 minutes, and then ultraviolet rays are used using an ultrahigh pressure mercury lamp. Was exposed. Thereafter, this substrate was heat-treated at 230 ° C. for 1 hour to obtain a red colored film.
The red colored film was measured for chromaticity (Y, x, y) with an F10 light source using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). Further, polarizing plates were overlapped on both sides of the substrate on which the red colored film was formed, and the ratio of luminance (Lp) when the polarizing plates were parallel and luminance (Lc) when they were orthogonal, Lp / Lc was calculated as contrast. The luminance was measured using a color luminance meter ("BM-5A" manufactured by Topcon) under the condition of a 2 ° visual field. Table 4 shows the measurement results.

Table 1 shows the dye derivatives used in the following production examples.

a) Production of fine pigments
[Production Example 1]
100 parts of diketopyrrolopyrrole red pigment PR254 ("Irgafoa Red B-CF" manufactured by Ciba Specialty Chemicals), 10 parts of pigment derivative (D-1), 1000 parts of crushed salt, and 120 parts of diethylene glycol 1 made of stainless steel It was charged in a gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. The mixture was added to 2000 parts of warm water, heated to about 80 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained the refined pigment (R-1). The average particle diameter of the obtained pigment was 25 nm.

[Production Example 2]
Stainless steel 1 gallon kneader (Inoue Seisakusho Co., Ltd.) 100 parts of anthraquinone red pigment PR177 (“chromophthaled red A2B” manufactured by Ciba Specialty Chemicals Co., Ltd.), 8 parts of pigment derivative (D-2), 700 parts of ground salt and 180 parts of diethylene glycol And kneaded at 70 ° C. for 4 hours. The mixture was put into 4000 parts of warm water, heated to about 80 ° C., stirred with a high speed mixer for about 1 hour to form a slurry, filtered and washed with water to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and the refined pigment (R-2) was obtained. The average particle diameter of the obtained pigment was 30 nm.

Next, preparation of the acrylic resin solution used in Examples and Comparative Examples will be described. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).
b) Production of acrylic resin solution (P) 370 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 20.0 parts of methacrylic acid and 10.0 parts of methyl methacrylate at the same temperature. , A mixture of 55.0 parts of n-butyl methacrylate, 15.0 parts of 2-hydroxyethyl methacrylate, and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. It was. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained. The weight average molecular weight of the acrylic resin was about 40,000. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Thus, an acrylic resin solution (P) was prepared.

c) Manufacture of pigment dispersion The mixture having the composition shown in Table 2 was stirred and mixed uniformly, and dispersed with an Eiger mill ("Mini Model M-250MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 1 mm. Various pigment dispersions were obtained by filtration through a 5 μm filter. Table 2 also shows the pigment content in each pigment dispersion. In Table 2, Y-1 is PY150, manufactured by LANXESS: “E4GN-GT”, Y-2 is PY139, manufactured by BASF: “PALIOTOL YELLOW D1819”.

d) Preparation of red coloring composition <Example 1>
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 5 μm filter to obtain a red colored composition.
-Dye: C.I. I. Solvent Red 89 0.68% by mass
Made by Clariant (Savinyl FireRed GLS)
Pigment dispersion (PR-1) 28.8% by mass
Pigment dispersion (PR-2) 0.8% by mass
Pigment dispersion (PY-1) 4.8% by mass
-Acrylic resin solution (P) 28.5% by mass
・ Multifunctional thiol 0.5% by mass
(Trimethylolpropane tristhiopropionate)
・ Acrylate polyfunctional monomer 2.4% by mass
(Aronix M402 manufactured by Toagosei Co., Ltd.)
・ Photo radical generator 0.8% by mass
("Irgacure-OXE02" manufactured by Ciba Geigy)
・ Photosensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.) 0.2% by mass
・ Organic solvent (PGMAc / cyclohexanone 1: 1 mixture) 32.5% by mass

<Examples 2 to 4>, <Comparative Examples 1 to 5>
A red colored composition was obtained in the same manner as in Example 1 except that the pigment dispersion and resin described in Table 3 were used as the resin used in the dye, pigment dispersion, and red colored composition.

[Preparation of red colored composition coating film]
After coating the red coloring composition shown in Table 3 on a glass substrate by spin coating, it was pre-baked at 70 ° C. for 20 minutes in a clean oven. Next, the substrate was cooled to room temperature and then exposed to ultraviolet rays using an ultrahigh pressure mercury lamp. Thereafter, the substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, and air-dried. Thereafter, post-baking was performed at 230 ° C. for 60 minutes in a clean oven to obtain a red coating film. The film thickness of the dried coating film was 1.8 μm in all cases.

[Sensitivity evaluation]
The sensitivity of each red coloring composition shown in Table 3 was evaluated as follows. That is, first, the obtained photosensitive composition was applied onto a glass substrate by spin coating, and then pre-baked at 70 ° C. for 15 minutes to form a coating film having a thickness of 2.3 μm. Next, UV exposure was performed through a photomask having a 50 μm fine line pattern by a proximity exposure method using UV as an exposure light source. The exposure amount was set to 8 levels of 30, 40, 50, 60, 70, 80, 90, and 100 mJ / cm ² .

Next, shower development was performed using a 1.25% by mass sodium carbonate solution, followed by washing with water and a heat treatment at 230 ° C. for 20 minutes to complete the patterning.
The film thickness of the obtained filter segment was divided by the film thickness (2.3 μm) of the unexposed / undeveloped portion to calculate the remaining film ratio. An exposure sensitivity curve was plotted with the horizontal axis representing the exposure amount and the vertical axis representing the remaining film ratio after development. From the resulting exposure sensitivity curve, the minimum exposure dose giving a residual film ratio reaches 80% or more and saturation exposure, ○ where saturation exposure amount is 50 mJ / cm ² or less, if it is 50~100mJ / cm ² Is Δ, and the case where it is larger than 100 mJ / cm ² is x. The results are shown in Table 4.

(Patternability evaluation)
The patterning performance of each photosensitive red coloring composition and cell gap control raised layer prepared in each Example and Comparative Example was evaluated as follows.
That is, first, the obtained black photosensitive composition was applied onto a glass substrate by spin coating, and prebaked at 70 ° C. for 15 minutes to form a coating film having a thickness of 2.3 μm. Next, ultraviolet exposure was performed through a photomask provided with a stripe pattern having a line width of 6 to 20 μm by a proximity exposure method using ultraviolet light as an exposure light source. The exposure amount was the saturation exposure amount described above.

  Next, it was washed with water after shower development using a 1.25% by mass sodium carbonate solution. The development time was set to an appropriate time for washing away the unexposed coating film. Next, heat treatment was performed at 230 ° C. for 20 minutes to produce a test substrate. The results are shown in Table 4.

In Example 1, the dye C.I. I. Solvent Red 89 contains 14% by mass of the total mass of the color material, and achieves higher brightness and contrast than Comparative Example 1 which does not contain a dye. Moreover, polyfunctional thiol contained 3.0% in the total solid content, and was sufficient exposure sensitivity. Similarly in Example 2, the dye was 12% by mass in the coloring material, and the brightness was higher than that of Comparative Example 1. In Example 3, the multifunctional thiol contained 7.3% by mass in the total solid content, and high sensitivity was realized. In Example 4, C.I. I. A combination of Solvent Red 89 and Pigment Yellow 1 39, C.I. I. 50% by mass of Solvent Red 89 is contained. Compared with Comparative Example 2 prepared by combining Pigment Red 177 and Pigment Yellow 139 with the same hue, the brightness and contrast are high. In Comparative Example 3, since the dye content was as high as 60% by mass in the coloring material, the sensitivity was insufficient even when polyfunctional thiol was contained. In Comparative Example 4, the content of thiol was small, and in Comparative Example 5, since no thiol was contained, the sensitivity was insufficient and a rectangular pattern could not be formed.

DESCRIPTION OF SYMBOLS 1 ... Transparent substrate 2 ... Black matrix 3R ... Red pixel 3G ... Green pixel 3B ... Blue pixel

Claims (5)

A) a coloring material, B) a binder resin, C) a radical polymerizable monomer, D) a photo radical generator, and E) a red coloring composition containing a polyfunctional thiol, wherein at least one kind of the A) coloring material E) the polyfunctional thiol is 1% by mass to 10% by mass in the total solid content,
As the dye, C.I. containing a dye having an azo skeleton or a metal complex of a dye having an azo skeleton . I. Solvent Red 124, or C.I. I. A red coloring composition, which is Solvent Red 89 . 2. The red color according to claim 1, wherein A) the color material is 10% by mass to 60% by mass in the total solid content, and A) the dye is within 30% by mass in the total mass of the color material. Coloring composition. The pigment contains at least one pigment selected from diketopyrrolopyrrole red pigments, anthraquinone red pigments, azo yellow pigments, and isoindoline yellow pigments. Item 3. The red coloring composition according to any one of Items 2 above. The diketopyrrolopyrrole pigment is C.I. I. Pigment Red 254, an anthraquinone red pigment is C.I. I. Pigment 177, an azo yellow pigment, C.I. I. Pigment Yellow 150, an isoindoline yellow pigment is C.I. I. Pigment
The red coloring composition according to claim 3 , which is Yellow 139. The color filter manufactured using the red coloring composition of any one of Claims 1-4 .

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