JP2010256767A - Blue photosensitive coloring composition, color filter using the same, and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive coloring composition that is used for a color filter, and has high patterning property, high resist temporal stability, high transmittance, and hence high lightness, and to provide a color filter using the photosensitive coloring composition. <P>SOLUTION: This photosensitive coloring composition contains at least transparent resin (a), photopolymerizable monomer (b), photopolymerization initiator (c), blue colorant (d), and solvent (e). The number of functional groups of the photopolymerizable monomer (b) is 2-4. The transmittance at 450 nm of a blue filter segment formed from the photosensitive coloring composition is 96% or higher when the transmittance at 600 nm is set at 10%. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a blue photosensitive coloring composition used for a color filter used in a color liquid crystal display device and the like, and a color filter using the same.

  Currently, liquid crystal display devices are rapidly spreading in many applications such as television image display devices, computer terminal display devices, mobile terminal liquid crystal display devices for mobile applications, and liquid crystal display devices for in-vehicle use. Competition in display image quality is intensifying.

  In recent years, TV images have been delivered to computer terminals and mobile terminals as well as TVs, and due to the impact of the start of terrestrial digital broadcasting, image quality requirements equivalent to or higher than conventional TV standards are required for all applications. Many liquid crystal display devices are required to have high contrast, high speed response, high color reproduction, high brightness, and the like.

  Among them, high color reproduction and high brightness are characteristics that depend on the backlight light source and color filter provided in the liquid crystal display device, but the color filter has high light transmittance and transparency. What is expensive is required.

A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.
On the color filter used in the color liquid crystal display device, a transparent electrode for driving the liquid crystal is generally formed by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. Has been. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to perform the formation process at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher.

For this reason, the current color filter manufacturing method is to apply a pigment or dye with excellent light resistance and heat resistance dispersed in a photosensitive transparent resin component to a transparent substrate such as glass, and then remove the solvent by drying. Then, pattern exposure of one filter color is performed, then the unexposed part is removed in the development process to form the first color pattern, and after processing such as heating as necessary, the same operation is performed on all filters. The method of repeating colors sequentially is the mainstream.

  However, in the above manufacturing method, particularly in the blue filter segment, the light transmittance is lowered due to the coloring and opacification of the photosensitive transparent resin component in the heating process at the time of manufacturing the color filter. As a result, a color filter with high light transmittance and high transparency has not been obtained. One of the reasons for this is the use of a polyfunctional group monomer having 5 to 6 functional groups in the photopolymerization monomer in order to increase photosensitivity. Therefore, there is a concern that the number of double bonds increases, and the coloring of the transparent resin component proceeds in the color filter manufacturing process.

JP-A-6-201913 JP-A-4-163552

The present invention is for solving the above-mentioned problems, and an object of the present invention is to provide a photosensitive coloring composition having a high transmittance and a high brightness when a blue filter segment is formed, and a color filter using the same. And

That is, the invention described in claim 1 is a photosensitive material containing at least a transparent resin (a), a photopolymerizable monomer (b), a photopolymerization initiator (c), a blue colorant (d), and a solvent (e). The photopolymerizable monomer (b) has a functional group number of 2 to 4, and the blue filter segment formed from the photosensitive coloring composition has a transmittance at 600 nm of 10%. The transmittance at 450 nm is 96% or more when the following is set.

The invention described in claim 2 is characterized in that the blue colorant (d) is a blue pigment having an average primary particle size of 0.005 to 0.05 μm.

（上記化学式１において、Ｒ_１は、水素原子またはメチル基を表し、Ｒ_２は、炭素数２〜１０ のアルキレン基を表し、Ｒ_３は、水素原子またはベンゼン環を含むこともある炭素数１〜２０のアルキル基を表す。ｎは１〜１５の整数を表す。） The invention described in claim 3 is characterized in that the transparent resin (a) contains an ethylenically unsaturated monomer represented by the following chemical formula 1 as a copolymerization component.

(In the above chemical formula 1, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or a benzene ring that may contain a benzene ring. Represents an alkyl group of -20. N represents an integer of 1-15.)

According to a fourth aspect of the present invention, there is provided a color filter comprising at least a black matrix, a plurality of transparent colored filter segments, and a transparent electrode on a transparent substrate, wherein the blue filter segment is the first to third aspects. It was manufactured using the blue photosensitive coloring composition in any one of.

A fifth aspect of the present invention is a color liquid crystal display device using the color filter according to the fourth aspect.

  According to the present invention, the blue filter segment prepared using a blue photosensitive coloring composition using a photopolymerizable monomer having a functional group number of 4 or less, that is, a functional group number of 2 to 4, has a transmittance of 600 nm. The spectral characteristic is such that the transmittance at 450 nm is 96% or more when the ratio is 10% or less. In addition, the patterning property and stability over time are good, and the lightness (BY value) at the same hue is higher than, for example, 40.4 or more as compared with the conventional blue filter segment, and the white lightness (WY value) is also high. For example, it becomes as high as 37.2 or more.

  Hereinafter, the present invention will be summarized first, and then the details of the material surface, the general production method of the photosensitive coloring composition, the production method of the color filter substrate, and the examples will be described in detail.

The blue photosensitive coloring composition according to the present invention includes, as its essential components, a transparent resin (a), a photopolymerizable monomer (b), a photopolymerization initiator (c), a blue colorant (d), and a solvent (e). It contains.
Moreover, you may contain additives, such as a dispersing agent, a photosensitizer, and a chain transfer agent.

  And when the number of functional groups of the photopolymerizable monomer in the blue photosensitive coloring composition is 2 to 4, and the transmittance at 600 nm of the blue filter segment formed from the photosensitive coloring composition is 10% The transmittance at 450 nm is 96% or more.

When the number of functional groups of the photopolymerizable monomer is lower than 2, patterning cannot be performed due to insufficient sensitivity in the exposure process when the blue photosensitive coloring composition is formed, and the number of functional groups exceeds 4. In the heating process when manufacturing the color filter, the transmittance decreases.

Next, each component constituting the blue photosensitive coloring composition according to the present invention will be described.
(Photopolymerizable monomer)
A photopolymerizable monomer is polymerized by irradiation with exposure light, and changes a colored photosensitive layer produced using the photosensitive coloring composition to be insoluble in a developer. Generally, it is a monomer whose polymerization is induced by radicals, but as the bi- to tetrafunctional photopolymerizable monomer that can be used in the present invention, tricyclodecane dimethylol di (meth) acrylate, polypropylene glycol di (meth) acrylate , Polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene Various acrylic acid esters and methacrylic acid esters, such as emissions oxide-modified trimethylolpropane tri (meth) acrylate Representative examples

(Transparent resin)
The transparent resin used for the coloring composition is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. The transparent resin includes a non-photosensitive resin such as a thermoplastic resin and a thermosetting resin, and a photosensitive resin. If necessary, the transparent resin can be used alone or in admixture of two or more monomers or oligomers that are precursors thereof that are cured by irradiation with radiation to produce a transparent resin.

The non-photosensitive transparent resin is a resin that does not have an ethylenically unsaturated double bond. Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, and polychlorinated resin. Vinyl, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polybutadiene, A polyimide resin etc. are mentioned. Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a phenol resin, a melamine resin, and a urea resin. However, these resins do not exhibit alkali solubility.

  At present, as the developer, an alkaline developer having a small influence on the environment is often used. For this reason, it is desirable to use an alkali-soluble resin as the resin binder. The alkali-soluble non-photosensitive transparent resin is a transparent resin having a property of dissolving in an alkaline aqueous solution and having no ethylenically unsaturated double bond. For example, an acidic functional group such as a carboxyl group or a sulfone group Examples include a non-photosensitive transparent resin having a weight average molecular weight of 1,000 to 500,000, preferably 5,000 to 10,000. Of the acidic functional groups, a carboxyl group is preferred. In order to stabilize dispersion and improve the development performance of the color filter coloring composition, the acid value of the non-photosensitive transparent resin is preferably higher than the acid value of the photosensitive transparent resin. The patterning property of the transparent colored coating film made of the composition is improved, and a transparent colored pixel having a stable shape is obtained.

  Specific examples of such alkali-soluble non-photosensitive resins include acrylic resins having acidic functional groups, α-olefin- (anhydrous) maleic acid copolymers, styrene- (anhydrous) maleic acid copolymers, and styrene. -Styrenesulfonic acid copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene- (anhydrous) maleic acid copolymer and the like. Among them, at least one resin selected from an acrylic resin having an acidic functional group, an α-olefin- (anhydrous) maleic acid copolymer, a styrene / (anhydrous) maleic acid copolymer, and a styrene styrene sulfonic acid copolymer. Are preferably used. Among these, acrylic resins having acidic functional groups are preferably used because of their high heat resistance and transparency. A resin having a weight average molecular weight of 1,000 to 500,000, preferably 5,000 to 100,000 can be preferably used.

As the photosensitive resin, a linear polymer having a reactive functional group is reacted with a (meth) acrylic compound having a substituent capable of reacting with the reactive functional group, cinnamic acid, etc. Examples thereof include resins in which a bond is introduced into the linear polymer. In addition, a linear polymer having a substituent capable of reacting with the reactive functional group is reacted with a (meth) acrylic compound having a reactive functional group, cinnamic acid, or the like, to thereby form an ethylenically unsaturated double bond. Resin introduced into the polymer. Examples of the reactive functional group include a hydroxyl group, a carboxyl group, and an amino group, and examples of the substituent capable of reacting with the reactive functional group include an isocyanate group, an aldehyde group, and an epoxy group.

  In addition, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Those half-esterified with can be used as the photosensitive resin.

The amount of ethylenically unsaturated double bonds introduced through a hydroxyl group or the like into the photosensitive transparent resin, which indicates the ease of photocuring, is indicated by the “double bond equivalent” of the resulting photosensitive transparent resin. .
The double bond equivalent of the photosensitive transparent resin in the present invention is preferably 200 to 1200, and more preferably 300 to 900. When the double bond equivalent of the photosensitive transparent resin is less than 200, the ratio of the ethylenically unsaturated monomer having a reactive substituent for introducing an ethylenically unsaturated double bond is increased, and various characteristics are maintained. A sufficient amount of other ethylenically unsaturated monomers cannot be copolymerized. When it exceeds 1200, sufficient sensitivity cannot be obtained because the number of ethylenically unsaturated double bonds is small. Moreover, the weight average molecular weight (Mw) of the photosensitive transparent resin is preferably 2000 to 200000, and more preferably 5000 to 50000, from the viewpoint of good dispersibility of the blue photosensitive coloring composition.

(Other components in transparent resin)
In the case of using a pigment as the colorant, it is preferable from the viewpoint of improving the dispersion stability of the pigment that the transparent resin contains the ethylenically unsaturated monomer (A) represented by the chemical formula 1 as a polymerization component.

In the chemical formula 1, the alkylene group of R ₂ preferably has 2 to 3 carbon atoms. The number of carbon atoms in the alkyl group of R ₃ may be any from 1 to 20, but more preferably 1 to 10, alkyl group of R ₃ may include a benzene ring. When the carbon number of the alkyl group of R ₃ is 1 to 10, the alkyl group becomes an obstacle and suppresses the approach between the resins and promotes adsorption / orientation to the pigment, but when the carbon number exceeds 10, The steric hindrance effect becomes high and shows a tendency to prevent even the adsorption / orientation of the benzene ring to the pigment. This tendency becomes more prominent as the carbon chain length of the alkyl group of R ₃ becomes longer. When the carbon number exceeds 20, the adsorption / orientation of the benzene ring is extremely reduced. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group and a 2-phenyl (iso) propyl group.

  Examples of the ethylenically unsaturated monomer (A) include phenol ethylene oxide (EO) modified (meth) acrylate, paracumylphenol EO or propylene oxide (PO) modified (meth) acrylate, nonylphenol EO modified (meth) Examples thereof include acrylate, PO-modified (meth) acrylate of nonylphenol, and the like. Among these compounds, EO or PO-modified (meth) acrylate of paracumylphenol is not only effective for the π-electron of the benzene ring, but also its steric effect, which is better for coloring materials such as pigments. Since the adsorption / orientation plane can be formed, the dispersion effect is higher.

In order to use the ethylenically unsaturated monomer (A) as a photosensitive transparent resin or a non-photosensitive transparent resin, it is necessary to copolymerize with another ethylenically unsaturated monomer (B). is there.
Other ethylenically unsaturated monomers (B) copolymerizable with the ethylenically unsaturated monomer (A) include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (iso ) Propyl (meth) acrylate, (iso) butyl (meth) acrylate, (iso) pentyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (Meth) acrylate, glycidyl (meth) acrylate, isobornyl (meth) acrylate, acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, 3-chloro-2-acid phosphooxyethyl (meth) acrylate, Acid Phospho Examples thereof include xylethylene glycol mono (meth) acrylate, and these can be used alone or in combination of two or more.

  A monomer (in a photosensitive or non-photosensitive transparent resin obtained by copolymerizing the ethylenically unsaturated monomer (A) represented by the chemical formula 1 with another ethylenically unsaturated monomer (B) ( The copolymerization ratio of C) is preferably from 0.1 to 50% by weight, more preferably from 10 to 35% by weight, based on the total amount of monomers combined with (A) and (B). When the copolymerization ratio of the monomer (C) is less than 0.1% by weight, the pigment dispersion effect is lowered. On the other hand, when the amount is more than 50% by weight, the hydrophobicity increases, and the developability of the coloring composition may be lowered or a residue may be caused.

(Coloring material)
The average primary particle diameter of the blue pigment contained in the blue photosensitive coloring composition of the present invention is preferably 0.005 to 0.05 μm, more preferably 0.005 to 0.03 μm. When the average primary particle diameter of the pigment is smaller than 0.005 μm, the pigment particles are not preferable because they aggregate. When larger than 0.05 μm, it is difficult to achieve the target spectral characteristics. Absent.

The specific example of the organic pigment which can be used for the blue photosensitive coloring composition of this invention is shown with a color index number.
Examples of blue pigments include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc., among which C.I. I. Pigment Blue 15: 6 is preferred.

Means for controlling the average primary particle size of the pigment include a method in which the pigment is mechanically pulverized to control the average primary particle size (referred to as a grinding method), and a solution dissolved in a good solvent is added to the poor solvent. There are a method of precipitating a pigment having an average primary particle diameter (referred to as a precipitation method) and a method for producing a pigment having a desired average primary particle diameter at the time of synthesis (referred to as a synthetic precipitation method). Depending on the synthesis method and chemical properties of the pigment to be used, an appropriate method can be selected for each pigment.
Each method will be described below, and any of the above methods may be used as a method for controlling the average primary particle size of the pigment contained in the photosensitive coloring composition of the present invention.

  In the grinding method, the pigment is mechanically kneaded with a grinding agent such as a water-soluble inorganic salt such as salt and a water-soluble organic solvent that does not dissolve the pigment using a ball mill, a sand mill, or a kneader (hereinafter, this step is referred to as this step). This method is called salt milling), and then the inorganic salt and the organic solvent are washed away with water and dried to obtain a pigment having a desired average primary particle size. However, since the pigment may crystallize by the salt milling treatment, a method of preventing crystal growth by adding a solid resin or a pigment dispersant that is at least partially dissolved in the organic solvent during the treatment is effective.

  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, 1 to 30 parts by weight, preferably 2 to 20 parts by weight of the inorganic salt is used per 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 solidified, and depending on the blending ratio of the pigment and the inorganic salt, the amount of the pigment is usually 50 to 300% by weight. Used.

More specifically, the salt milling is performed by adding a small amount of a water-soluble organic solvent as a wetting agent to a mixture of a pigment and a water-soluble inorganic salt, kneading with a kneader or the like, and then pouring the mixture into water. Stir with a speed mixer to make a slurry. Next, this slurry is filtered, washed with water, and dried to obtain a pigment having a desired average primary particle size.

  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 average primary particle size. Depending on the type and amount of the solvent, the precipitation temperature, the precipitation rate, etc. The specific surface area can be controlled. In general, pigments are difficult to dissolve in solvents, so the solvents that can be used are limited, but examples include strongly acidic solvents such as concentrated sulfuric acid, polyphosphoric acid, chlorosulfonic acid, or basic solvents such as liquid ammonia, dimethylformamide solution of sodium methylate, etc. It has been known.

(Dispersant)
When a pigment is used as the colorant, a dispersant such as a resin-type pigment dispersant, a dye derivative, or a surfactant can be appropriately used. Since the dispersant is excellent in pigment dispersion and has a great effect of preventing reaggregation of the pigment after dispersion, a red coloring composition obtained by dispersing the pigment in the photosensitive resin composition using the dispersant was used. In this case, a color filter having excellent transparency can be obtained.
The addition amount of the dispersant is not particularly limited, but is preferably 0.1 to 40 parts by weight, more preferably 0.1 to 30 parts by weight, and still more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the colorant. It can be used in an amount of 10 parts by weight.

(Resin type pigment dispersant)
The resin-type pigment dispersant has a pigment-affinity part that has the property of adsorbing to the pigment and a part that is compatible with the photosensitive transparent resin and the non-photosensitive transparent resin. It functions to stabilize dispersion in the resin composition. Resin-type pigment dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polycarboxylic acid esters Siloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amide formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Used. Moreover, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol,
Water-soluble resins such as polyvinylpyrrolidone, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and the like are also used. These can be used alone or in admixture of two or more.

  As the commercially available resin-type pigment dispersant, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, manufactured by Big Chemie 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS or Byk SOLSPERS E-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000 manufactured by Abyssia , 28000, 31845, 32000, 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, etc., EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, etc. 400, 401, 402, 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503 and the like.

  A pigment derivative is a compound in which a substituent is introduced into an organic pigment. Organic dyes include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used singly or in combination of two or more.

(Surfactant)
Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer; polyoxyethylene oleyl ether, polyoxyethylene Lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol Nonionic surfactants such as nolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; and amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines These can be used alone or in admixture of two or more.

(Storage stabilizer)
The red coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite. The storage stabilizer can be used preferably in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

(Polymerization initiator)
As the polymerization initiator, an oxime ester polymerization initiator can be preferably used. For example, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4 '-Methoxy-naphthyl) ethylidene) hydroxylamine.

In addition to the oxime ester polymerization initiator, other polymerization initiators can be used in combination. Examples of such polymerization initiators include acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, phosphine compounds, quinone compounds, borate compounds, carbazole compounds, and imidazole compounds. And titanocene compounds. Examples of acetophenone compounds include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, and 1-hydroxy. Cyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- Examples include 1-one. Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal. Examples of the benzophenone compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, and the like. Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone and the like. Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, and 2- (p-methoxyphenyl) -4,6-bis. (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pienyl-4,6-bis (trichloromethyl) -s-triazine, 2 , 4-Bis (trichloromethyl) -6-styryl s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1) -Yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4'- Tokishisuchiriru) -6-triazine and the like. Examples of the phosphine compound include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Examples of the quinone compound include 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone.
The amount of the polymerization initiator used is preferably 0.5 to 50% by weight, more preferably 3 to 30% by weight, based on the total solid content of the photosensitive coloring composition.

(Photosensitizer)
In addition to the polymerization initiator, it is preferable to add a photosensitizer to the photosensitive coloring composition according to the present invention. An example of the photosensitizer is an amine compound. For example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4-dimethylaminobenzoate 2-ethylhexyl acid, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethylamino) benzophenone, etc. is there.

  Further, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone or the like can also be used as a sensitizer. The amount of these sensitizers used is 0. 0 based on the total amount of photopolymerization initiator and sensitizer. 5-60 weight% is preferable, More preferably, it is 3-40 weight%.

(solvent)
In order to make it easy to form a filter segment by applying a blue photosensitive coloring composition on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm, the photosensitive coloring composition In order to optimize the viscosity of the product and sufficiently disperse the colorant uniformly in the photosensitive resin composition, a solvent can be contained. As the solvent, water, an organic solvent, or the like can be used. Examples of the organic solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, propylene glycol monomethyl ether 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. These may be used alone or in combination. The solvent can be used in an amount of preferably 800 to 4000 parts by weight, more preferably 1000 to 2500 parts by weight with respect to 100 parts by weight of the colorant.

Next, the preparation method of the photosensitive coloring composition which becomes this invention is demonstrated.
The blue photosensitive coloring composition according to the present invention includes, for example, the following (1) to (4) from a photopolymerizable monomer, a transparent resin (photosensitive transparent resin, non-photosensitive transparent resin), a pigment, a dispersant, and a solvent. It can be prepared by either method.

(1): A pigment composition prepared by previously mixing a pigment and a dispersant is added to a solution obtained by dissolving a photopolymerizable monomer and / or a transparent resin in a solvent and dispersed, and the remaining components are added. .
(2): A pigment and a dispersant are separately added and dispersed in a solution in which a photopolymerizable monomer and / or transparent resin or both are dissolved in a solvent, and then the remaining components are added.
(3): After dispersing the pigment in a solution in which the photopolymerizable monomer and / or transparent resin or both are dissolved in a solvent, the pigment dispersant is added, and then the remaining components are added.
(4): Prepare two types of solutions in which a photopolymerizable monomer or transparent resin or both are dissolved in a solvent, disperse the pigment and dispersant separately in advance, then mix them and add the remaining ingredients To do. One of the pigment and the dispersant may be dispersed only in the solvent.

  Here, the pigment and the dispersant can be dispersed using various dispersing devices such as a three-roll mill, a two-roll mill, a sand mill, a kneader, a dissolver, a high speed mixer, a homomixer, an attritor, and a paint conditioner.

  Moreover, when preparing a pigment composition by mixing a pigment and a dispersant in advance, it is possible to simply mix a powdered pigment and a powdered dispersant, but (b) a kneader, a roll, an attritor, a super mill, etc. Mix mechanically with various pulverizers, or (b) Disperse the pigment in the solvent, then add a solution containing the dispersant to adsorb the dispersant on the pigment surface, or (c) Strongly dissolve sulfuric acid, etc. It is preferable to employ a mixing method in which the pigment and the dispersant are co-dissolved in a powerful solvent and then co-precipitated using a poor solvent such as water.

Below, the manufacturing method for obtaining the color filter of this invention is described.
The color filter of the present invention is a color filter having filter segments (pixels) formed using the blue photosensitive composition of the present invention. The color filter includes an additive color mixture comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and at least one magenta filter segment, at least one cyan filter segment, And a subtractive color type with at least one yellow filter segment.

The red filter segment can be formed using a normal red photosensitive coloring composition. The red photosensitive coloring composition is, for example, C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 168, 177, 178, 184, It is a composition obtained by using red pigments such as 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, and 279. The red photosensitive coloring composition includes C.I. I. An orange pigment such as Pigment Orange 43, 71, 73 can be used in combination.

Moreover, a green filter segment can be formed using a normal green photosensitive coloring composition. The green photosensitive coloring composition is, for example, C.I. I. This is a composition obtained using a green pigment such as Pigment Green 7, 10, 36, 37. Green coloring compositions include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180 , 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214 and the like can be used in combination.

The color filter of the present invention can be manufactured by forming filter segments of each color on a transparent substrate by a photolithography method. As the transparent substrate, a glass plate or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.

The formation of each color filter segment by photolithography is performed by the following method. That is, the photosensitive coloring composition is applied on a transparent substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating so that the dry film thickness is 0.2 to 5 μm. 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. Then, after immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion and forming a desired pattern, the polymerization of the colored resist material is promoted as necessary. Heating can also be applied. According to the photolithography method, a color filter with higher accuracy than the printing method can be manufactured.

In development, 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.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  By repeating the above-described series of steps by changing the photosensitive coloring composition and the pattern as many times as necessary, it is possible to obtain a color filter including a colored pattern in which a necessary number of colors are combined, that is, a plurality of pixels.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited thereto without departing from the spirit of the present invention. In addition, the compounding ratio of each composition is a mass (weight) ratio unless otherwise specified.

[Resin adjustment]
(Synthesis Example 1 of transparent resin)
70 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 12.3 parts of benzyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 5.3 parts of methacrylic acid at the same temperature. , 2 parts of a mixture of 7.4 parts paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) as monomer (a) and 0.4 part of 2,2′-azobisisobutyronitrile. The polymerization reaction was carried out dropwise over time. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A photosensitive transparent resin copolymer solution was obtained. After cooling to room temperature, about 2 g of the non-photosensitive transparent resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The non-photosensitive transparent resin solution synthesized previously had a non-volatile content of 20% by weight. Cyclohexanone was added so that a non-photosensitive resin solution was prepared. The obtained transparent resin 1 had a weight average molecular weight Mw of 20000.

(Synthesis example 2 of transparent resin)
370 parts of cyclohexanone was put into a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate at the same temperature, A mixture of 15.0 parts of 2-hydroxyethyl methacrylate and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, 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 photosensitive transparent resin copolymer solution was obtained. After cooling to room temperature, about 2 g of the non-photosensitive transparent resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The non-photosensitive transparent resin solution synthesized previously had a non-volatile content of 20% by weight. Cyclohexanone was added so that a non-photosensitive resin solution was prepared. The weight average molecular weight Mw of the obtained transparent resin 2 was 46000.

[Preparation of photosensitive coloring composition]
Blue, red and green photosensitive coloring compositions were prepared as follows.
-Blue photosensitive coloring composition The blue pigment 1 which adjusted the average primary particle diameter with the following method was obtained. Table 1 shows the average primary particle sizes of the untreated pigment and the obtained pigment.
(Blue pigment 1)
Copper phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“Lionol Blue ES” manufactured by Toyo Ink Manufacturing Co., Ltd.) 500 parts, 2500 parts of sodium chloride, and 250 parts of polyethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) in a stainless gallon kneader (manufactured by Inoue Seisakusho) Charged and kneaded at 120 ° C. for 6 hours. Next, this mixture is poured into about 5 liters of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C., and then slurried, filtered, washed with water to remove sodium chloride and diethylene glycol, It was dried at 80 ° C. for 24 hours to obtain 490 parts of a salt milled pigment (blue pigment 1).

・ Blue photosensitive coloring composition 1
A mixture having the following composition was stirred and mixed uniformly, then dispersed in a sand mill for 5 hours using a glass bead having a diameter of 1 mm, and then filtered through a 5 μm filter to prepare a blue pigment dispersion 1.
Blue pigment: Blue pigment 1 10 parts Dispersant ("Solvers Bird 20000" manufactured by Zeneca) 2 parts Non-photosensitive transparent resin 1 (solid content 20%) 40 parts Propylene glycol monomethyl ether acetate 48 parts After stirring and mixing, the mixture was filtered through a 5 μm filter to obtain a blue photosensitive coloring composition 1.
18.8 parts of the above dispersion Transparent resin 1 (solid content 20%) 25.9 parts Photopolymerizable monomer (Aronix M270 manufactured by Toagosei Co., Ltd .: polypropylene glycol diacrylate) 4.7 parts Photoinitiator (Ciba Geigy) "Irgacure 907") 1.4 parts 49.3 parts propylene glycol monomethyl ether acetate

・ Blue photosensitive coloring composition 2
A blue photosensitive coloring composition 2 was obtained in the same manner except that the photopolymerizable monomer used in the blue photosensitive coloring composition 1 was changed to “Aronix M309” (trimethylolprohan triacrylate) manufactured by Toagosei Co., Ltd.

-Blue photosensitive coloring composition 3
The blue photosensitive coloring composition 3 was obtained in the same manner except that the photopolymerizable monomer used in the blue photosensitive coloring composition 1 was changed to “Aronix M408” (ditrimethylolpropane tetraacrylate) manufactured by Toagosei Co., Ltd.

-Blue photosensitive coloring composition 4
A blue photosensitive coloring composition 4 was obtained in the same manner except that the photopolymerizable monomer used in the blue photosensitive coloring composition 1 was changed to “Aronix M111” (nonylphenol EO modified acrylate) manufactured by Toagosei Co., Ltd.

-Blue photosensitive coloring composition 5
A blue photosensitive coloring composition 5 was obtained in the same manner except that the photopolymerizable monomer used in the blue photosensitive coloring composition 1 was changed to “Aronix M402” (dipentaerythritol penta and hexaacrylate) manufactured by Toagosei Co., Ltd. .

-Blue photosensitive coloring composition 6
A blue photosensitive coloring composition 6 was obtained in the same manner as in the blue photosensitive coloring composition 3 except that the blue pigment was changed to “Lionol Blue ES” manufactured by Toyo Ink Manufacturing Co., Ltd. as an untreated pigment.

-Blue photosensitive coloring composition 7
A blue photosensitive coloring composition 7 was obtained in the same manner except that the non-photosensitive transparent resin 1 was changed to the non-photosensitive coloring composition 2 in the blue photosensitive coloring composition 3.

-Red photosensitive coloring composition A mixture of the following composition is uniformly stirred and mixed, then dispersed in a sand mill for 5 hours using a glass bead having a diameter of 1 mm, and then filtered through a 5 μm filter to produce a red pigment dispersion. did.
Red pigment: C.I. I. Pigment Red 254
("Ilgar Forred B-CF" manufactured by Ciba Specialty Chemicals)
9.7 parts Red pigment: C.I. I. Pigment Red 177
("Chromophthal Red A2B" manufactured by Ciba Specialty Chemicals)
0.3 part Dispersant ("Ajisper PB821" manufactured by Ajinomoto Fine Techno Co., Ltd.) 2 parts Non-photosensitive transparent resin 1 (solid content 20%) 40 parts Propylene glycol monomethyl ether acetate 48 parts Thereafter, a mixture having the following composition is made uniform After stirring and mixing as described above, the mixture was filtered through a 5 μm filter to obtain a red photosensitive coloring composition.
30 parts of the dispersion Transparent resin 1 (solid content 20%) 16.4 parts Photopolymerizable monomer (dipentaerythritol penta / hexaacrylate, manufactured by Toagosei Co., Ltd .: “M402”) 4.4 parts Photoinitiator (Ciba Geigy) 0.96 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.36 parts Propylene glycol monomethyl ether acetate 47.9 parts

Green photosensitive coloring composition A mixture of the following composition is stirred and mixed uniformly, then dispersed in a sand mill for 5 hours using a glass bead having a diameter of 1 mm, and then filtered through a 5 μm filter to produce a green pigment dispersion. did.
(Green pigment dispersion)
Green pigment: C.I. I. Pigment Green 36
("Rionol Green 6Y501" manufactured by Toyo Ink Manufacturing Co., Ltd.)
14 parts Dispersant ("Disperbyk-163" manufactured by Big Chemie) 2 parts Non-photosensitive transparent resin 1 (solid content 20%) 20 parts Propylene glycol monomethyl ether acetate 64 parts Next, a mixture having the following composition was uniformly stirred and mixed. Thereafter, using a glass bead having a diameter of 1 mm, the mixture was dispersed in a sand mill for 5 hours, and then filtered through a 5 μm filter to prepare a yellow pigment dispersion.
(Yellow pigment dispersion)
Yellow pigment: C.I. I. Pigment Yellow 150
("Funcheon first yellow Y-5688" manufactured by Bayer) 10 parts Dispersant ("Disperbyk-163" manufactured by Big Chemie) 2 parts Non-photosensitive transparent resin 1 (solid content 20%) 40 parts Propylene glycol monomethyl ether acetate 48 Thereafter, the green pigment dispersion 1 and the yellow pigment dispersion 1 were used to stir and mix a mixture having the following composition uniformly, and then filtered through a 5 μm filter to obtain a green photosensitive coloring composition. .
Green pigment dispersion 22.5 parts Yellow pigment dispersion 13.5 parts Transparent resin 1 (solid content 20%) 18.3 parts Photopolymerizable monomer (dipentaerythritol penta / hexaacrylate, manufactured by Toagosei Co., Ltd .: “M402” 3.2 parts Photoinitiator ("Irgacure 907" manufactured by Ciba Geigy) 0.74 parts
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.21 part Propylene glycol monomethyl ether acetate 41.6 parts

The color filter produced using the blue photosensitive coloring composition 1-3 as a photosensitive coloring composition which produces a blue filter segment (pixel) is made into Examples 1-3, and blue photosensitive coloring composition 4-7 is used. The color filters produced in this manner were referred to as Comparative Examples 1 to 4.
In addition, a red photosensitive coloring composition is used for the photosensitive coloring composition for producing the red filter segment (pixel), and a green photosensitive coloring composition is used for the photosensitive coloring composition for producing the green filter segment (pixel). It was. At this time, the red filter segment was adjusted so that x = 0.640, the green filter segment y = 0.600, and the blue filter segment y = 0.220 in the C light source.

[Evaluation item]
(Stability evaluation over time)
E type viscometer ("ELD" manufactured by Toki Sangyo Co., Ltd.) was prepared by comparing the initial viscosity of the blue photosensitive coloring composition obtained in the above Examples and Comparative Examples on the next day and the time-lapsed viscosity for one week at 40 ° C. Using a viscometer ”), the measurement was performed at 25 ° C. under the condition of a rotational speed of 20 rpm.
Resist viscosity change rate with time = | [[initial viscosity] − [viscosity viscosity]] / [initial viscosity] × 100 |
With respect to stability over time, a resist having a rate of change in viscosity with time of within ± 10% was evaluated as “◯”, and a resisting viscosity exceeding ± 10% was evaluated as “x”.
(Spectral characteristic evaluation)
Spectral transmittance evaluation of blue filter segment The blue photosensitive coloring composition obtained in the above examples and comparative examples was applied by spin coating so that the transmittance at a light wavelength of 600 nm was 10%, and then dried, A blue colored layer was formed. Next, after pre-baking at 70 ° C. for 20 minutes, 100 mJ ultraviolet exposure was performed, shower development was performed using a 1.25% by mass sodium carbonate solution, followed by washing with water to complete patterning. The development time was set to an appropriate time for washing away the unexposed coating film. Next, a heat treatment was performed at 230 ° C. for 20 minutes to obtain an evaluation substrate. The spectral transmittance of this substrate was measured, and the transmittance at a light wavelength of 450 nm was compared.
-Lightness evaluation of color filter The lightness (WY value = White-Y in Table 2) in white display of color filters prepared using the blue photosensitive coloring compositions obtained in the above Examples and Comparative Examples was compared.
(Patternability)
When a color filter was produced using the blue photosensitive coloring composition obtained in the above-mentioned Examples and Comparative Examples, those having no pattern peeling and no abnormal appearance such as wrinkles were evaluated as ◯. An abnormality was marked as x.

[Evaluation results]
Table 2 shows the results of Examples 1 to 3 and Comparative Examples 1 to 4.

From the results in Tables 1 and 2, the following is clear. That is, in the blue photosensitive coloring composition, the number of functional groups of the photopolymerizable monomer is 2 to 4, and the transmittance at 450 nm when the transmittance of the formed blue filter segment at 600 nm is 10%. By using the one having a rate of 96% or more, the patterning property and the stability over time are good, and the blue lightness (BY value = Blue-Y in Table 2) when used as a color filter is as high as 40.4 or more. Thus, it can be seen that a brightness with white display (WY value = White-Y in Table 2) as high as 37.2 or higher is obtained.

Claims (5)

A photosensitive coloring composition containing at least a transparent resin (a), a photopolymerizable monomer (b), a photopolymerization initiator (c), a blue colorant (d), and a solvent (e), wherein the photopolymerization The number of functional groups of the photosensitive monomer (b) is 2 to 4, and the transmittance at 450 nm is 96 when the transmittance at 600 nm of the blue filter segment formed from the photosensitive coloring composition is 10%. % Blue photosensitive coloring composition characterized by the above-mentioned. The blue photosensitive coloring composition according to claim 1, wherein the blue colorant (d) is a blue pigment having an average primary particle diameter of 0.005 to 0.05 µm. The blue photosensitive coloring composition according to claim 1, wherein the transparent resin (a) contains an ethylenically unsaturated monomer represented by the following chemical formula 1 as a copolymerization component.
(In the following chemical formula 1, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ has 1 to 20 carbon atoms which may contain a hydrogen atom or a benzene ring. Represents an alkyl group, and n represents an integer of 1 to 15.)

The blue photosensitive coloring composition according to any one of claims 1 to 3, wherein the blue filter segment is a color filter comprising at least a black matrix, a plurality of transparent coloring filter segments, and a transparent electrode on a transparent substrate. A color filter manufactured using a product. A color liquid crystal display device using the color filter according to claim 4.