JP4597693B2 - Blue coloring composition for color filter and color filter - Google Patents

Description

  The present invention relates to a highly sensitive photosensitive coloring composition, and in particular, a highly sensitive blue coloring composition for a color filter used in the production of a color filter used for a color liquid crystal display device, a color imaging tube element, and the like, And a color filter formed using the same.

A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting 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.
Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher.

For this reason, at present, as a method for producing a colored composition for a color filter used for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.
In the case of the pigment dispersion method, a photosensitive coloring composition (pigment resist material) in which a pigment is dispersed in a photosensitive resin composition is applied to a transparent substrate such as glass, and the solvent is removed by drying. Perform pattern exposure, then remove the unexposed area in the development process to form the pattern for the first color, apply heat and other treatments as necessary, and then repeat the same operation for all filter colors in sequence. Can be manufactured.

  In forming a filter segment using a photosensitive coloring composition containing a pigment, high photosensitivity, solubility in a developer in a non-image area, and chemical resistance in an image area are important characteristics. In recent years, there has been an increasing demand for color filters with higher color density and black matrix with higher optical density (OD value), and there is a tendency for the colorant density in photosensitive coloring compositions to increase. However, when the colorant concentration is increased, other characteristics such as an insufficient curing of the exposed portion cannot be obtained due to an increase in light absorption of the colorant itself. Thus, there is a trade-off relationship between the increase in the colorant concentration and the maintenance of characteristics derived from the photosensitive resin composition including the photosensitivity.

In order to improve the photosensitivity and the solubility in a developer, a photosensitive coloring composition for a color filter using a photosensitive transparent resin having an ethylenically unsaturated double bond and a carboxyl group in the side chain is known. In order to use this as a photosensitive resin composition, the type and ratio of monomers constituting the photosensitive transparent resin are adjusted to satisfy many characteristics such as stability, solubility, and chemical resistance. Is required.
In the photosensitive coloring composition, while maintaining the dispersion stability of the coloring material, the sensitivity of the photosensitive coloring composition increases with increasing concentration, and good patternability (solubility of unexposed areas, photocured areas) To maintain the shape, etc.) is limited only by changing the design of the photosensitive transparent resin.
JP 2002-014468 A

  Therefore, the present invention aims to provide a blue coloring composition for a color filter that has both high sensitivity and excellent dispersion stability, patterning properties, maintenance of physical properties such as chemical resistance, and a color filter using the same. And

The blue coloring composition for a color filter of the present invention is a blue coloring composition containing a photosensitive transparent resin, a non-photosensitive transparent resin, a polyfunctional monomer having three or more ethylenically unsaturated double bonds, and a blue coloring material. The weight molar concentration of the ethylenically unsaturated double bond in the blue coloring composition is 3.5 × based on the total weight of the photosensitive transparent resin, the non-photosensitive transparent resin, and the polyfunctional monomer. 10 ⁻³ mol / g to 6.1 × 10 ⁻³ mol / g , the double bond equivalent of the photosensitive transparent resin is 200 to 1200, and the content of the photosensitive transparent resin is photosensitive. 15 to 80% by weight based on the total weight of the transparent resin and the non-photosensitive transparent resin .
Moreover, the color filter of this invention comprises the filter segment formed using the said blue coloring composition for color filters, It is characterized by the above-mentioned.

The blue coloring composition for a color filter of the present invention has a photosensitive transparent resin, a non-photosensitive transparent resin, and a polyfunctional monomer as essential components, and the concentration of the photoreactive site is controlled. Dispersion stability, high sensitivity, excellent patterning properties, and chemical resistance as a composition can be achieved.
In addition, the blue colored composition for color filters of the present invention has higher solvent resistance than conventional blue colored compositions for color filters and is highly sensitive, so it can be cured sufficiently with a small amount of exposure and has excellent productivity. ing. Therefore, by forming a filter segment using the blue coloring composition for a color filter of the present invention, a stable and high-quality transmissive / reflective color liquid crystal display device and a color filter for color separation of a solid-state image sensor are obtained. Can be manufactured.

First, the blue coloring composition for a color filter of the present invention will be described.
The blue coloring composition for a color filter of the present invention contains a photosensitive transparent resin, a non-photosensitive transparent resin, a polyfunctional monomer having three or more ethylenically unsaturated double bonds, and a blue coloring material.
The ethylenically unsaturated double bond weight molar concentration in the blue coloring composition of the present invention is the sum of the photosensitive transparent resin, the non-photosensitive transparent resin, and the polyfunctional monomer (hereinafter referred to as the photosensitive transparent resin, non-photosensitive). A composition composed of a transparent transparent resin and a polyfunctional monomer is referred to as a photosensitive resin composition.) A value calculated from the following formula based on the weight: 3.5 × 10 ⁻³ mol / g to 6.1 × 10 ⁻³ mol / g .
(Ethylene unsaturated double bond weight molar concentration) = (Weight of photosensitive transparent resin / Double bond equivalent of photosensitive transparent resin + Weight of polyfunctional monomer / Double bond equivalent of polyfunctional monomer) / (Photosensitivity) (Weight of transparent resin + weight of non-photosensitive transparent resin + weight of polyfunctional monomer)
The double bond equivalent is defined by the following formula and is a measure of the amount of double bonds contained in the molecule. If the compounds have the same molecular weight, the smaller the double bond equivalent value, the more The amount of introduced heavy bonds increases.
[Double bond equivalent] = [molecular weight of repeating structural unit] / [number of double bonds in repeating structural unit]

When the ethylenically unsaturated double bond weight molar concentration in the blue colored composition is lower than 3.0 × 10 ⁻³ mol / g, the photosensitivity is lowered, which is sufficient for forming a blue colored coating film. Curability cannot be obtained. In addition, when the ethylenically unsaturated double bond weight molar concentration in the blue coloring composition is higher than 7.0 × 10 ⁻³ mol / g, the sensitivity is high, but the dispersion stability is lowered and uniform. A blue colored coating film may not be obtained, developability may deteriorate, and patterning properties may deteriorate.
The photosensitive transparent resin and the non-photosensitive transparent resin preferably used in the present invention are resins 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 photosensitive transparent resin is a resin having an ethylenically unsaturated double bond, for example, a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, an amino group, an isocyanate group, an aldehyde group, an epoxy group, A functional group having an ethylenically unsaturated double bond such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a reactive substituent such as a carboxyl group or cinnamic acid. Resin. Specifically, a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated double bond are added to a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group and another ethylenically unsaturated monomer. Some of them are obtained by reacting the compounds they have. Examples of the functional group capable of reacting with a hydroxyl group include an isocyanate group and a carboxyl group, but an isocyanate group is particularly preferred in terms of reactivity, and specifically, a compound having an isocyanate group and an ethylenically unsaturated double bond. , 2-acryloyl ethyl isocyanate, 2-methacryloyl ethyl isocyanate and the like. In addition, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

The amount of the ethylenically unsaturated double bond introduced into the photosensitive transparent resin via a hydroxyl group or the like 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, more preferably 5000 to 50000, from the viewpoint of good dispersibility of the blue colorant.

  The non-photosensitive transparent resin is a resin that does not have an ethylenically unsaturated double bond, and includes a thermoplastic resin and a thermosetting resin. 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, styrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyimide resins, and the like. 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.

  When the filter segment is formed by alkali development using the blue coloring composition of the present invention, it is preferable to use an alkali-soluble type as the non-photosensitive transparent resin. 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 Non-photosensitive transparent resin having a weight average molecular weight of 1,000 to 500,000, preferably 5,000 to 100,000. Of the acidic functional groups, a carboxyl group is preferred. In order to stabilize dispersion and improve development performance of the blue coloring composition for color filters, 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 blue-colored coating film made of the blue-colored composition becomes good, and a filter segment having a stable shape is obtained. Specific examples of the alkali-soluble non-photosensitive transparent resin include acrylic resin having an acidic functional group, α-olefin / (anhydrous) maleic acid copolymer, styrene / (anhydrous) maleic acid copolymer, styrene / Examples thereof include styrene sulfonic acid copolymers, ethylene / (meth) acrylic acid copolymers, and isobutylene / (anhydrous) maleic acid copolymers. Among them, at least one 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. Resins, particularly acrylic resins having an acidic functional group, are preferably used because of their high heat resistance and transparency.

（式（１）において、Ｒ₁は、水素原子またはメチル基を表し、Ｒ₂は炭素数２〜１０のアルキレン基を表し、Ｒ₃は、水素原子またはベンゼン環を含んでもよい炭素数１〜２０のアルキル基を表す。ｎは１〜１５の整数を表す。） When a pigment is used as the blue colorant, the photosensitive transparent resin or the non-photosensitive transparent resin may contain an ethylenically unsaturated monomer (a) represented by the following formula (1) as a polymerization component. This is preferable from the viewpoint of improving the dispersion stability of the pigment.

(In 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 which may contain a benzene ring. Represents an alkyl group of 20. n represents an integer of 1 to 15.)

In the above formula (1), the number of carbon atoms in the alkylene group R ₂ is preferably 2-3. Although the carbon number of the alkyl group of R ₃ is 1 to 20, 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, and 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.

  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 Shi polyethylene glycol mono (meth) acrylate and the like, these can be used alone or in combination.

  Monomer in a photosensitive or non-photosensitive transparent resin obtained by copolymerizing the ethylenically unsaturated monomer (a) represented by the above formula (1) and another ethylenically unsaturated monomer (b). The copolymerization ratio of the body (a) is preferably 0.1 to 50% by weight, more preferably 10 to 35% by weight, based on the total amount of the monomers obtained by combining (a) and (b). When the copolymerization ratio of the monomer (a) 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 blue coloring composition may be lowered, or a residue may be caused.

The photosensitive transparent resin and the non-photosensitive transparent resin can be used in an amount of preferably 20 to 400 parts by weight, more preferably 50 to 250 parts by weight in total, with respect to 100 parts by weight of the colorant. .
In the blue coloring composition of the present invention, a photosensitive transparent resin and a non-photosensitive transparent resin are used in combination in order to increase sensitivity, but in order to sufficiently increase the sensitivity, the content of the photosensitive transparent resin is photosensitive. It is preferably 15 to 80% by weight based on the total weight of the transparent resin and the non-photosensitive transparent resin, more preferably 45 to 80% by weight.
When the content of the photosensitive transparent resin is less than 15% by weight, the photosensitivity of the blue coloring composition is lowered, and sufficient curability may not be obtained when forming a blue colored coating film. Even if the curability is supplemented with a functional monomer, the solvent resistance of the blue colored coating film may not be sufficient. In addition, when the content of the photosensitive transparent resin is more than 80% by weight, the sensitivity of the blue colored composition is increased, but the dispersion stability is lowered and a uniform blue colored coating film cannot be obtained, In some cases, the developability is lowered and the patterning property is lowered.

  Examples of polyfunctional monomers having three or more ethylenically unsaturated double bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and ethylene oxide modified trimethylol. Representative examples include various acrylic esters and methacrylic esters such as propane tri (meth) acrylate and propylene oxide-modified trimethylolpropane tri (meth) acrylate. It is preferable that a polyfunctional monomer has 3-12 ethylenically unsaturated double bonds from a viewpoint of the sensitivity improvement of a coloring composition. Polyfunctional monomers having three or more ethylenically unsaturated double bonds can be used alone or in admixture of two or more.

The polyfunctional monomer having three or more ethylenically unsaturated double bonds can be used in an amount of preferably 10 to 300 parts by weight, more preferably 10 to 200 parts by weight with respect to 100 parts by weight of the colorant. .
The ethylenically unsaturated double bond weight molarity (based on the weight of the photosensitive resin composition) of the polyfunctional monomer having three or more ethylenically unsaturated double bonds is the ethylenically unsaturated double bond of the photosensitive transparent resin. It is preferably 2 to 35 times, more preferably 5 to 25 times, still more preferably 5 to 15 times the bond molar concentration (based on the weight of the photosensitive resin composition). When the ratio of the ethylenically unsaturated double bond weight molarity of the monomer is less than 2 times, the sensitivity of the blue coloring composition is lowered, and sufficient curability cannot be obtained when forming a blue colored coating film. . On the other hand, when the ratio is more than 35 times, the sensitivity of the blue coloring composition is improved, but the dispersion stability may be deteriorated or the patterning property may be deteriorated.

As the blue colorant, organic or inorganic blue pigments can be used alone or in admixture of two or more. As the pigment, a pigment having high color developability and high heat resistance, particularly a pigment having high heat decomposition resistance is preferable, and an organic pigment is usually used. Below, the specific example of the organic pigment which can be used for the blue coloring composition of this invention is shown with a color index number.
In the case of forming a blue filter segment using the blue coloring composition of the present invention, for example, C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, and 64 can be used. Blue coloring compositions include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination.
When forming a cyan filter segment, for example, C.I. I. Blue pigments such as Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, and 81 can be used.
Examples of inorganic pigments include ultramarine blue and bitumen. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.

The blue coloring composition of the present invention can contain a dye within a range that does not decrease heat resistance for color matching.
The blue coloring composition of the present invention finely disperses the blue coloring material in the photosensitive resin composition using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, an attritor, and a paint conditioner. Can be manufactured.
When a pigment is used as the colorant, a dispersion aid such as a resin-type pigment dispersant, a dye derivative, or a surfactant can be appropriately used. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion, a blue coloring composition obtained by dispersing the pigment in the photosensitive resin composition using the dispersion aid is used. When used, a color filter excellent in transparency can be obtained. The dispersion aid can be used in an amount of preferably 0.1 to 40 parts by weight, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the colorant.

  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. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, and 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.

  Commercially available resin-type pigment dispersants include 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 Bykumen SOLSPERSE-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 320 manufactured by Abyssia 0, 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, etc., EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402, etc. , 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.

  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 laurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactants such as alkylimidazoline These can be used alone or in admixture of two or more.

  The blue 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 in an amount of preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

  Further, in the blue coloring composition of the present invention, the blue coloring material is sufficiently dispersed in the photosensitive resin composition, and is applied on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. In order to facilitate the formation of the filter segment, a solvent can be contained. 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, Examples include 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.

When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the blue colored composition of the present invention.
Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane Acetophenone photopolymerization initiators such as -1-one, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4 Benzophenone photopolymerization initiators such as phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 Thioxanthone photopolymerization initiators such as 2,4-diisopropylthioxanthone, 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 (trick (Romethyl) -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′-methoxystyryl) -6-triazine, etc. A polymerization initiator, a borate photopolymerization initiator, a carbazole photopolymerization initiator, an imidazole photopolymerization initiator, or the like is used. The photopolymerization initiator can be used in an amount of preferably 5 to 20 parts by weight, more preferably 10 to 150 parts by weight with respect to 100 parts by weight of the colorant.

  These photopolymerization initiators are used alone or in admixture of two or more. As a sensitizer, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl-9,10-phenanth Such as lenquinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. A compound can also be used in combination. The sensitizer can be used in an amount of preferably 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

The blue coloring material is contained in a ratio of 0.5 to 10% by weight in the blue coloring composition (coloring composition including all components such as a transparent resin, a polyfunctional monomer and a coloring material, and an initiator and a solvent). It is preferred that Further, the blue colorant is finally contained in the filter segment in a proportion of preferably 10 to 60% by weight, more preferably 20 to 50% by weight, and the remainder is a photosensitive transparent resin, a non-photosensitive transparent resin and It consists essentially of a polyfunctional monomer.
The blue-colored composition of the present invention is prepared by means of centrifugal separation, sintering filter, membrane filter or the like, 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 It is preferable to remove the dust.

Next, the color filter of the present invention will be described.
The color filter of this invention is a color filter which comprises the filter segment formed from the blue coloring composition for color filters of this 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 mixing type comprising at least one yellow filter segment, wherein a blue filter segment and a cyan filter segment are formed using the blue coloring composition of the present invention.

As each color coloring composition other than blue, it can be formed using each color pigment, the said non-photosensitive transparent resin, and the usual each color coloring composition containing the said polyfunctional monomer.
Examples of the red coloring composition include 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, Red pigments such as 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, and 279 are used. The red coloring composition includes C.I. I. An orange pigment such as Pigment Orange 43, 71, 73 can be used in combination.

  Examples of the green coloring composition include C.I. I. Green pigments such as Pigment Green 7, 10, 36, and 37 are used. 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.

Examples of the magenta coloring composition include C.I. I. Pigment Violet 1, 19, C.I. I. Purple pigments such as Pigment Red 144, 146, 177, 169, 81, and red pigments are used.
Examples of the yellow coloring composition 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 It can be used yellow pigments such 181,182,185,187,188,193,194,198,199,213,214.

The color filter of this invention can be manufactured by forming the filter segment of each color on a board | substrate using the blue coloring composition of this invention and each normal color coloring composition by the photolithographic method.
As the substrate, a glass plate having a high transmittance with respect to visible light, 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, each color coloring composition prepared as a solvent developing type or alkali developing type colored resist material that is cured by light irradiation is applied on a substrate by a coating method such as spray coating, spin coating, slit coating, roll coating, etc. It is applied so that the thickness is 0.2-5 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 to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. 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.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, “parts” means “parts by weight”. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).
(Synthesis example 1 of photosensitive transparent resin)
560 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 34.0 parts of methacrylic acid, 23.0 parts of methyl methacrylate, 23.0 parts of n-butyl methacrylate at the same temperature. , 22.0 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), 47.0 parts of glycerol monomethacrylate, 2,2′-azobisisobutyronitrile as monomer (a) 4.0 parts of the mixture was added dropwise over 1 hour to carry out the polymerization reaction. 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 55 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained.
Next, a mixture of 32.0 parts of 2-methacryloylethyl isocyanate, 0.4 parts of dibutyltin laurate, and 120.0 parts of cyclohexanone was added to 338 parts of the obtained transparent resin solution at 70 ° C. over 3 hours. The solution was dropped to obtain a photosensitive transparent resin solution. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The previously synthesized photosensitive transparent resin solution has a non-volatile content of 20% by weight. Cyclohexanone was added as follows. The obtained photosensitive transparent resin 1 had a weight average molecular weight Mw of 21,000 and a double bond equivalent of 470.

(Synthesis example 2 of photosensitive transparent resin)
570 parts of cyclohexanone is placed in a reaction vessel and heated to 80 ° C. while injecting nitrogen gas into the vessel. At the same temperature, 23.0 parts of methacrylic acid, 23.0 parts of methyl methacrylate, 35.0 parts of benzyl methacrylate, single amount As the body (a), 22.0 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), 48.0 parts of glycerol monomethacrylate, 2,2′-azobisisobutyronitrile 3.0 Part of the mixture was added dropwise over 1 hour to carry out the 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 resin solution was obtained.
Next, a mixture of 33.0 parts of 2-methacryloylethyl isocyanate, 0.4 parts of dibutyltin laurate and 130.0 parts of cyclohexanone was added to 336 parts of the obtained transparent resin solution at 70 ° C. over 3 hours. The solution was dropped to obtain a photosensitive transparent resin solution. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The previously synthesized photosensitive transparent resin solution has a non-volatile content of 20% by weight. Cyclohexanone was added as follows. The obtained photosensitive transparent resin 2 had a weight average molecular weight Mw of 32000 and a double bond equivalent of 460.

(Synthesis example 3 of photosensitive transparent resin)
520 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 7.0 parts of methacrylic acid, 7.0 parts of methyl methacrylate, 63.0 parts of 2-hydroxyethyl methacrylate at the same temperature. Then, a mixture of 66.0 parts of glycerol monomethacrylate 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, and then 1.0 part of azobisisobutyronitrile dissolved in 70 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained.
Next, with respect to 220 parts of the obtained transparent resin solution, a mixture of 26.0 parts of 2-methacryloylethyl isocyanate, 0.4 part of dibutyltin laurate, and 220.0 parts of cyclohexanone was added at 70 ° C. over 3 hours. The solution was dropped to obtain a photosensitive transparent resin solution. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The previously synthesized photosensitive transparent resin solution has a non-volatile content of 20% by weight. Cyclohexanone was added as follows. The obtained photosensitive transparent resin 3 had a weight average molecular weight Mw of 20000 and a double bond equivalent of 270.

(Synthesis example 4 of photosensitive transparent resin)
480 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 32.0 parts of methacrylic acid, 24.0 parts of methyl methacrylate, 16.0 parts of n-butyl methacrylate, 29.0 parts of benzyl methacrylate, 19.0 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) as monomer (a), 15.0 parts of glycerol monomethacrylate, 2,2′- A mixture of 4.0 parts of azobisisobutyronitrile was added dropwise over 1 hour to conduct a polymerization reaction. 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 80 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained.
Next, with respect to 445 parts of the obtained transparent resin solution, a mixture of 14.0 parts of 2-methacryloylethyl isocyanate, 0.4 parts of dibutyltin laurate and 55.0 parts of cyclohexanone was added at 70 ° C. over 3 hours. The solution was dropped to obtain a photosensitive transparent resin solution. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The previously synthesized photosensitive transparent resin solution has a non-volatile content of 20% by weight. Cyclohexanone was added as follows. The obtained photosensitive transparent resin 4 had a weight average molecular weight Mw of 21000 and a double bond equivalent of 1000.

(Synthesis example 5 of photosensitive transparent resin)
560 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 22.0 parts of methacrylic acid, 22.0 parts of n-butyl methacrylate, 2-hydroxyethyl methacrylate 104. A polymerization reaction was carried out by dropping a mixture of 0 part and 4.0 part of 2,2′-azobisisobutyronitrile over 1 hour. 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 resin solution was obtained.
Next, a mixture of 33.0 parts of 2-methacryloylethyl isocyanate, 0.4 parts of dibutyltin laurate and 130.0 parts of cyclohexanone was added to 338 parts of the obtained transparent resin solution at 70 ° C. over 3 hours. The solution was dropped to obtain a photosensitive transparent resin solution. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The previously synthesized photosensitive transparent resin solution has a non-volatile content of 20% by weight. Cyclohexanone was added as follows. The obtained photosensitive transparent resin 5 had a weight average molecular weight Mw of 20000 and a double bond equivalent of 470.

(Synthesis example 6 of photosensitive transparent resin)
570 parts of cyclohexanone was placed in a reaction vessel and heated to 80 ° C. while injecting nitrogen gas into the vessel. At the same temperature, 7.0 parts of methacrylic acid, 11.0 parts of methyl methacrylate, 32.0 parts of benzyl methacrylate, 2- Hydroxyethyl methacrylate 101.0 parts, 2,2′-azobisisobutyronitrile 3.0 parts A mixture of the following monomers and a thermal polymerization initiator 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 resin solution was obtained.
Next, a mixture of 33.0 parts of 2-methacryloylethyl isocyanate, 0.4 parts of dibutyltin laurate and 130.0 parts of cyclohexanone was added to 337 parts of the obtained transparent resin solution at 70 ° C. over 3 hours. The solution was dropped to obtain a photosensitive transparent resin solution. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The previously synthesized photosensitive transparent resin solution has a non-volatile content of 20% by weight. Cyclohexanone was added as follows. The obtained photosensitive transparent resin 6 had a weight average molecular weight Mw of 30,000 and a double bond equivalent of 460.

(Synthesis example 1 of non-photosensitive transparent resin)
370 parts of cyclohexanone was put in 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 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 earlier had a non-volatile content of 20% by weight. Cyclohexanone was added so that The obtained non-photosensitive transparent resin 1 had a weight average molecular weight Mw of 40000.

(Synthesis example 2 of non-photosensitive 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 n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, and 5.5 methacrylic acid at the same temperature. 3 parts, 7.4 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toa Gosei Co., Ltd.) as monomer (a), 0.4 part of 2,2'-azobisisobutyronitrile Was added dropwise over 2 hours to carry out the polymerization reaction. 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 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 earlier had a non-volatile content of 20% by weight. Cyclohexanone was added so that The obtained non-photosensitive transparent resin 2 had a weight average molecular weight Mw of 27000.

(Synthesis example 3 of non-photosensitive transparent resin)
70 parts of cyclohexanone is put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 14.4 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 3. 2 parts, a mixture of 7.4 parts paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toa Gosei Co., Ltd.) as monomer (a), 0.4 parts 2,2'-azobisisobutyronitrile Was added dropwise over 2 hours to carry out the polymerization reaction. 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 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 earlier had a non-volatile content of 20% by weight. Cyclohexanone was added so that The obtained non-photosensitive transparent resin 3 had a weight average molecular weight Mw of 25,000.

Photosensitive transparent resins 1 to 6 obtained in Synthesis Examples 1 to 6 of the photosensitive transparent resin, and non-photosensitive transparent resins 1 to 3 obtained in Synthesis Examples 1 to 3 of the non-photosensitive transparent resin Mw, double bond equivalent and acid value are shown in Table 1. The acid value was measured and calculated according to JIS-K-0070.

感光性透明樹脂１溶液 ９．９部
非感光性透明樹脂２溶液 ３０．１部
シクロヘキサノン ４８．０部 [Example 1]
(Method for producing pigment dispersion)
After the mixture having the following composition is uniformly stirred and mixed, the mixture is dispersed for 2 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A pigment dispersion was prepared.
ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6)
("Heliogen Blue L-6700F" manufactured by BASF) 11.0 parts 1.0 part of phthalocyanine pigment derivative (the following formula (2))

Photosensitive transparent resin 1 solution 9.9 parts Non-photosensitive transparent resin 2 solution 30.1 parts Cyclohexanone 48.0 parts

(Production method of blue coloring composition)
Next, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a blue colored composition having photosensitivity.
Pigment dispersion prepared in Example 1 45.0 parts Photosensitive transparent resin 1 solution obtained in Synthesis Example 1 15.9 parts Dipentaerythritol hexaacrylate 5.4 parts Photopolymerization initiator ("Irgacure" manufactured by Ciba Geigy) 907 ") 2.0 parts Sensitizer (" EAB-F "manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts Cyclohexanone 31.5 parts

[Examples 2-28 and Comparative Examples 1-5]
The photosensitive transparent resin solution, the non-photosensitive transparent resin solution and the polyfunctional monomer shown in Table 3 were blended so as to have the ratio shown in Table 3 (weight ratio of the solid content), and the same photosensitivity as in Example 1. A blue-colored composition (blue resist material) was obtained. About the photosensitive transparent resin and the non-photosensitive transparent resin, the photosensitive transparent resin solution and the non-photosensitive transparent resin solution were adjusted so that it might become the ratio shown in Table 3 with a polyfunctional monomer. The ratio of these three components in 100 parts by weight of the obtained blue coloring composition is the same for Examples 1 to 28 and Comparative Examples 1 to 5.
Table 2 shows a list of polyfunctional monomers used in Examples and Comparative Examples. Table 3 shows the content (% by weight) of the photosensitive transparent resin based on the total weight of the photosensitive transparent resin and the non-photosensitive transparent resin, the photosensitive transparent resin contained in the blue coloring composition, and the non-photosensitive transparent The ethylenically unsaturated double bond contained in the photosensitive transparent resin at a molar concentration (Cb) of ethylenically unsaturated double bond contained in the polyfunctional monomer based on the total weight of the resin and the polyfunctional monomer Based on the ratio (Cb / Ca) to the molar weight concentration (Ca), the total weight of the photosensitive transparent resin, the non-photosensitive transparent resin, and the polyfunctional monomer contained in the blue colored composition, The result of having calculated the weight molar concentration (functional group density) (mol / g) of an ethylenically unsaturated double bond is shown, respectively. (In Comparative Example 3, the ethylenically unsaturated double bond molar polymerization concentration of the blue colored composition was calculated using the double bond equivalent of the bifunctional monomer and the weight of the bifunctional monomer.)
However, Examples 3, 8, 15, 16, 17, and 20 are reference examples.

About the blue coloring composition obtained by the Example and the comparative example, viscosity stability, sensitivity, patterning property, and solvent resistance were evaluated by the following method.
(Viscosity stability evaluation) E type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.) was used to determine the initial viscosity of the next day after the blue colored composition was prepared and the time-lapse viscosity accelerated at 40 ° C. for one week. It was measured under the condition of a rotation speed of 20 rpm at 25 ° C. Table 4 shows the results of calculating the rate of change from the initial viscosity to the time-dependent viscosity.
[Change rate of resist viscosity with time] = | ([initial viscosity] − [viscosity with time]) / [initial viscosity] × 100 |

(Sensitivity evaluation) The blue coloring composition was applied onto a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater to form a coating film having a thickness of 2.0 μm. Next, after pre-baking at 70 ° C. for 20 minutes, ultraviolet exposure was performed through a mask having a fine line pattern of 50 μm. It was exposed with an exposure amount of 8 levels between ^{10mJ / cm 2 ~200mJ / cm 2} . After exposure, the film was developed with an alkaline developer for 90 seconds to form a stripe-shaped filter segment. The alkali developer is 1.5% by weight of sodium carbonate, 0.5% by weight of sodium bicarbonate, 8.0% by weight of an anionic surfactant (“PERILEX NBL” manufactured by Kao Corporation) and 90% by weight of water. What was used.
The residual film ratio after exposure / development at each exposure level when the film thickness of the obtained filter segment was defined as 100 for the unexposed / undeveloped portion was calculated. From the obtained residual film rate curve, the exposure amount at which the residual film rate reached saturation was determined as the saturated exposure amount, and the residual film rate was determined as the saturated residual film rate. Table 4 shows the obtained saturated exposure and saturated residual film ratio.

(Patternability evaluation) In sensitivity evaluation, the exposure amount of ultraviolet rays was set to a saturation exposure amount + 50 mJ / cm ² , and the development time with an alkali developer was set to an appropriate time for washing away the unexposed portions of the resist coating film. After the substrate is prepared in the same way, heat treatment is performed at 230 ° C. for 60 minutes, and the shape of the fine line pattern is changed to (1) pattern line width accuracy (number after patterning with respect to the mask pattern line width). (2) The cross sectional shape of the pattern was evaluated. (1) was evaluated using an optical microscope. The evaluation results are shown in Table 4. The ranks of the evaluation are as follows: ◯: The difference from the line width of the mask pattern is 5% or less, Δ: The difference from the line width of the mask pattern is 5 to 10%, and X: The difference from the line width of the mask pattern is 10% or more. It was. (2) was evaluated using a scanning electron microscope (SEM). The rank of evaluation was as follows: ○: forward tapered shape, Δ: non-tapered shape, ×: reverse tapered shape.

(Solvent resistance evaluation) A pre-baked coating film was prepared in the same manner as the sensitivity evaluation, and ultraviolet rays were used at a saturation exposure of +50 mJ / cm ² through a mask having a fine line pattern with a diameter of 50 μm using an ultrahigh pressure mercury lamp. Exposure was performed. After the exposure, development was performed with an alkaline developer for 90 seconds to form each color filter segment in a stripe shape on the substrate. The developed substrate was heat-treated at 230 ° C. for 60 minutes. A part of the substrate was immersed in N-methylpyrrolidone (NMP) for 30 minutes, and then the state of the pattern surface was observed with an optical microscope. A sample in which no change was observed was marked with ◯, a sample with slight cracks or the like was marked with Δ, and a sample with severe cracks or the like marked with ×. The results are shown in Table 4.

As shown in Table 4, when the mixing ratio of each component of the photosensitive transparent resin, the non-photosensitive transparent resin, and the polyfunctional monomer having three or more ethylenically unsaturated double bonds is not suitable, the functional group density is particularly high. When it is not in an appropriate range, the sensitivity as a blue coloring composition is insufficient, or the patterning property is poor. On the other hand, when the blending ratio of each component in the blue colored composition is appropriate, both high sensitivity and good patternability can be achieved. The dispersion stability and patterning property of the blue coloring composition are greatly influenced by the characteristics and ratios of the photosensitive transparent resin and the non-photosensitive transparent resin compounded in the blue coloring composition. In Examples 21, 22, 24, etc. By using a photosensitive transparent resin and a non-photosensitive transparent resin excellent in dispersibility and blending an appropriate amount of the photosensitive transparent resin in a balanced manner, both dispersion stability and good patterning properties are achieved. Moreover, the blue coating film excellent in the solvent resistance which has not been able to be obtained was able to be obtained by mix | blending appropriate amount of photosensitive transparent resin in a blue coloring composition.

Claims (5)

A blue coloring composition comprising a photosensitive transparent resin, a non-photosensitive transparent resin, a polyfunctional monomer having three or more ethylenically unsaturated double bonds, and a blue coloring material, wherein the blue coloring composition contains The molar concentration of ethylenically unsaturated double bonds is 3.5 × 10 ⁻³ mol / g to 6.1 × 10 based on the total weight of the photosensitive transparent resin, the non-photosensitive transparent resin, and the polyfunctional monomer. ^-3 mol / g der is, the double bond equivalent of the photosensitive transparent resin is 200 to 1,200, and the total weight of the content of the photosensitive transparent resin, photosensitive transparent resin and the non-photosensitive transparent resin A blue coloring composition for a color filter, characterized by being 15 to 80% by weight based on the above . The color filter according to claim 1, wherein the photosensitive transparent resin or the non-photosensitive transparent resin contains an ethylenically unsaturated monomer (a) represented by the following formula (1) as a copolymerization component. Blue coloring composition.

(In 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 which may contain a benzene ring. Represents an alkyl group of -20. N represents an integer of 1-15.) The blue colored composition for a color filter according to claim 1 or 2 , wherein the acid value of the photosensitive transparent resin is lower than the acid value of the non-photosensitive transparent resin. Multifunctional having 3 or more ethylenically unsaturated double bonds, based on the total weight of the photosensitive transparent resin, non-photosensitive transparent resin, and polyfunctional monomer having 3 or more ethylenically unsaturated double bonds ethylenically unsaturated double bond molal concentration of the monomer, 3 any one claims 1, characterized in that a 2 to 35 times the ethylenically unsaturated double bond molar concentration of the photosensitive transparent resin The blue coloring composition for color filters as described in any one of. A color filter comprising a filter segment formed from the blue coloring composition for a color filter according to any one of claims 1 to 4 .