CN1492283A - Photosensitive coloring composition and color filter - Google Patents

Abstract

Provided are a novel photosensitive coloring composition having excellent dispersion stability and fluidity and a color filter using the composition. A color filter has extremely reduced inferiority by using a color resist where the generation of insoluble agglomerate at the terminal part of a dispense nozzle or a slit die and the inside of an air operator or a pipe made of Teflon or polypropylene is remarkably reduced, by using the composition. The photosensitive coloring composition comprises a resin having a copolymer of at least one kind of compound represented by the formula I and another compound having an ethylenically unsaturated double bond; a monomer; and a colorant, wherein R1 is H or CH3; R2 is an alkylene group of C2-C3; R3 is H or an alkyl group of C1-C20 which may contains a benzene ring; and n is an integer of 1-15. Preferably the another compound having an ethylenically unsaturated double bond is at least one selected from the group consisting of (meth)acrylic acid and (meth)acrylate. The composition comprises further at least one selected from the group consisting of a basic group-having pigment derivative, a basic group-having anthraquinone derivative and a basic group-having triazine derivative.

Description

Photosensitive coloring composition and color filter

technical field

The present invention relates to a novel photosensitive coloring composition and color filter. The photosensitive coloring composition of the present invention is suitably used as an image forming material such as an optical color filter or a solder resist. In particular, the present invention relates to a photosensitive coloring composition and a color filter suitable for producing color filters used for color liquid crystal display devices, color imaging tube elements, and the like.

Background technique

Color filters used in color liquid crystal display devices, color imaging tube elements, etc. are colored images in which fine patterns such as stripes or mosaics of two or more different tones are formed on a transparent substrate such as a glass substrate. The pattern width is about 5 to 700 μm, which varies depending on the application of the color filter and each color. In addition, since the positional accuracy of overlapping patterns is several μm to several tens of μm, the color filter is manufactured using a microfabrication technique with high dimensional accuracy.

Various methods such as dyeing method, electrodeposition method, printing method, and pigment dispersion method are known as methods for manufacturing color filters. However, considering productivity, quality, and cost, etc., the actual situation is that the pigment dispersion method is the best. It is widely used as a manufacturing method of color filters. The pigment dispersion method is to manufacture a color filter by forming a colored image on a base material by lithography using a color resist composed of a photosensitive material colored by dispersing an organic pigment. resin composition.

However, in the pigment dispersion method, it is difficult to disperse the pigment stably, and it is particularly difficult to select a dispersion resin that greatly affects the dispersion stability of the pigment.

As a method of coating the above-mentioned color photoresist on a glass substrate, coating is usually performed with a spin coater, but in this case, if the fluidity of the pigment is insufficient, a uniform coating film cannot be obtained.

It is generally believed that the viscosity of a color photoresist as a pigment dispersion is determined by the shear rate. Since the film thickness of the color photoresist is proportional to its viscosity during spin coating, in order to obtain a uniform coating film, it is necessary to make the viscosity of the color photoresist coated on the center and outer circumference of the transparent substrate the same.

When the color resist is supplied onto the substrate and rotated, the apparent viscosity of the color resist is close to the viscosity when the shear rate is low because the linear velocity at the center is low. On the other hand, since the linear velocity at the peripheral peripheral portion of the substrate is high, the apparent density of the color photoresist is close to the viscosity when the shear velocity is high. Therefore, for thixotropic color photoresists, the apparent viscosity increases at the center of the substrate where the shear rate is low, and the film thickness becomes thicker, and the film thickness becomes thinner at the outer circumference where the shear rate is high and the apparent viscosity is large. . Since the color filter is required to have a uniform film thickness in the substrate, the color photoresist is required to be a fluid with uniform viscosity regardless of the shear rate, that is, a Newtonian fluid.

Since color filters are required to have particularly high transparency, those obtained by uniformly dispersing very fine pigments in a transparent vehicle (vehicle) are used.

It is known that when fine particles of a pigment are dispersed in a vehicle, it is difficult to obtain a stable dispersion, and various problems arise in terms of manufacturing operations and the value of the manufactured product. For example, a dispersion containing a pigment composed of fine particles often exhibits high viscosity, which not only makes it difficult to take out or transport the product from the disperser, but also sometimes gels during storage, making it difficult to use. Furthermore, the transparency of a color resist coating film falls, and malfunctions, such as poor leveling, may arise. Therefore, in order to produce a highly transparent color filter by the pigment dispersion method, a technique for stably dispersing finer pigments is required.

In addition, in the color photoresist, due to the gradual aggregation of the pigment particles over time, the viscosity increases, and the thixotropy gradually increases. After a period of time, the film thickness and film uniformity will be different.

As can be seen from the above, it is important that the color photoresist is a Newtonian fluid and that its physical properties do not change over a long period of time.

In addition, the color resist may be coated with a slot-spin coater, roll coater, curtain coater, etc. other than the spin coater. In addition, the color photoresist is supplied to the nozzle or narrow slit die from the chemical solution tank through tubes such as Teflon and polypropylene or pneumatic pumps.

Due to the low pigment dispersion stability of conventional photosensitive coloring compositions, when coating photoresist with the above-mentioned coater, the inside of tubes such as Teflon and polypropylene or the inside of an air pump, the front end of a spray nozzle or a slit die, etc. Insoluble agglomerates are generated at the site, and the agglomerates become a cause of defective foreign matter in the color filter, significantly reducing productivity.

In order to solve the above various problems, it is proposed to use organic pigments as the matrix, and the pigment derivatives containing acidic groups or basic groups as substituents on the side chains are used as dispersants (referring to Japanese Patent Publication No. 41-2466 communique for example) , U.S. Patent No. 2,855,403, JP-A-63-305173, JP-1-247468, JP-3-26767).

Also, the use of copolymers having an oxyalkylene group has been proposed (see, for example, JP-A-62-25164, JP-A-4-223468, and JP-A-5-39450).

However, the actual situation is that even if these methods are used, except for some methods, the remaining methods cannot obtain satisfactory results.

Contents of the invention

Therefore, the object of this invention is to provide the photosensitive coloring composition excellent in the dispersion stability of a pigment.

Another object of the present invention is to provide a color filter using the photosensitive coloring composition.

The present invention provides a photosensitive coloring composition containing a resin, a monomer and a colorant, wherein the resin is at least one compound (a) represented by the following general formula (I) and another A copolymer resin of at least one compound (b) containing an ethylenically unsaturated double bond.

In general formula (I), R ₁ is H or CH ₃ , R ₂ is an alkylene group with 2 or 3 carbons, R ₃ is hydrogen or an alkyl group with 1 to 20 carbons that may contain a benzene ring, n It is an integer from 1 to 15.

The present invention also provides a color filter including a transparent substrate and a coloring material layer formed on the transparent substrate using the photosensitive coloring composition of the present invention.

Detailed ways

The present invention will be described in more detail below.

The photosensitive coloring composition of the present invention contains a copolymer resin of the compound (a) represented by the above general formula (I) and another compound (b) containing an ethylenically unsaturated double bond. The resin (copolymer) can prevent the coagulation of the colorant (pigment) contained in the photosensitive coloring composition of the present invention, maintain the pigment in a finely dispersed state, and is useful for the manufacture of filters with high light transmittance and high color purity. Shades are very important substances.

The compound (a) represented by the general formula (I), which is the constituent component of the above-mentioned resin, improves the adsorption/orientation on the surface of the pigment due to the effect of π electrons in the benzene ring.

In the general formula (I), the alkylene group _R2 contains 2 to 3 carbon atoms. Also, the alkyl group _R3 contains 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. When the carbon number of the alkyl group _R3 is 1 to 10, the alkyl group becomes an obstacle, which prevents the resins from approaching each other, thereby promoting the adsorption/orientation on the pigment, but if the carbon number exceeds 10, the stereoscopic effect of the alkyl group The steric hindrance effect is enhanced, showing a tendency to hinder the adsorption/orientation of the alkyl-bonded benzene ring on the pigment. This tendency becomes more remarkable as the carbon chain of the alkyl _R3 increases, and when the carbon number exceeds 20, the adsorption/orientation of the benzene ring to which the alkyl group is bound decreases sharply. The benzene ring-containing alkyl group represented by R ₃ includes benzyl group, 2-phenyl(iso)propyl group and the like.

As compound (a), it includes ethylene oxide (EO) modified (meth)acrylate of phenol, EO or propylene oxide (PO) modified (meth)acrylate of p-cumylphenol, nonyl EO modified (meth)acrylate of phenol, PO modified (meth)acrylate of nonylphenol, etc. Compounds (a) can be used alone or in combination of two or more. Among these compounds, the EO or PO modified (meth)acrylate of p-cumylphenol not only has the above-mentioned π-electron effect of the benzene ring, but also has a stereoscopic effect, which can form a better adsorption/orientation surface for the pigment, So the effect is higher.

Compound (b) is a compound containing an ethylenically unsaturated double bond, and is a compound different from compound (a). Specific examples of the compound (b) include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, (iso)propyl (meth)acrylate, (iso)butyl (meth)acrylate ester, (iso)pentyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid Cyclohexyl ester, glycidyl (meth) acrylate, isobornyl (meth) acrylate, acid phosphoxyethyl (meth) acrylate (acid phosphoxyethyl (meth) acrylate), acid hydroxypropyl phosphate ( Meth)acrylate, 3-chloro-2-acid hydroxyethyl phosphate (meth)acrylate, acid hydroxypolyethylene glycol mono(meth)acrylate, etc. Compounds (b) can be used alone or in combination of two or more.

The proportion of the compound (a) in the resin of the present invention is 0.1 to 50% by weight, more preferably 10 to 35% by weight. If the ratio of the compound (a) is less than 10% by weight, the dispersion effect of the pigment will decrease, and if it is less than 0.1% by weight, a sufficient pigment dispersion effect will not be obtained. Moreover, if it is more than 35% by weight, the hydrophobicity will increase, the developability of the photosensitive coloring composition will decrease, and it may cause residues. The compatibility of components is remarkably lowered, and precipitation of a monomer or a photopolymerization initiator may occur.

The weight average molecular weight (Mw) of the resin (copolymer) of the present invention is preferably 5,000 to 100,000, more preferably 10,000 to 50,000.

When compound (b) uses acidic phosphate hydroxyethyl (meth)acrylate, acidic phosphate hydroxypropyl (meth)acrylate, 3-chloro-2-acidic phosphate hydroxyethyl (meth)acrylate When using phosphoric acid group-containing (meth)acrylates such as hydroxypolyethylene glycol mono(meth)acrylate acid phosphate, a higher pigment dispersion effect may be obtained in some cases.

The ratio of the phosphoric acid group-containing (meth)acrylate is 0.05 to 10% by weight, more preferably 0.1 to 5% by weight. When the ratio of the phosphoric acid group-containing (meth)acrylate is less than 0.05% by weight, a sufficient pigment dispersion effect cannot be obtained. Moreover, if it exceeds 10 weight%, the polarity of resin will increase, a developing speed will increase remarkably, the compatibility with other hydrophobic components will fall, and precipitation of resin will arise.

In addition, in order to react monomers or resins and improve the sensitivity of the photosensitive coloring composition, an ethylenic double bond may be introduced into the side chain of the resin (copolymer) of the present invention. Specifically, when the resin contains a reactive functional group such as a hydroxyl group, the functional group that reacts with the above-mentioned reactive functional group such as glycidyl (meth)acrylate and 2-(meth)acryloyloxyisocyanate and the resin containing ethylene can be used. A compound with a saturated group is reacted to introduce an ethylenically unsaturated double bond into the side chain.

The copolymer of the present invention can be carried out free radical polymerization by making compound (a) and compound (b) carry out free radical polymerization under inert gas flow under inert gas flow in the presence of free radical initiator, reaction 2～10 made in hours. This polymerization reaction can be performed in the presence of a solvent if necessary.

Specific examples of the above radical polymerization initiator include benzoyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, diisopropyl peroxycarbonate, di-tert-butyl peroxide, tert-butyl peroxide, Organic peroxides such as oxidized benzoate; azo compounds such as 2,2'-azobisisobutyronitrile, etc. It is preferable that the usage ratio of a radical polymerization initiator is 1-20 weight part with respect to 100 weight part of ethylenically unsaturated monomers (that is, the total amount of a compound (a) and a compound (b)).

Specific examples of solvents used for the above radical polymerization include water and/or water-miscible organic solvents or acetates such as ethylene glycol monoethyl ether acetate and propylene glycol monomethyl ether acetate; cyclohexanone, methyl isobutyl Ketones and other ketones; xylene, ethylbenzene, etc. Specific examples of the water-miscible organic solvent include alcohol-based solvents such as ethanol, isopropanol, and n-propanol, mono- or dialkyl ethers of ethylene glycol or diethylene glycol, and the like.

Since the resin of the present invention exhibits a good dispersion effect on almost all pigments, when the coloring material layer of a color filter is formed using the photosensitive coloring composition of the present invention in which the pigment is dispersed with the resin, pigment aggregates can be obtained Less layers of coloring material.

The (polymerizable) monomers constituting the photosensitive coloring composition of the present invention cannot be cured by active energy rays only in the resin (copolymer) of the present invention, so the pattern of the color filter cannot be formed by irradiation of active energy rays , but by adding a monomer (polymerizable monomer) containing the functional group (ethylenic double bond), it can be cured by active energy rays. A monomer containing only one functional group (ethylenic double bond) in one molecule is a monofunctional monomer, and a monomer containing two or more functional groups (ethylenic double bond) in one molecule is a polyfunctional monomer. The larger the number of functional groups (ethylenic double bonds) in one molecule, the higher the reactivity of the monomer. Specific examples of the monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, tricyclodecanyl (meth)acrylate Various acrylates and methacrylates; (meth)acrylic acid, styrene, vinyl acetate, (meth)acrylamide, N-methylol (meth)acrylamide, acrylonitrile and other monofunctional mono body; polyethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, epoxy (meth)acrylate, EO modified bisphenol A di( Meth)acrylate, 1,4-butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythr Diol di(meth)acrylate, polyester(meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(acryloyloxyethyl)isocyanurate, tris(methacrylic acid) Acyloxyethyl) isocyanurate, dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexaacrylate, bis(trimethylolpropane)tetra(meth)acrylate, epoxy acrylate ester, pentaerythritol tetra(meth)acrylate and other polyfunctional monomers.

The pigment used as a colorant constituting the photosensitive coloring composition of the present invention is not particularly limited as long as it is commonly used. Specific examples of the pigment include: diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and metal-free copper phthalocyanine. Pigments; aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, yellow anthrone, anthrone anthrone, indanthrene (standard vat blue), pyranthrone, Violanthron (C.I. vat blue 20) Anthraquinone pigments; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; isoindolin pigments; isoindolinone Pigments; quinophthalone pigments; Shihlin pigments; organic pigments such as metal complex pigments; or titanium oxide, zinc white, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon black, alumina white , kaolin, talc, bentonite, black iron oxide, cadmium red, iron oxide red, molybdenum red, molybdenum orange, chrome vermilion, lead chromate, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, Velidian pigment ( C.I. Pigment Green 18), Titanium Cobalt Green, Cobalt Green, Cobalt Chrome Green, Victoria Green, Ultramarine Blue, Prussian Blue, Cobalt Blue, Cellulian Blue (C.I. Pigment Blue 15), Cobalt Silicon Blue, Cobalt Zinc Silicon Blue, Manganese Violet, cobalt violet and other inorganic pigments; or carbon black such as acetylene carbon black, channel black, furnace black and so on. These pigments preferably have an average particle diameter of 0.01 μm to 1 μm.

The weight ratio of the copolymer resin, monomer, and colorant (pigment) contained in the photosensitive coloring composition of the present invention is preferably 1-50:1-10:1-15.

In order to further improve the effect of the copolymer resin of the present invention, preferably, the photosensitive coloring composition of the present invention contains a pigment derivative with a basic group, an anthraquinone derivative with a basic group, or an anthraquinone derivative with a basic group. At least one selected from basic-based triazine derivatives.

The so-called pigment derivatives refer to compounds that combine sulfonic acid, amine, sulfonamide, etc. on the group that removes an appropriate number of hydrogen atoms from the matrix of the organic pigment, that is, the organic pigment skeleton. The dispersion stability of the pigment in the permanent coloring composition is improved.

The pigment derivatives containing basic groups, anthraquinone derivatives or triazine derivatives containing basic groups used in the present invention contain the following formulas (1), (2), (3) and (4) at least one substituent.

In the above formulas (1) to (4),

X represents -SO ₂ -, -CO-, -CH ₂ NHCOCH ₂ -, -CH ₂ - or a direct combination.

m represents the integer of 1-10.

R ₄ and R ₅ are independent of each other and are alkyl groups that may be substituted, alkenyl groups that may be substituted, or phenyl groups that may be substituted, or R ₄ and R ₅ are integrated to represent nitrogen, oxygen or sulfur atoms, Heterocycles that may be substituted. It is preferable that the carbon number of an alkyl group and an alkenyl group is 1-10.

R ₆ represents an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group. It is preferable that the carbon number of an alkyl group and an alkenyl group is 1-10.

R ₇ , R ₈ , R ₉ , and R ₁₀ are independent of each other and represent a hydrogen atom, an alkyl group that may be substituted, an alkenyl group that may be substituted, or a phenyl group that may be substituted. It is preferable that the carbon number of an alkyl group and an alkenyl group is 1-5.

Y represents -NR ₁₁ -Z-NR ₁₂ - or a direct combination.

R ₁₁ and R ₁₂ are independent of each other and represent a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or a phenyl group which may be substituted. It is preferable that the carbon number of an alkyl group and an alkenyl group is 1-5.

Z represents an optionally substituted alkylene group, an optionally substituted alkenylene group or an optionally substituted phenylene group. It is preferable that the carbon number of an alkylene group and an alkenylene group is 1-8.

P represents a substituent represented by formula (5) or a substituent represented by the following formula (6).

Q represents a hydroxyl group, an alkoxy group, a substituent represented by the following formula (5), or a substituent represented by the following formula (6).

In formula (5) and formula (6), R ₄ to R ₁₀ and m are the same as those defined above.

The amine components used to form substituents represented by formulas (1) to (6) are, for example, dimethylamine, diethylamine, N,N-ethylisopropylamine, N,N-ethylpropylamine, N,N- Methylbutylamine, N,N-methylisobutylamine, N,N-butylethylamine, N,N-tert-butylethylamine, diisopropylamine, dipropylamine, N,N-sec-butylpropylamine, Dibutylamine, di-sec-butylamine, diisobutylamine, N,N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di(2-ethylhexyl)amine, dioctylamine, N,N-Methyloctadecylamine, Didecylamine, Diallylamine, N,N-Ethyl-1,2-Dimethylpropylamine, N,N-Methylhexylamine, Dioleylamine, Distearylamine Amide, N,N-dimethylaminomethylamine, N,N-dimethylaminoethylamine, N,N-dimethylaminopentylamine, N,N-dimethylaminobutylamine, N,N- Diethylaminoethylamine, N,N-diethylaminopropylamine, N,N-diethylaminohexylamine, N,N-diethylaminobutylamine, N,N-diethylaminopentylamine, N,N-dipropylaminobutylamine, N,N-dibutylaminopropylamine, N,N-dibutylaminoethylamine, N,N-dibutylaminobutylamine, N,N-diisobutyl Aminopentylamine, N,N-Methyldodecylaminopropylamine, N,N-Ethylhexylaminoethylamine, N,N-Distearylaminoethylamine, N,N-Dioleoylaminoethylamine Amine, N, N-distearylaminobutylamine, piperidine, 2-piperoline, 3-piperoline, 4-piperoline, 2,4-dimethylpiperidine, 2,6-bis Methylpiperidine, 3,5-dimethylpiperidine, 3-piperidinemethanol, pipecolic acid, isopiperidine acid, isopiperidine methyl ester, isopiperidine ethyl ester, 2-piperidine ethanol, Pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipercoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl -2-pipercoline, N-aminopropyl-4-pipercoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylpiperazine, 1- Cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine.

Organic pigments constituting basic-based pigment derivatives include, for example, diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, and polyazo, phthalocyanine pigments, diaminodianthraquinone, anthracene Pyrimidine, yellow anthrone, anthrone, anthrone, indanthrene (standard vat blue), pyranthrone, violanthron (C.I. vat blue 20) and other anthraquinone pigments, quinacridone, dioxazine , Perinon-based pigments, perylene-based pigments, thioindigo-based pigments, isoindolin-based pigments, isoindolinone-based pigments, quinphthalone-based pigments, Shihlin-based pigments, metal complex-based pigments, etc. .

Anthraquinone derivatives containing basic groups may also have alkyl groups such as methyl and ethyl groups; amino groups, nitro groups, hydroxyl groups, or alkoxy groups such as methoxy groups and ethoxy groups; or halogens such as chlorine and other substituents.

Triazine derivatives containing basic groups can have methyl, ethyl and other alkyl or amino or dimethylamino, diethylamino, dibutylamino and other alkylamino or nitro or hydroxyl or methoxy Alkoxy groups such as ethoxy, butoxy, or halogens such as chlorine, or phenyl substituted with methyl, methoxy, amino, dimethylamino, hydroxy, etc., or substituted with methyl, ethyl, methoxy , ethoxy, amino, dimethylamino, diethylamino, nitro, hydroxyl and other substituents such as anilino substituted 1,3,5-triazine.

The basic group-containing pigment derivative or anthraquinone derivative of the present invention can be synthesized through various synthetic routes. For example, after introducing substituents represented by the following formulas (7) to (10) into organic pigments or anthraquinones, react with the above substituents to form amine components of formulas (1) to (4), such as N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4-[4-hydroxy-6-[3-(dibutylamino)propylamine]-1,3,5-triazine-2 - Base amino] aniline and other reactions, thus obtained.

-SO ₂ Cl (7)

-COCl (8)

-CH ₂ NHCOCH ₂ Cl(9)

_-CH2Cl (10)

Also, when the organic pigment is an azo-based pigment, the substituents represented by the formulas (1) to (4) can also be introduced into the disazo component or the coupling component in advance, and then the azo-based pigment can be produced by performing a coupling reaction. Pigment derivatives.

The basic group-containing triazine derivatives of the present invention can be synthesized by various synthetic routes. For example, using cyanuric chloride as a starting material, the amine components forming the substituents represented by formulas (1) to (4), such as N, N-dimethylaminopropylamine or N-methylpiperazine, etc. It is prepared by reacting with at least one chlorine of cyanuric chloride, and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols, etc.

The proportion of the above-mentioned basic group-containing pigment derivative, basic group-containing anthraquinone derivative and/or basic group-containing triazine derivative is 1 to 30 parts by weight based on 100 parts by weight of the pigment.

In addition to the above-mentioned pigment derivatives, pigment dispersants such as alkylene oxide polymers may be contained in the photosensitive coloring composition of the present invention.

The so-called alkylene oxide polymer refers to a polymer containing ethylene oxide and/or propylene oxide units in the molecule. Due to the amphiphilicity generated by the hydrophilic group and the hydrophobic group, it is adsorbed on the pigment and/or pigment dispersant. On the surface, while improving the dispersion stability of the pigment in the photosensitive coloring composition obtained, flow characteristics are improved. The use ratio of the pigment dispersion such as an alkylene oxide polymer is 1-50 weight part with respect to 100 weight part of pigments.

In addition, in order to impart various properties such as alkali developability, adhesiveness, solvent resistance, and heat resistance, in addition to the above-mentioned resins, common acrylic resins, α- Olefin/maleic acid (anhydride) copolymer, styrene/maleic acid (anhydride) copolymer, isobutylene/maleic acid (anhydride) copolymer, styrene/styrenesulfonic acid copolymer, ethylene/(meth)acrylic acid copolymer and other resins. In the photosensitive coloring composition, these general resins may be used in an amount of 1 to 50% by weight.

Moreover, when hardening the photosensitive coloring composition of this invention with an ultraviolet-ray, this composition is made to contain a photoinitiator.

Examples of the photopolymerization initiator include: 4-phenoxydichloroacetophenone, 4-tert-butyldichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl) -2-Hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan- Acetophenone-based photopolymerization initiators such as 1-ketone; benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, etc. Department of photopolymerization initiator; benzophenone-based photopolymerization initiators such as base sulfides; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, etc. Thioxanthone-based photopolymerization initiators; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methyl Oxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperone Base-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphthalene-1-acyl )-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphthalene-1-yl)-4,6-bis(trichloromethyl)-s-triazine triazine light Polymerization initiator; Carbazole-based photopolymerization initiator; Imidazole-based photopolymerization initiator, etc. These photopolymerization initiators can be used alone or in combination of two or more. The usage ratio of the photopolymerization initiator is 0.5-80 weight part with respect to 100 weight part of monomers.

A sensitizer can also be used together with the photopolymerization initiator mentioned above. Examples of sensitizers include α-acyloxy esters, acylphosphine oxides, methylphenyl glyoxylate, benzyl-9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'- Diethylisophthaloylbenzene, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 4,4'-diethylaminophenone, etc. The usage ratio of the sensitizer is 0.1-50 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

Moreover, water, an organic solvent, etc. can be added in order to fully disperse|distribute a pigment in the photosensitive coloring composition of this invention, and apply|coat uniformly and thinly on a transparent substrate. Organic solvents can be used alone or in combination.

The photosensitive coloring composition of this invention can be manufactured by the method of following 1-4, for example.

1. Add the pigment composition obtained by mixing the pigment and, if necessary, the pigment dispersion (pigment dispersant other than the pigment derivative) in advance to the monomer and copolymer resin or its organic solvent solution or aqueous solution, make it scattered. Even if the pigment powder and the powder of the pigment dispersant are simply mixed and prepared, the pigment composition can fully obtain the desired effect. However, if mechanical mixing is performed with various pulverizers such as a kneader, a fine grinder, a roller, and a super mixer, or a solution containing a pigment dispersant is added to a dispersion formed by dispersing a pigment in water or an organic solvent In the process, the pigment dispersion is adsorbed on the surface of the pigment, or the pigment and the pigment dispersant are dissolved together in a solvent with strong solubility such as sulfuric acid, and a weak solvent such as water is used to make the co-precipitation and other intimate mixing methods, etc., can obtain more good result.

2. A pigment and, if necessary, a pigment dispersant (a pigment dispersant other than a pigment derivative) are added to the monomer and copolymer resin or its organic solvent or aqueous solution to disperse them.

3. After dispersing the pigment and the pigment dispersant (pigment dispersant other than the pigment derivative) in the monomer and copolymer resin or its organic solvent solution or aqueous solution, respectively, these are mixed in advance. In this case, the pigment dispersant can be dispersed using only a solvent.

4. Add the pigment dispersant after dispersing the pigment into the monomer and copolymer resin or its organic solvent solution or aqueous solution.

The dispersion of pigments and pigment dispersants in monomers and copolymer resins or their organic solvent solutions or aqueous solutions can use three-roll mixers, two-roll mixers, sand mills, kneaders, high-speed dispersers, and high-speed mixers , homogeneous mixer, fine grinder and other dispersing devices. In addition, various surfactants may be added in order to facilitate dispersion at the time of dispersion.

The photosensitive coloring composition of the present invention removes coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more coarse particles and mixed dust by means of centrifugal separation, sintered filter, membrane filter and the like.

The color filter using the photosensitive coloring composition of the present invention is produced by a method called lithographic printing, which is to uniformly apply the photosensitive coloring composition of the present invention on a transparent substrate, and then pass through a photomask with ultraviolet rays. Pattern exposure is performed with active energy rays such as electron beams and electron beams, and the unexposed parts are washed off with solvent or alkaline aqueous solution to obtain the desired pattern.

The photosensitive coloring composition of the present invention is coated onto a transparent substrate by a coating method such as a spray coater, a spin coater, or a roll coater.

As the transparent substrate, resins such as glass plates, polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used.

Currently, almost no solvents are used in development due to environmental concerns, and alkaline development has become the mainstream. As an alkaline developer, an aqueous solution of an inorganic base such as sodium carbonate or sodium hydroxide or an organic base such as dimethylbenzylamine or triethanolamine is used. A defoamer or surfactant may also be added to this alkaline developer.

In addition, in order to increase the exposure sensitivity, after coating and drying the photosensitive coloring composition of the present invention, an aqueous solution or an alkaline water-soluble resin, such as polyvinyl alcohol or a water-soluble acrylic resin, can be coated and dried to form Exposure is performed after producing a polymerization-inhibited film.

Below in conjunction with embodiment the present invention is described in more detail. Here, production examples of the copolymer of the present invention, production examples of the basic group-containing pigment derivative, and examples of the present invention are given. The following "%" means "% by weight". "Part" means "part by weight". The molecular weight of the copolymer is a polystyrene-equivalent weight average molecular weight measured by GPC (gel permeation chromatography).

Production example of copolymer

Manufacturing example 1

Put 70.0 parts of cyclohexanone into a detachable 4-neck flask equipped with a thermometer, cooling tube, nitrogen inlet tube, dropper and stirring device, raise the temperature to 80°C, replace the inside of the flask with nitrogen, and use a dropper to Add 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of ethylene oxide modified acrylate (East Asia) in 2 hours. A mixture of Aronix M110 manufactured by Seisei Co., Ltd.) and 0.4 parts of 2,2'-azobisisobutyronitrile. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a solution of the desired copolymer (1) having a solid content of 30%. The weight average molecular weight of this copolymer (1) was 26,000.

Manufacturing example 2

Put 70.0 parts of cyclohexanone into a detachable 4-neck flask equipped with a thermometer, cooling tube, nitrogen inlet tube, dropper and stirring device, raise the temperature to 80°C, replace the inside of the flask with nitrogen, and use a dropper to 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of nonylphenoxypolyethylene glycol acrylate (Toagosei Co. Aronix M111) and a mixture of 0.4 parts of 2,2'-azobisisobutyronitrile. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a solution of the desired copolymer (2) having a solid content of 30%. The weight average molecular weight of this copolymer (2) was 28,000.

Manufacturing example 3

Put 70.0 parts of cyclohexanone into a detachable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropper and a stirring device, raise the temperature to 80°C, replace the inside of the reaction vessel with nitrogen, and then use a dropper Add 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, and 7.4 parts of nonylphenoxy polypropylene glycol acrylate (manufactured by Toagosei Co., Ltd.) dropwise for 2 hours. Aronix M117) and a mixed solution of 0.4 parts of 2,2'-azobisisobutyronitrile. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a solution of the desired copolymer (3) having a solid content of 30%. The weight average molecular weight of this copolymer (3) was 22,000.

Manufacturing example 4

Put 70.0 parts of cyclohexanone into a detachable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropper and a stirring device, raise the temperature to 80°C, replace the inside of the reaction vessel with nitrogen, and then use a dropper 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, and 7.4 parts of phenoxydiethylene glycol acrylate (Aronix, manufactured by Toagosei Co., Ltd.) were added dropwise over a period of 2 hours. M101) and a mixed solution of 0.4 parts of 2,2'-azobisisobutyronitrile. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a solution of the desired copolymer (4) having a solid content of 30%. The weight average molecular weight of this copolymer (4) was 26,000.

Manufacturing Example 5

Put 70.0 parts of cyclohexanone into a detachable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropper and a stirring device, raise the temperature to 80°C, replace the inside of the reaction vessel with nitrogen, and then use a dropper 14.1 parts of n-butyl methacrylate, 4.0 parts of 2-hydroxyethyl methacrylate, 3.9 parts of methacrylic acid, 7.4 parts of ethylene oxide modified acrylate ( A mixed solution of Toagosei Co., Ltd. Aronix M110), 0.3 parts of acid hydroxyethyl phosphate methacrylate (Nippon Kayaku Co., Ltd. Hosma-M), and 0.3 parts of 2,2'-azobisisobutyronitrile. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a solution of the desired copolymer (5) having a solid content of 30%. The weight average molecular weight of this copolymer (5) was 30,000.

Manufacturing example 6

Put 70.0 parts of cyclohexanone into a detachable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropper and a stirring device, raise the temperature to 80°C, replace the inside of the reaction vessel with nitrogen, and then use a dropper A mixed solution of 17.7 parts of n-butyl methacrylate, 6.1 parts of 2-hydroxyethyl methacrylate, 5.8 parts of methacrylic acid, and 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise to the tube within 2 hours. . After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a solution of the desired copolymer (6) having a solid content of 30%. The weight average molecular weight of this copolymer (6) was 27,000.

Manufacturing example 7

Put 70.0 parts of cyclohexanone into a detachable 4-neck flask equipped with a thermometer, cooling tube, nitrogen inlet tube, dropper and stirring device, raise the temperature to 80°C, replace the inside of the flask with nitrogen, and use a dropper to 21.5 parts of n-butyl methacrylate, 4.0 parts of 2-hydroxyethyl methacrylate, 3.9 parts of methacrylic acid, 0.3 parts of acid phosphate hydroxyethyl methacrylate (Nippon Kayakusha) were added dropwise in 2 hours. A mixed solution of Hosema-M), 2,2'-azobisisobutyronitrile. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a solution of the desired copolymer (7) having a solid content of 30%. The weight average molecular weight of this copolymer (7) was 31,000.

Manufacture of pigment derivatives containing basic groups

Manufacturing example 8

After carrying out chlorosulfonation of 50 parts of copper phthalocyanine as a pigment component, it was reacted with 14 parts of N,N-dimethylaminopropylamine as an amine component to obtain 62 parts of pigment derivatives having the following structure (1 ).

Pigment Derivatives (1):

In the formula, CuPc represents copper phthalocyanine residue.

Manufacturing example 9

After chlorosulfonating 50 parts of copper phthalocyanine as a pigment component, it was reacted with 40 parts of dibutylamine as an amine component to obtain 95 parts of a pigment derivative (2) having the following structure.

Pigment Derivatives (2):

In the formula, CuPc represents copper phthalocyanine residue.

Manufacturing example 10

A pigment derivative (3) having the following structure was obtained in the same manner as in Production Example 8, using diphenyldiketopyrrolopyrrole as the pigment component and N-aminopropylmorpholine as the amine component.

Pigment derivatives (3):

Manufacturing example 11

Using dioxazine violet (Pigment Violet 23) as a pigment component and a compound represented by the following formula (11) as an amine component, a pigment derivative (4) having the following structure was prepared in the same manner as in Production Example 8.

Manufacturing example 12

42 parts of cyanuric chloride forming an amine component, 28 parts of N,N-dimethylaminopropylamine and 50 parts of diaminodianthraquinone (pigment red 177) as a pigment component were reacted to obtain 108 parts of the following structure pigment derivatives (5).

Pigment Derivatives (5):

Manufacturing Example 13

Make 50 parts of disazo components with amine components shown in the following formula (12) and 30 parts of 5-acetylacetamido benzimidazolone as coupling components to carry out diazo coupling reaction to obtain 79 parts of the following formula structure pigment derivatives (6).

Pigment derivatives (6):

In the same manner as in Examples 8 to 13, by reacting a pigment component, anthraquinone or triazine with an amine component, or by coupling a compound containing an amine component to synthesize a pigment, various compounds used in the present invention can be prepared. Pigment derivatives.

Examples 1-10, Comparative Examples 1-6

Preparation and Evaluation of Pigment Photoresist (Photosensitive Coloring Composition)

Dispersion (1) and dispersion (2) having the compositions shown in Table 1 were prepared using zirconia beads with a star ball mill. For the examples (Examples 1-7, Example 10, Comparative Examples 1-4, Comparative Example 6) using dispersion (1) and dispersion (2), in the mixture after mixing the two dispersions, for only Using other examples (embodiments 8-9, comparative example 5) of the dispersion (1), in the dispersion (1), mix the mixed solvent (cyclohexanone/propylene glycol monoethyl ether acetate) in the ratio shown in table (1) (weight ratio 6/4)), copolymer, polyfunctional monomer (dipentaerythritol hexaacrylate), photopolymerization initiator (2-methyl-1-[(4-methylthio)phenyl]-2 -morpholinopropan-1-one) and a sensitizer (4,4'-di(diethylamino)benzophenone), and then filtered through a 1 μm sieve to obtain a pigment photoresist.

The viscosity of the prepared pigment photoresist was measured with an EL type viscometer (temperature 25° C.). In order to investigate the occurrence of aggregates, the prepared pigment photoresist was circulated in a Teflon tube for 72 hours, then spin-coated on a 100×100mm glass substrate, and after drying, it was exposed, developed, and post-baked. color filter. The number of agglomerates on the color filter was counted. The results are shown in Table 1.

Table 1 Photoresist Composition (%) Dispersion (1) Dispersion (2) pigment Pigment derivatives Copolymer mixed solvent pigment Pigment derivatives Copolymer mixed solvent Example 1 3.80 Pigment Red 254 0.40 Pigment Derivatives (3) 9.50 Copolymer (1) 21.80 0.20 Pigment Yellow 139 0.01 Pigment Derivatives (6) 0.77 Copolymer (4) 1.30 Comparative example 1 3.80 Pigment Red 254 0.40 Pigment Derivatives (3) 9.50 Copolymer (6) 21.80 0.20 Pigment Yellow 139 0.01 Pigment Derivatives (6) 0.77 Copolymer (6) 1.30 Example 2 4.20 Pigment Red 254 9.50 Copolymer (1) 21.80 0.20 Pigment Yellow 139 0.01 Pigment Derivatives (6) 0.77 Copolymer (4) 1.30 Example 3 4.20 Pigment Red 254 9.50 Copolymer (1) 21.80 0.21 Pigment Yellow 139 0.77 Copolymer (4) 1.30 Example 4 3.80 Pigment Red 177 0.40 Pigment Derivatives (5) 9.50 Copolymer (4) 21.80 0.20 Pigment Yellow 139 0.01 Pigment Derivatives (6) 0.77 Copolymer (4) 1.30 Comparative example 2 3.80 Pigment Red 177 0.40 Pigment Derivatives (5) 9.50 Copolymer (6) 21.80 0.20 Pigment Yellow 139 0.01 Pigment Derivatives (6) 0.77 Copolymer (6) 1.30 Example 5 3.80 pigment red 48:3 0.40 Pigment Derivatives (6) 9.50 Copolymer (4) 21.80 0.20 Pigment Yellow 139 0.01 Pigment Derivatives (6) 0.77 Copolymer (4) 1.30 Comparative example 3 3.80 pigment red 48:3 0.40 Pigment Derivatives (6) 9.50 Copolymer (7) 21.80 0.20 Pigment Yellow 139 0.01 Pigment Derivatives (6) 0.77 Copolymer (6) 1.30 Example 6 3.58 Pigment Green 36 0.2 Pigment derivatives (2) 8.39 Copolymers (1) 13.03 1.54 Pigment Yellow 150 0.08 Pigment derivatives (6) 5.39 Copolymer (5) 9.19 Example 7 3.58 Pigment Green 36 0.2 Pigment derivatives (2) 8.39 Copolymers (2) 13.03 1.54 Pigment Yellow 150 0.08 Pigment derivatives (6) 5.39 Copolymer (5) 9.19 Comparative example 4 3.58 Pigment Green 36 0.2 Pigment derivatives (2) 8.39 Copolymer (7) 13.03 1.54 Pigment Yellow 150 0.08 Pigment derivatives (6) 5.39 Copolymer (7) 9.19 Example 8 4.36 pigment blue 15:6 0.51 Pigment Derivatives (1) 16.22 Copolymers (1) 17.82 Comparative Example 5 4.36 pigment blue 15:6 0.51 Pigment Derivatives (1) 16.22 Copolymers (6) 17.82 Example 9 4.87 pigment blue 15:6 16.22 Copolymers (1) 17.82 Example 10 4.14 Pigment blue 15:6 0.48 Pigment Derivatives (1) 15.41 Copolymers (1) 16.93 0.22 Pigment Violet 23 0.03 Pigment Derivatives (4) 0.81 Copolymer (3) 0.89 Comparative Example 6 4.14 Pigment blue 15:6 0.48 Pigment Derivatives (1) 15.41 Copolymers (6) 16.93 0.22 Pigment Violet 23 0.03 Pigment Derivatives (4) 0.81 Copolymer (7) 0.89

Table 1 (continued) Photoresist Composition (%) Viscosity (mPas) Photoresist condensation (piece) Copolymer multifunctional monomer Photoinitiator Sensitizer mixed solvent Example 1 8.32 Copolymers (1) 5.40 1.80 0.80 45.9 7.2 0 Comparative example 1 8.32 Copolymers (6) 5.40 1.80 0.80 45.9 17.6 221 Example 2 8.32 Copolymers (1) 5.40 1.80 0.80 45.9 9.8 34 Example 3 8.32 Copolymers (1) 5.40 1.80 0.80 45.9 11.0 41 Example 4 8.32 Copolymers (1) 5.40 1.80 0.80 45.9 6.7 1 Comparative example 2 8.32 Copolymers (6) 5.40 1.80 0.80 45.9 12.4 126 Example 5 8.32 Copolymers (1) 5.40 1.80 0.80 45.9 8.1 0 Comparative example 3 8.32 Copolymers (6) 5.40 1.80 0.80 45.9 19.1 324 Example 6 3.50 Copolymer (1) 5.00 1.70 0.70 47.7 6.5 1 Example 7 3.50 Copolymer (1) 5.00 1.70 0.70 47.7 7.3 1 Comparative example 4 3.50 Copolymer (6) 5.00 1.70 0.70 47.7 12.2 154 Example 8 1.80 Copolymer (1) 5.30 1.49 1.10 51.4 6.2 2 Comparative Example 5 1.80 Copolymer (6) 5.30 1.49 1.10 51.4 13.4 166 Example 9 1.80 Copolymer (1) 5.30 1.49 1.10 51.4 10.1 32 Example 10 1.80 Copolymer (1) 5.30 1.49 1.10 51.4 8.1 0 Comparative example 6 1.80 Copolymer (6) 5.30 1.49 1.10 51.4 11.1 139

As can be seen from the results shown in Table 1, the photosensitive coloring composition of the present invention rarely generates aggregates in piping and the like, and exhibits excellent dispersion stability of the pigment.

As described above, the present invention provides a photosensitive coloring composition having excellent dispersion stability of a pigment and excellent fluidity. Use of this photosensitive coloring composition provides a color resist in which insoluble aggregates are remarkably reduced in piping such as Teflon or polypropylene, inside an air pump, a spray nozzle, or the front end of a slot die. Using this color resist can provide a color filter with very few undesirable foreign substances.

Claims (9)

1. photosensitive coloring composition that contains resin, monomer and colorant, it is characterized in that above-mentioned resin is that at least a of the compound (a) shown in the following general formula (I) contains at least a copolymer resins of the compound (b) of ethene unsaturated double-bond with another

Wherein, R ₁Be H or CH ₃, R ₂For carbon number is 2 or 3 alkylidene, R ₃The carbon number that maybe can contain phenyl ring for hydrogen is 1～20 alkyl, and n is 1～15 integer.

2. according to the photosensitive coloring composition of claim 1 record, it is characterized in that at least a compound of described compound (b) for from the group of (methyl) acrylic acid and (methyl) acrylate composition, choosing.

3. according to the photosensitive coloring composition of claim 2 record, it is characterized in that described resin is the copolymer resins of described compound (a) and (methyl) acrylic acid and (methyl) acrylate.

4. according to the photosensitive coloring composition of claim 3 record, it is characterized in that described resin is the copolymer resins of (methyl) acrylate of (methyl) acrylic acid of compound (a), 10～55 weight % of 10～35 weight % and 10～80 weight %.

5. according to the photosensitive coloring composition of claim 1 record, it is characterized in that described compound (a) is to the oxirane of cumylphenol or epoxy pronane modification (methyl) acrylate.

6. according to the photosensitive coloring composition of claim 1 record, it is characterized in that described compound (b) is for containing (methyl) acrylate of phosphate.

7. according to the photosensitive coloring composition of claim 1 record, it is characterized in that described resin contains the two keys of ethene on side chain.

8. according to the photosensitive coloring composition of claim 1 record, it is characterized in that it also contains from the pigment derivative that contains basic group, contains the anthraquinone derivative of basic group or contain choose among the pyrrolotriazine derivatives of basic group at least a.

9. color filter, the bepainting material layer that it comprises transparency carrier and uses photosensitive coloring composition of claim 1 record to form on this transparency carrier.