KR20110039033A - A colored photosensitive resin composition, color filter and liquid crystal display device having the same - Google Patents

Abstract

PURPOSE: A colored photosensitive resin composition, a color filter, and a liquid crystal display device including the same are provided to improve the tact time of a vacuum drying operation and uniformly forming a coating layer. CONSTITUTION: A colored photosensitive resin composition includes a coloring material, a binder resin, a photo-polymerizable compound, a photo-polymerization initiator, and a solvent. The solvent includes a solvent with the 40 to 70 of evaporation speed, and a solvent with the 10 to 40 of evaporation speed, and a solvent with the 0.01 to 10 of evaporation speed, based on the evaporation speed of n-butyl acetate.

Description

Colored photosensitive resin composition, color filter, and liquid crystal display device having the same {A COLORED PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER AND LIQUID CRYSTAL DISPLAY DEVICE HAVING THE SAME}

The present invention relates to a colored photosensitive resin composition, a color filter, and a liquid crystal display device having the same.

The color filter used for a color liquid crystal display device, an image pick-up element, etc. normally uses the coloring photosensitive resin composition which contains as a coloring agent the pigment corresponding to each color of red, green, and blue on the drive board | substrate with which the thin-film transistor (TFT) was arrange | positioned. After applying uniformly, a series of processes of exposing and developing the coating film formed by heat drying (hereinafter also referred to as 'pre-firing') and heat curing (hereinafter also referred to as 'post-firing') as necessary. It is produced by repeating the operation for each color to form the pixel for each color.

In the above process, the method of uniformly applying the colored photosensitive resin composition is generally known by the spin method, the slit-en spin method and the slit method depending on the substrate size and the application. Among them, the slit method is suitable for large substrates by discharging the coating liquid while the slit nozzle is moved, and has the advantage of reducing the coating liquid.

After applying the colored photosensitive resin composition, a vacuum drying (Vacumm dry, hereinafter referred to as 'VD') process of removing the solvent is performed. At this time, in the line using a large-sized substrate, the vacuum capacity is increased in the VD process immediately after the coating process as compared to the general line to shorten the VD tact time, which is a solvent removal time, to increase productivity.

However, in the colored photosensitive resin composition used in the art, rapid drying occurs at high vacuum under reduced pressure, and at this time, fine bubbles contained in the colored photosensitive resin composition are simultaneously ejected to form crater stains (hereinafter referred to as 'VD stains'). There is a problem of lowering the production yield by generating a surface defect.

In particular, in the process of a COA (Color Filter on Array) structure, a colored layer including a pixel and / or a black matrix of a color liquid crystal display device is formed on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device. Due to stains, it is difficult to regenerate expensive TFTs when defects occur in subsequent processes.

SUMMARY OF THE INVENTION An object of the present invention is that even when a high vacuum pressure is reduced in a line using a large-sized substrate, crater staining does not occur to form a uniform coating film, and in particular, to provide a colored photosensitive resin composition having excellent VD tact time. have.

Another object of the present invention is to provide a color filter of good quality without crater staining.

Still another object of the present invention is to provide a liquid crystal display device having the color filter.

The present invention for achieving the above object comprises a coloring material (A), a binder resin (B) photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E), wherein the solvent (E) Is a solvent (E-1) having an evaporation rate of 0.01 or more and less than 10, a solvent (E-2) having an evaporation rate of 10 or more and less than 40 and a solvent having an evaporation rate of 40 or more and 70 or less based on 100 evaporation rates of n-butyl acetate. It provides the coloring photosensitive resin composition characterized by including (E-3).

3-40 mass% of solvents (E-1), 30-90 mass% of solvents (E-2), and 3-40 of solvents (E-3) by mass fraction with respect to the solvent total amount in the said colored photosensitive resin composition. It is preferable that mass% is included.

The solvent (E-1) may include at least one selected from propylene glycol diacetate and ethylene glycol mono n-butyl ether acetate.

The colored photosensitive resin composition is used to form a colored layer on a driving substrate of a thin film transistor (TFT) method, and the coloring material (A) is 3 to 40 mass% in mass fraction with respect to the solid content in the colored photosensitive resin composition. May be included.

The driving substrate may be a large substrate having a size of 1870 mm × 200 mm or more.

In order to achieve the other object of the present invention, the present invention provides a color filter comprising a colored layer formed by applying the colored photosensitive resin composition according to the present invention on a substrate and exposed and developed in a predetermined pattern. .

The substrate may be a driving substrate on which a thin film transistor (TFT) is disposed.

In order to achieve another object of the present invention, the present invention provides a liquid crystal display device comprising the color filter.

According to the present invention, even after applying the colored photosensitive resin composition in a line using a large substrate, a uniform coating film can be formed without causing crater staining even when high vacuum is decompressed, and the coloring photosensitive property with excellent VD tact time is excellent. It provides a resin composition. Therefore, when the colored photosensitive resin composition is used, it is possible to provide a high quality color filter and a liquid crystal display device.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The coloring photosensitive resin composition which concerns on this invention contains a coloring material (A), binder resin (B) photopolymerizable compound (C), a photoinitiator (D), and a solvent (E). The said colored photosensitive resin composition may further contain the additive (F) as needed.

Hereinafter, each component contained in the coloring photosensitive resin composition of this invention is demonstrated in detail.

Coloring material (A)

As said coloring material (A), the organic pigment or inorganic pigment generally used in the art can be used. If necessary, a dye may be used as the coloring material (A), which is also included in the present invention.

Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts. Specifically, oxides or composite metals of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony Oxides; and the like.

Specific examples of the organic pigment and inorganic pigment include compounds classified as pigments in the Color Index (published by The society of Dyers and Colorists), and more specifically, pigments having the following color index (CI) numbers. Although these are mentioned, It is not necessarily limited to these.

C.I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185

C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38

C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64, and 76

C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58

C.I Pigment Brown 28

C.I pigment black 1 and 7, etc.

The said coloring material (A) can be used individually or in combination of 2 types or more, respectively.

Content of a coloring material (A) is 3-60 mass% with respect to solid content in colored photosensitive resin composition, Preferably it is the range of 5-55 mass%. In particular, when the colored photosensitive resin composition according to the present invention is used to form a colored layer on a thin film transistor (TFT) type driving substrate, the coloring material (A) may be used as a mass fraction with respect to the solid content in the colored photosensitive resin composition. It is preferable that it is 3-40 mass%. If the content of the coloring material (A) is in the range of 3 to 60 mass% based on the above criteria, even if a thin film is formed, the color density of the pixel is sufficient, and residues are generated because the omission of the non-pixel portion does not decrease during development. It is preferable because it is difficult.

Binder Resin (B)

The binder resin (B) usually has reactivity and alkali solubility due to the action of light or heat and acts as a dispersion medium of the coloring material.

The binder resin (B) contained in the colored photosensitive resin composition of the present invention may be used as long as it is a binder resin that acts as a binder resin for the coloring material (A) and is soluble in an alkaline developer used in the developing step for producing a color filter. Can be.

The binder resin (B) according to the present invention contains an unsaturated group obtained by reacting (B3) with a copolymer obtained by a copolymerization reaction of a compound containing the following (B1) and (B2), followed by further reaction (B4). Resin.

(B1): a compound having an unsaturated bond and an epoxy group in one molecule;

(B2): a compound having an unsaturated bond copolymerizable with (B1);

(B3): a compound represented by the following formula (1);

<Formula 1>

(Wherein R 1 and R 2 are each independently substituted with a halogen element or a C 1 to C 6 alkyl group including a ketone group, an ester group, a thiol group or an unsubstituted C 1 to C 6 alkyl group, A is a halogen group, a methoxy group, Ethoxy group substituted or unsubstituted aliphatic polycyclic group, allyl group, phenyl group, benzyl group, halogen element or C1 to C8 ethoxy group, n and m are 0 or 1.

(B4): polybasic acid anhydride.

That is, the binder resin (B) contained in the coloring photosensitive resin composition of this invention is an unsaturated group containing resin characterized by imposing the compound of the said General formula (1) on an epoxy group of a principal chain.

The binder resin (B) may be polymerized together by adding other monomers in addition to the compounds of (B1) to (B4). That is, the binder resin (B) according to the present invention is included in the present invention even when monomers other than the above (B1) to (B4) are further included and polymerized.

As used herein, (meth) acrylate means acrylate and / or methacrylate.

In one embodiment of the present invention, the compound (B1) having an unsaturated bond and an epoxy group in one molecule may be used without limitation as long as it is a compound having an unsaturated bond and an epoxy group at the same time. Specific examples of the (B1) include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, methylglycidyl (meth ) Acrylates and the like. Of these, glycidyl (meth) acrylate can be preferably used as (B1). The above-mentioned (B1) can be used individually or in combination of 2 or more types, respectively.

In one embodiment of the present invention, as the compound (B2) having an unsaturated bond copolymerizable with the above (B1), any compound having an unsaturated double bond capable of polymerization can be used without limitation. Specific examples of the above (B2) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, aminoethyl (meth) acrylate, and the like. Unsubstituted or substituted alkyl ester compound of unsaturated carboxylic acid, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth ) Acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mendidienyl (Meth) acrylate, isobornyl (meth) acrylate, finanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, pineneyl (meth) acrylate Monounsaturated carboxylic ester compound of glycols, such as unsaturated carboxylic ester compound containing alicyclic substituents, such as oligoethylene glycol monoalkyl (meth) acrylate, benzyl (meth) acrylate, and phenoxy (meth) Unsaturated carboxylic ester compounds containing substituents having aromatic rings such as acrylates, aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, vinyl carboxylates such as vinyl acetate and vinyl propionate, and (meth Vinyl cyanide compounds such as acrylonitrile and α-chloroacrylonitrile, maleimide compounds such as N-cyclohexyl maleimide and N-phenylmaleimide. (B2) illustrated above can be used individually or in combination of 2 or more types, respectively.

In one embodiment of the present invention, the compound (B3) represented by the following formula (1) added to the copolymer of (B1) and (B2) is not particularly limited, but is preferably represented by the following formulas (2) to (6). Compounds can be exemplified.

<Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

<Formula 6>

According to the present invention, in the process of reacting (B3) with the copolymer of (B1) and (B2), unsaturated carboxylic acid can be reacted together as necessary.

Specific examples of the unsaturated carboxylic acid include acrylic acid and methacrylic acid. In addition to these acrylic acid and methacrylic acid, one or more other acids may be used. As another acid, it is also possible to specifically use together the carboxylic acid chosen from 1 type or more of other unsaturated carboxylic acids, such as crotonic acid, itaconic acid, maleic acid, and fumaric acid. Moreover, you may use together the monomer containing a hydroxyl group and a carboxyl group in the same molecule, such as (alpha)-(hydroxymethyl) acrylic acid. The said unsaturated carboxylic acid can be used individually or in combination of 2 types or more, respectively.

In one embodiment of the present invention, the polybasic acid anhydride (B4) is not particularly limited as long as it is generally used in the art. Specific examples of the above (B4) include coharic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, Pyromellitic anhydride, and the like. In the above, tetrahydrophthalic anhydride and coharic anhydride can be preferably used. (B4) illustrated above can be used individually or in combination of 2 types or more, respectively.

As described above, the binder resin (B) according to the present invention is a copolymer obtained by copolymerizing the above-mentioned (B1) and (B2) (which is included in the present invention even when monomers other than B1 and B2 are further included and copolymerized). In the case of an unsaturated group-containing resin obtained by reacting (B3) and then further reacting (B4), the copolymer obtained by copolymerizing the above (B1) and (B2) is derived from each of the above (B1) and (B2). It is preferable that the ratio of a structural unit exists in the following ranges by mole fraction with respect to the total number of moles of the structural unit which comprises said copolymer.

The ratio of the structural unit derived from each of said (B1) and (B2) is 2 to 80 mol% derived from said (B1) with respect to the total number of moles of the said copolymer structural unit, and is derived from said (B2) It is 2 to 90 mol% of structural units, More preferably, it is 5 to 80 mol% of structural units derived from said (B1), and 5 to 90 mol% of structural units derived from said (B2).

(B3) is preferably 2 to 100 mol% based on the epoxy equivalent of (B1), and (B4) is preferably reacted at 2 to 100 mol% based on the hydroxyl group equivalent produced through the reaction of (B3) and (B1). In particular, the (B3) is 5 to 100 mol% based on the epoxy equivalent of (B1), the (B4) is reacted at 5 to 100 mol% relative to the equivalent of the hydroxyl group generated through the reaction (B3) and (B1) desirable.

If said composition ratio is in the said range, since the balance of developability, solubility, and heat resistance is favorable, a preferable binder resin (B) can be obtained.

An example of the manufacturing method in the case where the said binder resin (B) is unsaturated group containing resin obtained by making (B4) react with (B3) further after making (B3) react with the copolymer obtained by copolymerizing (B1) and (B2) is Same as

To a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a nitrogen introduction tube, 0.5 to 20 times the amount of solvent was introduced on a mass basis with respect to the total amount of (B1) and (B2), and the atmosphere in the flask was changed from air to nitrogen. Replace. Then, after heating up a solvent at 40-140 degreeC, 0-20 times of a solvent and a polymerization initiator are mentioned on a mass basis with respect to the predetermined amount of (B1) and (B2), and the total amount of (B1) and (B2). To the total moles of (B1) and (B2), 0.1-10 mol% of the solution (stirred and dissolved under room temperature or heating) was added dropwise to the flask over 0.1 to 8 hours from the dropping lot, and then at 40 to 140 ° C. The mixture is stirred for further 1 to 10 hours to obtain a copolymer.

Here, in the said process, one part or whole quantity of a polymerization initiator may be put in a flask, and a part or whole quantity of (B1) and (B2) may be put in a flask. Moreover, in order to control molecular weight and molecular weight distribution, (alpha) -methylstyrene dimer and a mercapto compound can also be used as a chain transfer agent. The usage-amount of (alpha) -methylstyrene dimer and a mercapto compound is 0.005 to 5% by mass with respect to the total amount of said (B1) and (B2). In addition, the said polymerization conditions can also adjust suitably an input method and reaction temperature in consideration of a calorific value, such as a manufacturing facility and superposition | polymerization.

In addition, the solvent used in the said process can use the solvent used at the time of a normal radical polymerization reaction. Specifically, the solvent is tetrahydrofuran, dioxane, ethylene glycol dimethylethyl, diethylene glycol dimethylethyl, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ethyl acetate , 3-methoxybutyl acetate, methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, toluene, xylene, ethylbenzene, chloroform, dimethyl sulfoxide and the like. These solvents can be used individually or in combination of 2 or more types.

Moreover, as a polymerization initiator used for said process, the polymerization initiator normally used can be added, It does not restrict | limit in particular. Specifically, diisopropyl benzene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxy isopropyl carbonate, t-amyl peroxy-2-ethylhexanoate, t-butyl Organic peroxides such as peroxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylbareronitoryl), dimethyl-2,2'-azobis (2-methylpropionate) Nitrogen compounds, such as these, are mentioned. These can be used individually or in combination of 2 or more types.

By doing in this way, the copolymer of the said (B1) and (B2) compound can be obtained.

Subsequently, after making (B3) react with the copolymer obtained by the above, a suitable amount of (B4) component is added as it is, about 50-150 degreeC, Preferably it heats at 80-130 degreeC and makes it react. There is no need to add a catalyst in particular.

Thereby, binder resin (B) which is a copolymer containing the unsaturated group obtained by making said (B3) and (B4) react with the copolymer obtained by copolymerizing the said (B1) and (B2) one by one sequentially can be obtained.

It is preferable that the weight average molecular weight of polystyrene conversion of the said binder resin (B) exists in the range of 3,000-100,000, and it is more preferable that it exists in the range of 5,000-50,000. When the weight average molecular weight of binder resin (B) exists in the range of 3,000-100,000, film | membrane decrease hardly arises at the time of image development, and since the missing property of a non-pixel part at the time of image development is preferable, it is preferable.

It is preferable that it is 1.5-6.0, and, as for the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the said binder resin (B), it is more preferable that it is 1.8-4.0. When the said molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is 1.5-6.0, since developability is excellent, it is preferable.

The binder resin (B) has an acid value in the range of 30 to 150 (mgKOH / g). If the acid value is less than 30mgKOH / g, there is a concern that the developability of the developer is low and residues remain on the substrate. If the acid value is more than 150mgKOH / g, there is a problem that the desorption of the pattern increases. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can usually be obtained by titration using an aqueous potassium hydroxide solution.

Content of the said binder resin (B) is 5-90 mass% normally with a mass fraction with respect to the total solid in colored photosensitive resin composition, Preferably it is the range of 10-70 mass%. When the content of the binder resin (B) is within the range of 5 to 90% by mass based on the above criteria, the solubility in the developing solution is sufficient, and development residues are less likely to occur on the substrate of the non-pixel portion. It is preferable because the film reduction hardly occurs and the omission of the non-pixel portion is good.

Photopolymerizable Compound (C)

The said photopolymerizable compound (C) is a compound which can superpose | polymerize by the action | action of light and the photoinitiator mentioned later, A monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrroly Money, etc.

Specific examples of the bifunctional monomers include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate etc. are mentioned.

Of these, bifunctional or higher polyfunctional monomers are preferably used.

The photopolymerizable compound (C) is usually used in the range of 5 to 50% by mass, preferably 7 to 45% by mass, based on the mass fraction with respect to the solid content in the colored photosensitive resin composition. Since the intensity | strength and smoothness of a pixel part become it favorable that the said photopolymerizable compound (C) is 5-50 mass% on the said reference | standard, it is preferable.

Photopolymerization Initiator (D)

Although the said photoinitiator (D) is not restrict | limited, 1 or more types of compounds chosen from the group which consists of a triazine type compound, an acetophenone type compound, a biimidazole type compound, and an oxime compound can be used. The coloring photosensitive resin composition containing said photoinitiator (D) is highly sensitive, and the film | membrane formed using this composition becomes favorable the intensity | strength and surface smoothness of the pixel part.

As said triazine type compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl)-, for example. 6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2 -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-tri Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

As said acetophenone type compound, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2 -Hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane And oligomers of -1-ones. Moreover, as said acetophenone type compound, the compound represented by following formula (7) is mentioned, for example.

<Formula 7>

In Formula 7, R1 to R4 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group unsubstituted or substituted by an alkyl group having 1 to 12 carbon atoms, a benzyl group unsubstituted or substituted by an alkyl group having 1 to 12 carbon atoms, or It is a naphthyl group which is substituted or unsubstituted by the C1-C12 alkyl group.

Specific examples of the compound represented by Formula 7 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethane-1 -One, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl-2 -Amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholino Phenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one , 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. may be mentioned. .

As said biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2,3-, for example) Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimi Dazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, and a phenyl group at the 4,4', 5,5 'position is carbo The imidazole compound substituted with the alkoxy group etc. are mentioned. Among them, 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole is preferably used.

As said oxime compound, the compound etc. which are represented by following formula (8)-10 are mentioned, for example.

<Formula 8>

<Formula 9>

<Formula 10>

Moreover, as long as it does not impair the effect of this invention, the other photoinitiator etc. which are normally used in this field can also be used together. As another photoinitiator, a benzoin compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound etc. are mentioned, for example. These can be used individually or in combination of 2 or more types, respectively.

As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As said benzophenone type compound, benzophenone, methyl 0- benzoyl benzoate, 4-phenylbenzo phenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3,3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. Can be mentioned.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be mentioned.

Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl, a titanocene compound, etc. are mentioned as another photoinitiator.

Moreover, as said photoinitiator (D), what has a group which can cause chain transfer can be used, As this photoinitiator, what is described in Unexamined-Japanese-Patent No. 2002-544205 is mentioned, for example.

You may use combining the photoinitiator (D-1) with the said photoinitiator (D). When the photopolymerization initiator (D-1) is used in combination with the photopolymerization initiator (D), the colored photosensitive resin composition containing these is more sensitive, and thus the productivity at the time of forming a color filter using the composition is preferable. Do.

As said photopolymerization start adjuvant (D-1), an amine compound and a carboxylic acid compound are used preferably.

Specific examples of the amine compound in the photopolymerization initiation assistant (D-1) include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamino Isoamyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoic acid, 2-dimethylaminoethyl benzoic acid, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone), Aromatic amine compounds, such as 4,4'-bis (diethylamino) benzophenone, are mentioned. Among them, as the amine compound, an aromatic amine compound is preferably used.

Specific examples of the carboxylic acid compound in the photopolymerization initiation assistant (D-1) include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid and dimethoxyphenyl And aromatic heteroacetic acids such as thioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

The usage-amount of the said photoinitiator (D) is 0.1-40 mass% in mass fraction with respect to the total amount of binder resin (B) and a photopolymerizable compound (C) based on solid content, Preferably it is 1-30 mass%. In addition, the usage-amount of the said photoinitiator auxiliary agent (C-1) is 0.1-50 mass% on the said reference | standard, Preferably it is 1-40 mass%. When the usage-amount of the said photoinitiator (D) exists in the said range on the said reference | standard, since the coloring photosensitive resin composition becomes high sensitivity and the intensity | strength of the pixel part formed using this composition and the smoothness in the surface of this pixel part become favorable, it is preferable. Do. Moreover, since the sensitivity of a coloring photosensitive resin composition becomes higher and the productivity of the color filter formed using this composition improves, when the usage-amount of a photoinitiator auxiliary (D-1) exists in said range on the said reference | standard.

Solvent (E)

The solvent (E) is a solvent (E-1) having an evaporation rate of 0.01 or more and less than 10, a solvent (E-2) having an evaporation rate of 10 or more and less than 40, based on the evaporation rate of n-butyl acetate as 100. It comprises the solvent (E-3) which is 40 or more and 70 or less.

The relative evaporation rate of the other solvent (E) when the evaporation rate of n-butyl acetate is assumed to be 100 can be calculated as follows.

First, evaporate a predetermined amount of n-butyl acetate in 25 degreeC and 760 mmHg conditions, and measure the time (T-1) required until it fully evaporates. Subsequently, the time (T-2) until the same amount of solvent (E) is evaporated under the same conditions and completely evaporated is measured. By dividing the T-2 value by the T-1 value and multiplying by 100, it is possible to know the relative evaporation rate of the solvent (E) when the evaporation rate of n-butyl acetate is 100.

In the present invention, the evaporation rate of the solvent (E) means the evaporation rate of the sole solvent when the solvent (E) is used alone, the mixed solvent when the solvent (E) is used by mixing two or more kinds Means the evaporation rate.

Specific examples of the solvent (E-1) include ethyl-3-ethoxypropionate (evaporation rate 10), propyleneglycol diacetate (evaporation rate 4), propyleneglycolcomonophenyl ether (evaporation rate 0.2), propylene glycol Rylcolmono n-butyl ether (evaporation rate 9.3), ethyleneglycolmono n-butylether (evaporation rate 7.9), ethyleneglycolmono n-butylether acetate (evaporation rate 7), tripropyleneglycolmono n-propylether (Evaporation rate 0.085), tripropylene glycol alcohol monomethyl ether (evaporation rate 0.26), dipropylene glycol alcohol mono n-butyl ether (evaporation rate 0.6), dipropylene glycol alcohol mono-propyl ether (evaporation rate 1.4),

Dipropyleneglycol monomethyl ether (evaporation rate 3.5),

Dipropyleneglycol monomethyl ether acetate (evaporation rate 1.5) and the like. Among them, propyleneglycol diacetate (evaporation rate 4) and ethyleneglycol monon-butyl ether acetate (evaporation rate 7) can be particularly preferably used for compatibility and processability. These solvents (E-1) can be used individually or in combination of 2 types or more, respectively.

Specific examples of the solvent (E-2) include propylene glycol monomethyl ether acetate (evaporation rate 33), propylene glycol monoethyl ether acetate (evaporation rate 19), ethyl-3-ethoxypropionate (evaporation rate 10). ), Propylene glycol mono n-propyl ether (evaporation rate 21), 3-methoxybutyl acetate (evaporation rate 34), methyl-3-methoxy propionate (evaporation rate 32), ethylene glycol monoethyl ether acetate (evaporation) Speed 21), ethylene glycol monomethyl ether acetate (evaporation rate 31), ethylene glycol monopropyl ether (evaporation rate 20), and the like. Among these, in particular, propylene glycol monomethyl ether acetate (evaporation rate 33) is excellent in compatibility and processability, and thus it can be preferably used. These solvents (E-2) can be used individually or in combination of 2 types or more, respectively.

Specific examples of the solvent (E-3) include n-butyl propionate (evaporation rate 45),

Propylene glycol monoethyl ether (evaporation rate 46), propylene glycol monomethyl ether (evaporation rate 62), ethylene glycol monoethyl ether (evaporation rate 66), and the like. Among these, in particular, propylene glycol monomethyl ether (evaporation rate 62) is excellent in re-dissolution property and can be preferably used. These solvents (E-3) can be used individually or in combination of 2 types or more, respectively.

In addition, the said solvent (E) can be used without a restriction | limiting in particular if the evaporation rate exists in the said range among the various organic solvents used in the field of colored photosensitive resin composition.

Content of the said solvent (E-1), (E-2), and (E-3) is a solvent (E-1) and solvent (E-3) 3-in mass fraction with respect to the solvent total amount in a coloring photosensitive resin composition. It is preferable to be contained in 40 mass% and 30-90 mass% of solvents (E-2). In particular, the content of the solvent (E-1), (E-2) and the solvent (E-3) is the solvent (E-1) and the solvent (E-3) in a mass fraction with respect to the total amount of the solvent in the colored photosensitive resin composition. It is more preferable to be contained in 5-40 mass% and 35-90 mass% of solvents (E-2). When content of the said solvent (E-1), (E-2), and (E-3) is included in the said range on the said reference | standard, When coloring colored photosensitive resin composition is applied to the line using a large sized board | substrate, colored photosensitive resin composition Even if high vacuum is applied immediately after coating, the crater staining does not occur, and thus a uniform coating film can be formed. In particular, the VD tact time is excellent, which is preferable.

Content of the said solvent (E) is 60-90 mass% in mass fraction with respect to the coloring photosensitive resin composition whole quantity containing it, Preferably it is 70-85 mass%. When the content of the solvent (E) is within the above range, the coating property is applied when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), or inkjet. It is preferable because it becomes good.

Additive (F)

In the coloring photosensitive resin composition of this invention, it is also possible to use additives (F), such as a filler, another high molecular compound, a pigment dispersing agent, an adhesion promoter, antioxidant, a ultraviolet absorber, and an aggregation inhibitor, as needed.

Specific examples of the filler include glass, silica, alumina, and the like.

Specific examples of the other polymer compound include curable resins such as epoxy resins and maleimide resins, polyvinyl alcohols, polyacrylic acids, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, and thermoplastic resins such as polyurethanes. Can be.

Commercially available surfactants may be used as the pigment dispersant, and specific examples thereof include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants. These can be used individually or in combination of 2 types or more, respectively.

Specific examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, and polyethyleneimines. And KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products, Inc.), and Mega Pack. (MEGAFAC) (manufactured by Dainippon Ink Chemical Co., Ltd.), Florard (manufactured by Sumitomo 3M Inc.), Asahi guard, Suflon (manufactured by Asahi Glass Co., Ltd.), Solsperth (SOLSPERSE) (made by Genka Corporation), EFKA (made by EFKA Chemicals Corporation), PB 821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.

Specifically, the adhesion promoter may include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimeth Oxysilane, etc. are mentioned.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone and the like.

Specific examples of the aggregation inhibitor include sodium polyacrylate.

The coloring photosensitive resin composition of this invention mentioned above can be manufactured, for example by the following methods. The coloring material (A) is previously mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the coloring material is about 0.2 µm or less. Under the present circumstances, a pigment dispersant is used as needed and one part or all part of binder resin (B) may be mix | blended. The remainder of binder resin (B), the photopolymerizable compound (C) photoinitiator (D), the additive (F) used as needed, and the additional solvent as needed in the obtained dispersion liquid (henceforth a mill base). Is further added to a predetermined concentration to obtain a desired colored photosensitive resin composition.

Hereinafter, the color filter according to the present invention will be described.

The color filter according to the present invention comprises a colored layer formed by applying the above-described colored photosensitive resin composition on a substrate and exposing and developing in a predetermined pattern.

In the above, the substrate is not limited, and for example, a layer including solids of glass, a silicon wafer, plastic, or a previously formed colored photosensitive resin composition may be used. Amorphous polyolefin, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, polynorbornene, polyether sulfone, polyether ketone, etc. are mentioned as a raw material of the said plastic used as a board | substrate.

Preferably, the substrate may be a driving substrate on which a thin film transistor (TFT) is disposed. At this time, the driving substrate is preferably a large substrate of size 1870mm × 200mm or more. The coloring photosensitive resin composition which concerns on this invention is apply | coated on the said board | substrate, and volatile components, such as a solvent, are removed through vacuum drying (VD) and predrying, and a smooth coating film is obtained. Although the thickness of a coating film is not necessarily limited, it is preferable that it is about 1-4 micrometers. In this case, the colored photosensitive resin composition according to the present invention does not generate crater stains even when high vacuum is applied when the line is applied to a line using a large-sized substrate as the substrate, thereby forming a uniform coating film, in particular, a VD tact time (Tact time ) Is excellent.

In order to obtain the desired pattern to the coating film obtained as mentioned above, ultraviolet-ray is irradiated to the specific area | region of a coating film through a mask. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that a parallel light beam may be irradiated uniformly to the whole exposure part, and a mask and a board | substrate will be correctly aligned.

Thereafter, the coating film after curing is brought into contact with an aqueous alkali solution, which is a developer, to dissolve and develop a non-exposed area, thereby making it possible to produce a desired pattern. After image development, it can carry out after about 10 to 60 minutes of drying at 150-230 degreeC as needed.

The developing solution used for the said image development is an aqueous solution containing an alkaline compound and surfactant normally.

The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, hydrogen carbonate Sodium, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like. Specific examples of the organic alkaline compounds include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine and the like. These inorganic and organic alkaline compounds can be used individually or in combination of 2 or more types, respectively.

The concentration of the alkaline compound in the alkaline developer is in the range of 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

The surfactant in the alkaline developer may be used either among nonionic surfactants, anionic surfactants or cationic surfactants.

Specific examples of the non-ionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

Specific examples of the anionic surfactants include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the cationic surfactant include amine salts and quaternary ammonium salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride.

These surfactant can be used individually or in combination of 2 or more types, respectively.

The concentration of the surfactant in the alkaline developer is usually 0.01 to 10% by mass, preferably 0.05 to 8% by mass, more preferably 0.1 to 5% by mass.

As described above, a pixel or a black matrix corresponding to the color of the coloring material in the photosensitive resin composition is obtained by applying the colored photosensitive resin solution, drying, patterning exposure to the resulting dried coating film, and developing. The color filter can be obtained by repeating the operation by the number of colors required for the color filter. Since the configuration and manufacturing method of the color filter are well known in the art, detailed description thereof will be omitted.

The color filter is usually a black matrix and three primary color pixels of red, green and blue arranged on a substrate, but by performing the above operation using the colored photosensitive resin composition of the present invention containing a coloring material corresponding to a certain color. The black matrix and the three primary color pixels are disposed on a substrate by obtaining the black matrix or the pixel of the color and performing the same operation using the colored photosensitive resin composition of the present invention containing the coloring material corresponding to the desired color for other colors. can do. Of course, the photosensitive resin composition of this invention can also be apply | coated only to one color, two colors, or three colors of a black matrix and three primary colors. In addition, although the black matrix which is a light shielding layer can also use the coloring (colored black) photosensitive resin of this invention, since it is formed by the chromium layer etc., for example, the coloring photosensitive resin composition of this invention for formation of a black matrix. There is no need to use.

The color filter manufactured using the coloring photosensitive resin composition of this invention has little in-plane film thickness difference, For example, it can make in-plane film thickness difference 0.15 micrometer or less and further 0.05 micrometer or less with the film thickness of 1-3 micrometers. . Therefore, the color filter obtained in this way is excellent in smoothness, and it can manufacture a liquid crystal display device of excellent quality by high yield by assembling this to a color liquid crystal display device.

Hereinafter, a liquid crystal display device according to the present invention will be described. The liquid crystal display device of the present invention includes a configuration known in the art, except that the above-described color filter is provided. That is, all of the liquid crystal display devices to which the color filter of the present invention can be applied are included in the present invention. For example, a transmissive liquid crystal display device in which a counter electrode substrate including a thin film transistor (TFT element), a pixel electrode, and an alignment layer is faced at predetermined intervals, and a liquid crystal material is injected into the gap to form a liquid crystal layer. Can be. There is also a reflective liquid crystal display device in which a reflective layer is provided between the substrate of the color filter and the colored layer.

As another example, a liquid crystal display device including a TFT (Thin Film Transistor) substrate joined on a transparent electrode of a color filter, and a backlight fixed at a position where the TFT substrate overlaps the color filter. The TFT substrate includes an outer frame made of a light-proof resin surrounding a peripheral surface of a color filter, a liquid crystal layer made of a nematic liquid crystal imposed in the outer frame, and a plurality of pixel electrodes provided for each region of the liquid crystal layer. , A transparent glass substrate on which the pixel electrode is formed, and a polarizing plate formed on the exposed surface of the transparent glass substrate.

The polarizing plate has a polarizing direction that traverses vertically and is made of an organic material such as polyvinyl alcohol. A plurality of pixel electrodes are connected with a plurality of thin film transistors each formed on a glass substrate of a TFT substrate. If a predetermined potential difference is applied to a specific pixel electrode, a predetermined voltage is applied between the specific pixel electrode and the transparent electrode. Therefore, the electric field formed according to the voltage changes the orientation of the region corresponding to the specific pixel electrode of the liquid crystal layer.

Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by an Example. In addition, "%" and "part" which show content in a following example and a comparative example are a mass reference | standard unless there is particular notice.

Synthesis Example 1 Synthesis of Binder Resin A-1

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, and the atmosphere in the flask was changed from nitrogen to air. 3.6 g of 2,2'-azobis (isobutyronitrile) was added to a mixture containing 82.5 g (0.6 mol) of rate, 35.40 g (0.4 mol) of p-vinyltoluene and 136 g of propylene glycol monomethyl ether acetate. Was added dropwise to the flask over 2 hours from the dropping lot, and further stirring was continued at 80 ° C for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, 88.8 g of a compound represented by the formula (4) [0.6 mol (100 mol% based on the epoxy group of glycidyl methacrylate used in the present reaction)], and a reaction catalyst trisdimethylaminomethylphenol 0.9 g and 0.145 g of hydroquinone, a polymerization inhibitor, were added to the flask and the reaction was continued at 110 ° C. for 4 hours, followed by 45.6 g of THPA (tetrahydrophthalic anhydride) [0.3 mol (100 based on the hydroxy group generated in the previous reaction). Mol%)] was added, and the reaction was continued for 2 hours at 110 ° C. to obtain a resin A-1 having a solid acid value of 100 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 17,000, and molecular weight distribution (Mw / Mn) was 2.3.

At this time, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin was measured using a HLC-8120GPC (manufactured by Tosoh Corporation) apparatus, and the column was used by serially connecting TSK-GELG4000HXL and TSK-GELG2000HXL. The column temperature was 40 ° C, the mobile phase solvent was tetrahydrofuran, the flow rate was 1.0 ml / min, the injection amount was 50 µl, the detector RI was used, and the measurement sample concentration was 0.6 mass% (solvent = tetrahydrofuran), for calibration. TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation) was used as a standard material. The ratio of the weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution (Mw / Mn).

<Examples 1 to 6 and Comparative Examples 1 to 5>

In each component of the following Table 1, it mixes so that the total amount of the pigment which is a coloring material (D), and the pigment dispersant which is an additive (F) may be 20 mass% with respect to the mixture of a pigment, a pigment dispersant, and a propylene glycol monomethyl ether acetate. After the pigment was sufficiently dispersed using the bead mill, the bead mill was separated, and the solvent (E) was further added and mixed to obtain a colored photosensitive resin composition. In this case, the solvents shown in Tables 2 and 3 were used.

Coloring material (D) C.I. Pigment Green 36 5.51 parts C.I. Pigment Yellow 150 2.43 parts Binder Resin (A) Resin A-1 (solid content calculation) of Synthesis Example 1 6.59 parts Photopolymerizable Compound (B) Dipentaerythritol hexaacrylate
(KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 5.71 parts
Photopolymerization Initiator (C) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1one (Irgacure 369; manufactured by Ciba Specialty Chemical) 1.46 parts
4,4'-bis (diethylamino) benzophenone
(EAB-F; manufactured by Hodogaya Kagaku Co., Ltd.) 0.49 parts
Solvent (E) See Table 1 76.0 parts Additive (F) Pigment Dispersant (Polyester) 1.20 parts Epoxy resin (SUMI-EPOXY ESCN-195XL; manufactured by Sumitomo Kagaku Kogyo Co., Ltd.) 0.61 parts

Example One 2 3 4 5 6 E-1 Propylene Glycol Diacetate
(Evaporation rate 4) Ethylene glycol mono n-butyl ether acetate (evaporation rate 7) Propylene Glycol Diacetate
(Evaporation rate 4) Propylene Glycol Diacetate
(Evaporation rate 4) Ethylene glycol mono n-butyl ether acetate (evaporation rate 7) Ethylene glycol mono n-butyl ether acetate (evaporation rate 7) 10% by weight 10% by weight 10% by weight 20 wt% 20 wt% 10% by weight Propylene Glycol Diacetate
(Evaporation rate 4) 10% by weight E-2 Propylene glycol monomethyl ether acetate (evaporation rate 33) Propylene glycol monomethyl ether acetate (evaporation rate 33) Propylene glycol monomethyl ether acetate (evaporation rate 33) Propylene glycol monomethyl ether acetate (evaporation rate 33) Propylene glycol monomethyl ether acetate (evaporation rate 33) Propylene glycol monomethyl ether acetate (evaporation rate 33) 80 wt% 80 wt% 60% by weight 70 wt% 65% by weight 65% by weight Ethyl-3-ethoxypropionate (evaporation rate 10) Ethyl-3-ethoxypropionate (evaporation rate 10) Ethyl-3-ethoxypropionate (evaporation rate 10) Ethyl-3-ethoxypropionate (evaporation rate 10) 20 wt% 5 wt% 10% by weight 10% by weight E-3 Propylene Glycol Monomethyl Ether (Evaporation Rate 62) Propylene Glycol Monomethyl Ether (Evaporation Rate 62) Propylene glycol monomethyl ether (evaporation rate 62) Ethylene Glycol Monoethyl Ether (Evaporation Rate 66) Propylene Glycol Monoethyl Ether (Evaporation Rate 46) Propylene Glycol Monoethyl Ether (Evaporation Rate 46) 10% by weight 10% by weight 10% by weight 5 wt% 5 wt% 5 wt%

Comparative example One 2 3 4 5 E-1
Propylene Glycol Diacetate
(Evaporation rate 4) Propylene Glycol Diacetate
(Evaporation rate 4) 75 wt% 2 wt% E-2


Propylene glycol monomethyl ether acetate (evaporation rate 33) Propylene glycol monomethyl ether acetate (evaporation rate 33) Propylene glycol monomethyl ether acetate (evaporation rate 33) Propylene glycol monomethyl ether acetate (evaporation rate 33) Propylene glycol monomethyl ether acetate (evaporation rate 33) 100 wt% 80 wt% 80 wt% 25% by weight 98% by weight Ethyl-3-ethoxypropionate (evaporation rate 10) 20 wt% E-3
Propylene glycol monomethyl ether (evaporation rate 62) 20 wt%

Experimental Example

A glass substrate of 2 square inches (# 1737, manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. On the glass substrate, the colored photosensitive resin composition prepared in the above Examples and Comparative Examples is exposed at an exposure amount (365 nm) of 100 mJ / cm 2, and spin is performed so that the film thickness after post-firing is 3.0 μm when the developing step is omitted. The coating was then carried out under a reduced pressure vacuum process, followed by preliminary drying at 100 ° C for 3 minutes in a clean oven. After cooling, the gap between the substrate coated with the colored photosensitive resin composition and a quartz glass photomask (having a pattern for changing the transmittance stepwise in the range of 1 to 100% and a line / space pattern from 1 µm to 50 µm) Was made into 100 micrometers, and it irradiated with the exposure amount (365 nm) of 100 mJ / cm <2> in air | atmosphere using the ultrahigh pressure mercury lamp (brand name USH-250D) by Ushio Denki Corporation. Thereafter, the coating film was immersed at 26 ° C. for a predetermined time in an aqueous developer containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide, and then dried at 220 ° C. for 30 minutes after washing with water.

The vacuum decompression process was performed in the same manner as the following method for evaluating the splitting hole and VD tact time, and the results of the splitting hole staining and VD tact time are shown in Tables 4 and 5 below.

*One. Crater Stain Evaluation

The coated colored photosensitive resin composition was coated on a 500 mm x 500 mm glass substrate (# 1737, manufactured by Corning Corporation) by spin coating, and then the substrate was coded in a vacuum chamber, followed by a primary vacuum valve (sub valve). After depressurizing for 10 sec after opening, after opening the secondary vacuum valve (main valve), let the pressure gauge of the vacuum chamber depressurize to 65 Pa for a certain period of time, release the depressurization of the vacuum chamber and make an optical microscope (VF-7510, manufactured by KEYENCE). Observe the surface with).

(Circle): 5 micrometers or more of stains are not recognized on the coating film surface.

X: 100 or more stains of 5um or more are recognized on the surface of the coating film

*2. VD Tact time

During the VD decompression process, the Tact time evaluation is performed according to the time to wait a predetermined time so that the pressure gauge of the vacuum chamber is reduced to 65 Pa. The evaluation criteria are as follows. When X takes longer than 30 seconds, the same trend can be confirmed in actual line evaluation.

Good: It takes 30 seconds to reach 65Pa.

Poor: It takes more than 30 seconds to 65 Pa.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Crater Stains * 1 O O O O O O Tack time * 2 Good Good Good Good Good Good

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Crater Stains * 1 X X X X X Tack time * 2 Good Good Good Bad Good

As shown in Tables 4 and 5, in Examples 1 to 6 using three mixed solvents having different evaporation rates as solvents, there was no crater staining compared to the comparative examples, and the VD tack time was It can be confirmed that it is excellent.

Claims (8)

It comprises a coloring material (A), binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E), The solvent (E) is a solvent (E-1) having an evaporation rate of 0.01 or more and less than 10, a solvent (E-2) having an evaporation rate of 10 or more and less than 40, based on the evaporation rate of n-butyl acetate as 100. The coloring photosensitive resin composition containing the solvent (E-3) which is 40 or more and 70 or less. The solvent (E-1) is 3-40 mass%, the solvent (E-2) is 30-90 mass%, and a solvent (E-3) in mass fraction with respect to the solvent total amount in the said colored photosensitive resin composition. ) Is contained 3 to 40% by mass, the colored photosensitive resin composition. The colored photosensitive resin composition according to claim 1, wherein the solvent (E-1) comprises at least one selected from propylene glycol diacetate and ethylene glycol mono n-butyl ether acetate. The method according to claim 1, wherein the colored photosensitive resin composition is used to form a colored layer on a thin film transistor (TFT) drive substrate and the coloring material (A) is 3 by mass fraction based on the solid content in the colored photosensitive resin composition. It is contained 40 mass%-The coloring photosensitive resin composition characterized by the above-mentioned. The colored photosensitive resin composition according to claim 4, wherein the driving substrate is a large substrate having a size of 1870 mm x 200 mm or more. A color filter comprising the colored layer formed by applying the coloring photosensitive resin composition of any one of Claims 1-4 on a board | substrate, and exposing and developing in a predetermined pattern. The color filter of claim 6, wherein the substrate is a driving substrate on which a thin film transistor (TFT) is disposed. A liquid crystal display device comprising the color filter according to claim 6.