KR20120035995A - Colored photosensitive resin composition, color filter and liquid crystal display using same - Google Patents

Abstract

PURPOSE: A coloring photo-sensitive resin composition, a color filter, and a liquid crystal display device are provided to improve the long-term storing stability and the chemical resistance characteristic to solvent of the composition. CONSTITUTION: A coloring photo-sensitive resin composition includes alkali soluble resin, a coloring agent with pigment or dye, photo-polymerizable compound, photo-polymerization initiator, and solvent. The alkali soluble resin includes a structural unit derived from acid anhydride which is represented by chemical formula 1. In chemical formula 1, R1 and R2 are respectively hydrogen, aliphatic or aromatic hydrocarbon with/without C1 to C12 hetero atom. The polystyrene-reduced weight molecular weight of the alkali soluble resin is between 3.000 and 100,000.

Description

Colored photosensitive resin composition, color filter and liquid crystal display device {COLORED PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER AND LIQUID CRYSTAL DISPLAY USING SAME}

The present invention relates to a colored photosensitive resin composition, a color filter and a liquid crystal display device, and a colored photosensitive resin composition capable of producing a color filter having excellent compatibility with dyes and improved reliability, a liquid crystal using a color filter and a color filter using the same. It relates to a display device.

The color filter is embedded in a color photographing device of an image sensor such as a complementary metal oxide semiconductor (CMOS) or a charge coupled device (CCD), and may be used to actually obtain a color image. In addition, it is widely used in photographing devices, plasma display panels (PDPs), liquid crystal displays (LCDs), field emission displays (FELs), and light emitting displays (LEDs), and its application range is rapidly expanding. In particular, in recent years, the use of LCD has been further expanded, and thus color filters have been recognized as one of the most important parts in reproducing the color tone of LCDs.

Such a color filter is manufactured by the method of forming a desired coloring pattern using the coloring photosensitive resin composition containing a coloring agent. Specifically, it is produced by forming a coating layer made of a colored photosensitive resin composition on a substrate, repeating a series of processes of forming a pattern on the formed coating layer, exposing and developing, heating and thermosetting.

Pigment was used as a colorant, but in recent years, there is an attempt to use a dye having high brightness and excellent heat resistance. When only a dye is used as the colorant, it is preferable to implement all excellent properties of the dye, but the dye has a limitation in its use because it is less compatible with other components of the composition than the pigment. Therefore, a method of using a hybrid type colorant using both a pigment and a dye as a colorant has been attempted, but until now, the problem of using a colorant including a dye has not been completely solved.

When manufacturing a color filter using the coloring photosensitive resin composition containing a dye as a coloring agent, a foreign material arises at the time of formation of a colored layer by lack of compatibility with the material used. In addition, in the case of manufacturing the color filter, the developing speed is low and the sensitivity is insufficient, so that the peeling of the pattern formed during the developing process by the alkaline developing solution occurs frequently. Accordingly, there is a need for development of a colored photosensitive resin composition suitable for a lyso process that can solve the problem of including a dye as a colorant or using a dye alone as a colorant.

The present invention is to solve the above-mentioned problems, an object of the present invention is a color photosensitive resin composition which can produce a color filter having excellent compatibility with dyes and improved reliability, a liquid crystal using a color filter and a color filter using the same It is to provide a display device.

The coloring photosensitive resin composition according to an aspect of the present invention for achieving the above object is a coloring photosensitive resin composition containing a colorant, a photopolymerizable compound, a photopolymerization initiator and a solvent containing an alkali-soluble resin, a pigment or a dye, Soluble resin includes the structural unit derived from the acid anhydride (A1) represented by General formula (1).

 <Formula 1>

In formula, R <_1> and R <_2> is respectively independently hydrogen, the aliphatic, or aromatic hydrocarbon which contains or does not contain the hetero atom of C1-C12.

The alkali-soluble resin is a copolymer of an acid anhydride (A1) and a compound (A2) having an unsaturated bond copolymerizable with the acid anhydride (A1), or a compound (A3) having a functional group capable of bonding such a copolymer with an acid anhydride (A1). It may be a compound combined with.

The ratio of the structural unit derived from the acid anhydride (A1) with respect to the total number of moles of all the structural units of the alkali-soluble resin may be 2 to 80 mol%.

The ratio of the structural unit derived from the compound (A2) which has an unsaturated bond copolymerizable with an acid anhydride (A1) with respect to the total mole number of all the structural units of an alkali-soluble resin may be 2 to 95 mol%.

The ratio of the structural unit derived from the compound (A3) which has a functional group couple | bonded with an acid anhydride (A1) may be 2-95 mol% with respect to the mole number of the structural unit of (A1) in alkali-soluble resin.

Compound (A2) having an unsaturated bond copolymerizable with acid anhydride (A1) includes unsaturated carboxylic acid, unsubstituted or substituted alkyl ester compound of unsaturated carboxylic acid, unsaturated carboxylic acid ester compound including alicyclic substituent, monosaturated carboxylic acid ester of glycols It may be at least one selected from the group consisting of a compound, an unsaturated carboxylic acid ester compound including a substituent having an aromatic ring, an aromatic vinyl compound, a carboxylic acid vinyl ester, a vinyl cyanide compound, and a maleimide compound.

Compound (A2) which has an unsaturated bond copolymerizable with an acid anhydride (A1) is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, aminoethyl (meth) acrylate, cyclopentyl ( Meta) 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, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, pina Neyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, pineneyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl ( Meta) acrylic , 3,4-epoxycyclohexylmethyl (meth) acrylate, methylglycidyl (meth) acrylate, oligoethylene glycol monoalkyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) acrylic Latex, styrene, α-methylstyrene, vinyltoluene, vinyl acetate, vinyl propionate, (meth) acrylonitrile, α-chloroacrylonitrile, N-cyclohexylmaleimide, N-phenylmaleimide, acrylic acid, methacrylic acid, At least one compound selected from the group consisting of crotonic acid, itaconic acid, maleic acid and fumaric acid.

Compound (A3) which has a functional group couple | bonded with an acid anhydride (A1) is hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3- chloropropyl (meth) acrylate. , 4-hydroxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 3- (acryloyloxy)- It may be at least one selected from the group consisting of 2-hydroxypropyl methacrylate.

The alkali-soluble resin preferably has a weight average molecular weight of 3,000 to 100,000 in terms of polystyrene.

According to another aspect of the present invention, there is provided a color filter comprising a colored layer comprising the colored photosensitive resin composition according to the present invention.

According to another aspect of the present invention, there is provided a liquid crystal display device comprising the color filter according to the present invention.

The colored photosensitive resin composition according to the present invention has excellent compatibility with pigments or dyes whose constituents are colorants, and includes a pigment and a dye, but also has a high development speed and excellent sensitivity and adhesion, thereby causing a peeling of the pattern during the developing process. There is no solvent resistance.

In addition, it is excellent in chemical resistance to the solvent used in the color photosensitive resin composition color filter manufacturing process according to the present invention, has excellent long-term storage stability has the effect of improving reliability.

1A to 1C are views illustrating a manufacturing procedure of a color filter according to the present invention.
2A and 2B are perspective views of a color filter according to the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. However, embodiments of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

The coloring photosensitive resin composition which concerns on this invention contains the coloring agent (B) containing an alkali-soluble resin (A), a pigment, or dye, a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E). Hereinafter, each component contained in the coloring photosensitive resin composition of this invention is demonstrated in detail.

Alkali  Soluble Resin (A)

The alkali-soluble resin (A) added to the coloring photosensitive resin composition of this invention as a binder resin generally has reactivity and alkali solubility by the action of light or heat, and acts as a dispersion medium of a coloring agent (B).

Alkali-soluble resin (A) contains the structural unit derived from the acid anhydride (A1) represented by following formula (1).

In formula, R <_1> and R <_2> is respectively independently hydrogen, the aliphatic, or aromatic hydrocarbon which contains or does not contain the hetero atom of C1-C12.

Alkali-soluble resin (A) is an unsaturated group containing resin containing the structural unit which can be obtained by superposing | polymerizing (including copolymerization) of the compound of General formula (1). That is, the compound of formula 1 is polymerized alone or together with other compounds to constitute an alkali soluble resin (A). There is no limitation on the conditions of the other compound to be polymerized with the compound of Formula 1 and all are included in the present invention.

The alkali-soluble resin (A) according to the present invention may be a copolymer of an acid anhydride (A1) and a compound (A2) having an unsaturated bond copolymerizable with the acid anhydride (A1). In addition, the alkali-soluble resin (A) according to the present invention has a functional group capable of bonding a copolymer of an acid anhydride (A1) and a compound (A2) having an unsaturated bond copolymerizable with the acid anhydride (A1) with an acid anhydride (A1). It can obtain by combining with compound (A3).

In one embodiment of the present invention, the compound (A2) having an unsaturated bond copolymerizable with the acid anhydride (A1) includes an unsaturated carboxylic acid, an unsubstituted or substituted alkyl ester compound of an unsaturated carboxylic acid, and an unsaturated carboxylic acid ester containing an alicyclic substituent. At least one or more selected from the group consisting of a compound, a monosaturated carboxylic acid ester compound of glycols, an unsaturated carboxylic acid ester compound including a substituent having an aromatic ring, an aromatic vinyl compound, a carboxylic acid vinyl ester, a vinyl cyanide compound and a maleimide compound Can be.

Compound (A2) which has an unsaturated bond copolymerizable with an acid anhydride (A1) is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, aminoethyl (meth) acrylate, cyclopentyl ( Meta) 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, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, pina Neyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, pineneyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl ( Meta) acrylic , 3,4-epoxycyclohexylmethyl (meth) acrylate, methylglycidyl (meth) acrylate, oligoethylene glycol monoalkyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) acrylic Latex, styrene, α-methylstyrene, vinyltoluene, vinyl acetate, vinyl propionate, (meth) acrylonitrile, α-chloroacrylonitrile, N-cyclohexylmaleimide, N-phenylmaleimide, acrylic acid, methacrylic acid, At least one compound selected from the group consisting of crotonic acid, itaconic acid, maleic acid and fumaric acid.

In one embodiment of the present invention, in the copolymer obtained by copolymerizing (A1) and (A2) (which is included in the present invention even when monomers other than A1 to A2 are further included and copolymerized), (A1) and ( A2) The ratio of the structural units derived from each of the ratio of the structural units derived from the acid anhydride (A1) to the total moles of the total structural units of the alkali-soluble resin may be from 2 to 80 mol%, acid anhydride (A1) The ratio of the structural unit derived from the compound (A2) having an unsaturated bond copolymerizable with may be 2 to 95 mol%.

That is, when the alkali-soluble resin (A) is a copolymer of (A1) and (A2), the structural units derived from (A1) and (A2) are contained in the range of 2 to 80 mol% and 2 to 95 mol%, respectively. It is preferable. In addition, when the alkali-soluble resin (A) is a copolymer of (A1) and (A2), the structural units derived from (A1) and (A2) are included in the range of 5 to 70 mol% and 5 to 80 mol%, respectively. More preferred. When each structural unit is in this range, since the balance of developability, solubility, and heat resistance is favorable, a preferable copolymer can be obtained.

The compound (A3) having a functional group bondable with the acid anhydride (A1) can impart photocurability or thermosetting to the alkali-soluble resin (A).

Compound (A3) which has a functional group couple | bonded with an acid anhydride (A1) is hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3- chloropropyl (meth) acrylate. , 4-hydroxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 3- (acryloyloxy)- It may be at least one selected from the group consisting of 2-hydroxypropyl methacrylate. These may be used alone or in combination of two or more, respectively, but are not limited thereto.

The ratio of the structural unit derived from the compound (A3) which has a functional group couple | bonded with an acid anhydride (A1) may be 2 to 95 mol% with respect to the mole number of the structural unit of (A1) in alkali-soluble resin. More preferably, it is 10-90 mol%. If the composition ratio of (A3) is within such a range, sufficient photocurability and thermosetting are obtained, and since a sensitivity and pencil hardness are compatible, and it is excellent in reliability, it is preferable.

In one Embodiment of this invention, when alkali-soluble resin (A) is a copolymer of (A1) and (A2), it can manufacture as follows.

To the flask equipped with the stirrer, the thermometer, the reflux cooling tube, the dropping lot and the gas introduction tube, 0.5 to 20 times the amount of the solvent (E) was introduced together with respect to the total amount of (A1) and (A2) and the atmosphere in the flask was introduced. Substitute in nitrogen for air. Then, after heating up the solvent (E) at 40-140 degreeC, 0-20 times of the solvent (E) and azobisisobutyronitrile or a tert by weight with respect to the total amount of (A1) and (A2). A solution obtained by adding 0.1 to 10 mol% of a polymerization initiator such as butyperoxy 2-ethylhexyl carbonate to the total number of moles of (A1) and (A2) (stirred and dissolved under room temperature or heating) is added dropwise from 0.1 to 8 hours. It is dripped at the said flask over and stirred for 1 to 10 hours further at 40-140 degreeC.

In addition, one part or whole quantity of a polymerization initiator may be put in a flask, and a part or whole quantity of (A1)-(A2) may be put in a flask. In addition, in order to control molecular weight and molecular weight distribution, an alpha -methylstyrene dimer or a mercapto compound can also be used as a chain transfer agent. The usage-amount of an alpha -methylstyrene dimer or a mercapto compound is based on the total amount of (A1)-(A2). 0.005 to 5% by weight. The polymerization conditions may be controlled differently from the charging method or the reaction temperature in consideration of the amount of heat generated by the production equipment or polymerization.

In one embodiment of the present invention, when the alkali-soluble resin (A) is a compound in which a compound (A3) having a functional group bondable with an acid anhydride (A1) is bonded to the copolymer of (A1) and (A2) as follows. It can be produced together.

The atmosphere in the flask was replaced by nitrogen to air, and the reaction catalyst of the acid anhydride and the alcohol of 3 to 95 mol% (A3) in molar fraction with respect to the structural unit derived from the copolymer of (A1) and (A2). For example, dimethylaminoethyl methacrylate is 0.01 to 5% by weight relative to the total amount of (A1) to (A3) and the polymerization inhibitor, for example, hydroquinone to the total amount of (A1) to (A3) On the basis of 0.001 to 5% in a flask and reacted for 1 to 10 hours at 60 to 130 ℃, the copolymer of (A1) and (A2) and (A3) can be reacted. The polymerization conditions may be controlled differently from the charging method or the reaction temperature in consideration of the amount of heat generated by the production equipment or polymerization.

The alkali-soluble resin (A) may have a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, preferably 5,000 to 50,000. When the weight average molecular weight of alkali-soluble resin (A) exists in the range of 3,000-100,000, film | membrane reduction hardly arises at the time of image development, and since the missing property of a non-pixel part at the time of image development tends to be favorable, 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 alkali-soluble resin (A), it is more preferable that it is 1.8-4.0. If the molecular weight distribution of alkali-soluble resin (A) is 1.5-6.0, since it is excellent in developability, it is preferable.

The content of the alkali-soluble resin (A) in the colored photosensitive resin composition is usually in the range of 5 to 90% by weight, preferably 10 to 70% by weight based on the total solids of the colored photosensitive resin composition. If the content of the alkali-soluble resin (A) is 5 to 90% by weight, the solubility in the developer is sufficient, so that development residues are less likely to occur on the substrate of the non-pixel portion, and it is difficult to reduce the film portion of the pixel portion of the exposed portion during development. It is preferable because the omission of the pixel portion tends to be good.

Colorant (B)

The coloring agent (B) used for the coloring photosensitive resin composition of this invention can contain a pigment and dye, respectively, or together.

As the pigment, organic pigments or inorganic pigments generally used in the art may be used, and these may be used alone or in combination of two or more kinds.

The pigment may be organically treated to remove impurities by surface treatment with a resin derivative, a pigment derivative having an acidic group or a basic group introduced therein, graft treatment on the surface of the pigment with a high molecular compound or the like, or a fine particle treatment by a sulfate atomization method or the like. A washing treatment with a solvent, water, or the like, an ionic impurity removing treatment by an ion exchange method, or the like can also be performed.

As the pigment, various pigments used in inkjet inks and the like may be used, and specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindolin pigments, perylene pigments, and perri Non pigments, dioxazine pigments, anthraquinone pigments, dianthhraquinoneyl pigments, anthrapyrimidine pigments, ananthronerone pigments, indanthrone pigments, pravantron pigments, pyranthrone pigments, and dike Topiro pyrrole pigment etc. are mentioned.

As inorganic pigments, metal compounds such as metal oxides and metal complex salts can be used. Specific examples thereof include metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black. Oxides or composite metal oxides;

In particular, as a pigment, a compound specifically classified as a pigment may be used in the color index (Published by The society of Dyers and Colourists), and more specifically, a pigment having the following color index (CI) number may be used. 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.

Illustrated C.I. Among pigment pigments, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 6, C.I. Pigment Green 7, C.I. Pigment Green 36 or C.I. Pigments selected from Pigment Green 58 may be preferably used.

It is preferable to use the pigment dispersion liquid in which the particle size was disperse | distributed uniformly. As an example of the method for uniformly dispersing the particle size of the pigment, a method of containing and dispersing the pigment dispersant may be used. According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine, and these may be used alone or in combination of two or more. have.

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), Mega Pack (MEGAFAC) (manufactured by Dainippon Ink & Chemicals Co., Ltd.), Florard (manufactured by Sumitomo 3M Inc.), Asahi guard, Suflon (manufactured by Asahi Glass Co., Ltd.), SOLSPERSE ) (Manufactured by Genka Corporation), EFKA (manufactured by EFKA Chemicals Co., Ltd.), PB 821 (manufactured by Ajinomoto Co., Ltd.), and the like.

The pigment dispersant is usually used in an amount of 1 part by weight or less, preferably 0.05 to 0.5 parts by weight, based on 1 part by weight of the pigment. When the pigment dispersant is used in such a content, it is preferable because a dispersed pigment of uniform particle size can be obtained.

The dye can be used without limitation so long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye which has solubility in an organic solvent and can ensure reliability such as solubility, heat resistance and solvent resistance in an alkaline developer.

The dye may be selected from acid dyes having acidic groups such as sulfonic acid and carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof, and azo, xanthene, and phthalocyanine compounds. Acid dyes and derivatives thereof can also be selected.

Preferably, the dye includes a compound classified as a dye in the color index (Published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (color dyed yarn).

Specific examples of the dyes include C.I. As solvent dyes,

C.I. Yellow dyes such as solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;

C.I. Red dyes such as solvent red 45, 49, 122, 125, and 130;

C.I. Orange dyes such as solvent orange 2, 7, 11, 15, 26, 56 and the like;

C.I. Blue dyes such as solvent blue 35, 37, 59, 67 and the like; And

C.I. Green dyes, such as solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. are mentioned.

See also C.I. As an acid dye,

CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 Yellow dyes such as, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251 ;

CI acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 , 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349 Red dyes such as, 382, 383, 394, 401, 412, 417, 418, 422, 426;

Orange dyes such as C.I. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

CI acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103 , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1 Blue dyes such as, 335 and 340;

Violet dyes such as C.I. acid violet 6B, 7, 9, 17, 19 and the like; And

Green dyes, such as C.I. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. are mentioned.

Also as a C.I. direct dye,

CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 Yellow dyes such as, 136, 138, and 141;

CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 Red dyes such as, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246 and 250;

Orange dyes such as C.I.direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

CI direct blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 Blue dyes such as, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, etc .;

Violet dyes such as C.I. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104 and the like; And

Green dyes, such as C.I. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. are mentioned.

In addition, C.I. As a modanto dye,

Yellow dyes such as C.I. modanto yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

CI Modanto Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, Red dyes such as 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95 and the like;

CI Modanto Orange Orange such as 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, etc. dyes;

CI Modanto Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, Blue dyes such as 43, 44, 48, 49, 53, 61, 74, 77, 83, 84 and the like;

Violet dyes such as C.I. modanto violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58 and the like; And

Green dyes, such as C.I. modanto green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, etc. are mentioned.

The content of the dye in the colorant (B) is preferably contained 0.5 to 80% by weight, more preferably 0.5 to 60% by weight, particularly preferably 1 to 50% by weight, based on the weight of solids in the colorant (B). . When the content of the dye in the colorant (B) is in this range, it is possible to prevent the problem of lowering the reliability of the dye eluted by the organic solvent after the pattern formation, it is preferable because the sensitivity is excellent.

The content of the coloring agent (B) is preferably contained 5 to 70% by weight, preferably 10 to 50% by weight relative to the solid content in the colored photosensitive resin composition. When the colorant (B) is included in the range of 5 to 70% by weight, the color density of the pixel is sufficient even when a thin film is formed, and since the omission property of the non-pixel portion does not decrease during development, it is preferable that no residue occurs.

In the present invention, the total solid content in the colored photosensitive resin composition means the total content of the remaining components excluding the solvent from the colored photosensitive resin composition.

Photopolymerization  The compound (C)

The photopolymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by the action of a photopolymerization initiator described below, but is preferably a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound, or a trifunctional or higher polyfunctional photopolymerizable compound. There is this.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrroli Commercial goods include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nipbon Kayaku), and Biscot 158 (Osaka Yuki Kagaku High School).

Specific examples of the bifunctional monomer 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, and 3-methylpentanediol di (meth) acrylate, and the like, and commercially available products such as Aronix M-210, M-1100, 1200 (Doagosei), KAYARAD HDDA (Nippon Kayaku), Biscot 260 (Osaka Yuki Kagaku High School), AH-600, AT-600, and UA-306H (Kyoeisha Chemical Co., Ltd.).

Specific examples of the trifunctional or higher polyfunctional photopolymerizable compound include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxylated trimethylolpropane tri (meth) acrylate. , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxysilane Tied dipentaerythritol hexa (meth) acrylate and dipentaerythritol hexa (meth) acrylate are commercially available products such as Aronix M-309, TO-1382 (Doagosei), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPHA-40H (Nippon Kayaku).

Among the exemplified photopolymerizable compounds (C), trifunctional or higher (meth) acrylic acid esters and urethane (meth) acrylates are particularly preferable in terms of excellent polymerizability and improving strength. In addition, the illustrated photopolymerizable compound (C) can be used individually or in combination of 2 types or more, respectively.

The content of the photopolymerizable compound (C) is preferably contained in a weight fraction of 5 to 45% by weight, more preferably 7 to 45% by weight, based on the solid content in the colored photosensitive resin composition. When 5 to 45 weight% of photopolymerizable compounds (C) are contained, since the intensity | strength and smoothness of a pixel part become favorable, it is preferable.

Photopolymerization Initiator (D)

The photopolymerization initiator (D) can be used without particular limitation as long as it can polymerize the photopolymerizable compound (C). In particular, the photopolymerization initiator (D) is an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound, and a thike from the viewpoint of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and price. It is preferable to use at least one compound selected from the group consisting of acid compounds.

Specific examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy Ethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1- And 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one and the like.

As a benzophenone type compound, for example, benzophenone, methyl 0- benzoyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3, 3 ', 4, 4'- tetra (tert) -Butyl peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -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-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, and 2,4-bis (trichloro Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichloro Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4, The imidazole compound etc. which the phenyl group of a 4'5,5'- tetraphenyl- 1,2'- biimidazole or a 4,4 ', 5,5' position are substituted by the carboalkoxy group 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, and 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole are preferred Used.

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the like, and commercially available products include BASF's OXE01 and OXE02.

As a thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. There is this.

Moreover, as long as it does not impair the effect of this invention, another photoinitiator etc. can also be used together. As another photoinitiator, a benzoin 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 a benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

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. have.

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

You may use combining a photoinitiator with a photoinitiator (D). When a photoinitiator adjuvant is used together with a photoinitiator (D), since the photosensitive resin composition containing these becomes more sensitive and improves productivity, it is preferable.

As the photopolymerization start adjuvant, for example, one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group can be preferably used.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-amylaminobenzoic acid isoamyl and 4-dimethyl Aminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively Michler's ketone), and 4,4'-bis ( Aromatic amine compounds, such as diethylamino) benzophenone, are mentioned. As an amine compound, an aromatic amine compound is used preferably.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthio And aromatic heteroacetic acids such as acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane and 1,3,5-tris (3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropanetris (3-mergaptopropionate), pentaerythritol tetrakis (3-mercaptobutyl Rate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate) and the like Can be mentioned.

The amount of the photopolymerization initiator (D) used is 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the solid content, based on the total amount of the alkali-soluble resin (A) and the photopolymerizable compound (C). When the photopolymerization initiator (D) is in the range of 0.1 to 40% by weight, the colored photosensitive resin composition is highly sensitive and the exposure time is shortened, so productivity is improved and high resolution can be maintained, and the intensity of the pixel portion formed using the composition is preferred. The smoothness on the surface of this pixel portion is preferable, because this is preferable.

In addition, when using a photoinitiation adjuvant, the usage-amount of a photoinitiation adjuvant is 0.1-50 weight% by weight with respect to the total amount of alkali-soluble resin (A) and a photopolymerizable compound (C) based on solid content, Preferably it is 1 to 40 wt%. When the usage-amount of a photoinitiator is in the range of 0.1-50 weight%, since the sensitivity of a coloring photosensitive resin composition becomes higher and the productivity of the color filter formed using this composition improves, it is preferable.

Solvent (E)

The solvent (E) can be used without particular limitation as long as it is effective to disperse or dissolve the other components included in the colored photosensitive resin composition, and in particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, etc. This is preferred.

The solvent (E) is specifically ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether , Diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl Ethers such as ether and dipropylene glycol dibutyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; And ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3- Methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene Glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate or γ- Butyrolactone Esters such as these; Etc. can be mentioned.

In view of the applicability and dryness in the exemplified solvent, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butalactate, ethyl 3-ethoxypropionate, or Methyl 3-methoxypropionate can be used.

The illustrated solvent (E) can be used individually or in mixture of 2 or more types, respectively.

The content of the solvent (E) is 60 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the colored photosensitive resin composition including the same. Applicability when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (or die coater), and inkjet when the content of the solvent (E) is in the range of 60 to 90% by weight based on the above criteria. Since this becomes favorable, it is preferable.

additive

Additives can be selectively added as needed, for example, other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents and the like.

Specific examples of other high molecular compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, and polyurethanes. Can be mentioned.

The curing agent is used to increase the core hardening and mechanical strength, and specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds and the like.

Specific examples of the epoxy compound in the curing agent include a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol F epoxy resin, a noblock type epoxy resin, other aromatic epoxy resins, and an alicyclic epoxy resin. , Glycidyl ester resins, glycidylamine resins, or brominated derivatives of such epoxy resins, aliphatic, cycloaliphatic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co) polymer epoxides, isoprene ( Co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like.

Specific examples of the oxetane compound in the curing agent include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, and cyclohexane dicarboxylic acid bis oxetane.

A hardening | curing agent can use together the hardening auxiliary compound which can make ring-opening-polymerize the epoxy group of an epoxy compound, and the oxetane skeleton of an oxetane compound with a hardening | curing agent. Examples of the curing aid compound include polyhydric carboxylic acids, polyhydric carboxylic anhydrides, and acid generators. As the polyhydric carboxylic acid anhydride, a commercially available product can be used as the epoxy resin curing agent. As a specific example of an epoxy resin hardening | curing agent, a brand name (Adekahadona EH-700) (made by Adeka Industry Co., Ltd.), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), and a brand name (MH-700) (New Nippon Ewha Co., Ltd.) etc. are mentioned. The hardening | curing agent illustrated can be used individually or in mixture of 2 or more types.

Surfactant can be used in order to improve the film formation property of the photosensitive resin composition further, A fluorine-type surfactant or silicone surfactant can be used preferably.

Silicone surfactants include, for example, DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc. of Dow Corning Toray Silicone Co., Ltd., and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 and the like. Fluorine-based surfactants include, for example, Megapieces F-470, F-471, F-475, F-482, F-489, etc. of Dainippon Ink & Chemicals Co., Ltd. as commercially available products. The illustrated surfactant can be used individually or in combination of 2 types or more, respectively.

Specific examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxy Silane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. Illustrative adhesion promoters can be used individually or in combination of 2 types or more, respectively. The adhesion promoter may be included in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the solids content of the colored photosensitive resin composition.

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 absorbent include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone and the like.

Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

The coloring photosensitive resin composition of this invention can be manufactured by the following methods, for example. The coloring agent (B) 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. At this time, a pigment dispersant is used as needed, and some or all of alkali-soluble resin (A) may be mix | blended. The remainder of alkali-soluble resin (A), the photopolymerizable compound (C) and a photoinitiator (D), the additive used as needed, and the additional solvent (E) as needed are further added to the obtained dispersion liquid so that it may become a predetermined concentration, The desired colored photosensitive resin composition is obtained.

According to another aspect of the present invention, there is provided a color filter comprising a colored layer comprising the colored photosensitive resin composition according to the present invention. The color filter according to the present invention comprises a colored layer formed by coating a colored photosensitive resin composition on a substrate and exposing and developing the film in a predetermined pattern. A partition may be further formed between each colored pattern, and a black matrix may be added. In addition, a protective film may be further formed on the color filter.

1A to 1C are views illustrating a manufacturing procedure of a color filter according to the present invention. When manufacturing a color filter using the coloring photosensitive resin composition which concerns on this invention, the coloring photosensitive resin composition is pattern-processed, for example, and the coloring pattern 3 'is formed. That is, after forming the color layer 3 which consists of colored photosensitive resin composition on the board | substrate 1 (FIG. 1A), and irradiates this formed color layer 3 in a predetermined pattern (FIG. 1B), it develops. (FIG. 1C). The pre-formed coloring pattern 2 may be on the substrate 1. After development, a heating process may be performed.

The substrate 1 is not limited and may be the substrate of the color filter itself, or may be a portion where the color filter is located in a display device or the like. The substrate 1 may be a glass plate, a silicon wafer and a plastic plate such as poly ether sulfate (PES), polycarbonate, or the like. That is, the substrate 1 may be silicon (Si), silicon oxide (SiOx), a glass substrate, or a polymer substrate.

In order to form the colored layer 3 made of the colored photosensitive resin composition on the substrate 1 as shown in FIG. 1A, for example, the colored photosensitive resin composition diluted with a solvent is spin-slit, spin-slit, After coating on the substrate by a coating method such as a roll, spray, inkjet method, volatile components such as a solvent and the like are volatilized. Thereby, the colored layer 3 which consists of colored photosensitive resin composition is formed, Comprising: The colored layer 3 consists of solid components of a colored photosensitive resin composition, and contains few volatile components.

The thickness of the colored layer 3 is determined by the coating conditions such as the viscosity of the composition, the concentration of solid content, the coating speed, and the like, and in the case of using the colored photosensitive resin composition of the present invention, the colored layer 3 having a thickness of 0.5 to 5 μm. Can be obtained.

Subsequently, as shown in Fig. 1B, the colored layer 3 made of the colored photosensitive resin composition is exposed to light. In order to expose, for example, the colored layer 3 is irradiated with the light beam 20 in a predetermined pattern through the photomask 10. As light, ultraviolet rays g line (wavelength: 436 nm), h line, i line (wavelength: 365 nm) and the like are usually used. Light rays pass through the pattern of the photomask 10. The photomask 10 provides a light shielding layer 12 that shields light rays in a predetermined pattern on the surface of the glass plate 11. Light ray 20 is shielded by light shielding layer 12. The part of the glass plate 11 in which this light shielding layer 12 is not provided is the light transmission part 13 which the light ray 20 transmits. The colored layer 3 is exposed according to the pattern of the light transmitting part 13. The irradiation amount of the light beam 20 is suitably selected according to the coloring photosensitive resin composition used. The portion where the light beam 20 is irradiated has a much lower solubility than the portion where the light beam 20 is not irradiated, thereby maximizing the difference in solubility between them.

After the exposure operation described above, it is developed as shown in Fig. 1C. For development, for example, the colored photosensitive resin composition layer after exposure is immersed in a developer. As a developer, an aqueous solution of an alkali compound such as sodium carbonate, sodium hydroxide, potassium hydroxide, potassium carbonate, or tetramethylammonium hydroxide is used.

By development, the non-light-irradiated area | region which was not irradiated by the light ray in a colored layer is removed. On the contrary, the light irradiation area irradiated by the light rays remains to constitute the coloring pattern 3 '. After development, it is generally washed with water and dried. Moreover, you may heat-process after drying. The colored pattern 3 'formed by the heat treatment is cured, whereby the mechanical strength is improved. Thus, since the mechanical strength of the coloring pattern 3 'can be improved by heat treatment, it is preferable to use a coloring photosensitive composition containing a curing agent. Heating temperature is usually 180 degreeC or more, Preferably it is 200-250 degreeC.

As is well known, the color filter is usually a black matrix and three primary color pixels of red, green, and blue arranged on a substrate, but using the colored photosensitive resin composition of the present invention containing a coloring material corresponding to any color, By performing the operation, a black matrix or pixel of the color is obtained, and the same operation is performed using the colored photosensitive resin composition of the present invention containing the coloring material corresponding to the desired color for other colors, thereby performing the black matrix and the three primary color pixels. It can be placed on a substrate. Of course, you may apply the coloring photosensitive resin composition of this invention only to 1 color, 2 color, or 3 colors of a black matrix and three primary colors.

2A and 2B are perspective views of a color filter according to the present invention. In the present invention, the coloring pattern means, for example, RGB color pixels (2, 3 ', 4'), black matrix (5), etc., wherein the color pixels are colored transparent layers, and the black matrix is a layer for shielding light. to be. These color pixels and black matrix are usually formed on the substrate 1 to constitute a color filter. Since the color pixels 2, 3 ', 4' are transparent and colored, the light transmitted through these color pixels represents the color of each color pixel. Since the black matrix 5 is a layer which shields light, it looks black. This colored pattern may exist in the form of a lattice (mosaic) (FIG. 2A) or in the form of a line (FIG. 2B).

According to another aspect of the present invention, there is provided a liquid crystal display device comprising the color filter according to the present invention. The liquid crystal display device includes a configuration known to those skilled in the art except for providing a color filter. 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 light-proof resin surrounding the peripheral surface of the color filter, a liquid crystal layer made of nematic liquid crystal imposed in the outer frame, a plurality of pixel electrodes provided for each region of the liquid crystal layer, A transparent glass substrate having a pixel electrode formed thereon, and a polarizing plate formed on an exposed surface of the transparent glass substrate.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

"%" And "part" showing content in the following Examples and Comparative Examples are based on weight unless there is particular notice, and addition amount is a ratio with respect to the whole coloring photosensitive resin composition.

In order to prepare a colored photosensitive resin composition, first, a pigment dispersion was prepared, and an alkali-soluble resin was prepared according to Synthesis Examples 1 to 9.

Preparation of Pigment Dispersion

Pigment Dispersion M1

C.I. Pigment Green 36, 16.2 parts by weight, C.I. 1.8 parts by weight of Pigment Yellow 150, 4.2 parts by weight of Azispa PB821 (manufactured by Ajino Moto Fine Techno Co., Ltd.) as a dispersant, 50 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 27.8 parts of cyclohexanone on a bead mill The mixture was dispersed and dispersed for 12 hours to prepare a pigment dispersion (M1).

Synthesis of Alkali-Soluble Resin (A)

&Lt; Synthesis Example 1 &

426.1 g of propylene glycol monomethyl ether acetate and 176.4 g (1.8 mol) of maleic anhydride were 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 nitrogen in air. After the temperature was raised to 120 ° C., terbutyryl peroxy 2-ethylhexylcarbonate 24.4 was added to a mixture containing 66.0 g (0.3 mol) of dicyclopentanyl methacrylate, 106.2 g (0.9 mol) of vinyltoluene, and 136 g of propylene glycol monomethyl ether acetate. The solution to which g was added was dripped at the flask over 2 hours from the dropping lot, and it stirred further at 120 degreeC for 2 hours, and obtained the precursor of a polymer. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 139.2 g (1.2 mol) of 2-hydroxyethyl acrylate, 1.5 g of dimethylaminoethyl methacrylate and 1.5 g of methylhydroquinone were added to the copolymer solution at 120 ° C. The reaction was continued to obtain a resin having a solid acid value of 180 mg kOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 6,700, and molecular weight distribution (Mw / Mn) was 2.3.

&Lt; Synthesis Example 2 &

426.1 g of propylene glycol monomethyl ether acetate and 176.4 g (1.8 mol) of maleic anhydride were 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 nitrogen in air. After the temperature was raised to 120 ° C., terbutyryroxy 2-ethylhexyl was added to a mixture containing 50.4 g (0.3 mol) of cyclohexyl methacrylate, 1 g (0.9 mol) of cyclohexyl methacrylate, and 136 g of propylene glycol monomethyl ether acetate. The solution to which 24.4 g of carbonate was added was dripped at the flask over 2 hours from the dropping lot, and further stirred at 120 degreeC for 2 hours, and obtained the precursor of a polymer. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 139.2 g (1.2 mol) of 2-hydroxyethyl acrylate, 1.5 g of dimethylaminoethyl methacrylate and 1.5 g of methylhydroquinone were added to the copolymer solution at 120 ° C. The reaction was continued to obtain a resin having a solid acid value of 173 mgkOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 8,900, and molecular weight distribution (Mw / Mn) was 2.4.

&Lt; Synthesis Example 3 &

426.1 g of propylene glycol monomethyl ether acetate and 58.8 g of maleic anhydride were 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 nitrogen in air. After the temperature was raised to 120 ° C., terbutyryl peroxy 2-ethylhexyl carbonate 24.4 was added to a mixture containing 264.0 g (1.2 mole) of dicyclopentanyl methacrylate, 141.6 g (1.2 mole) of vinyltoluene, and 136 g of propylene glycol monomethyl ether acetate. The solution to which g was added was dripped at the flask over 2 hours from the dropping lot, and it stirred further at 120 degreeC for 2 hours, and obtained the precursor of a polymer. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 59.2 g (0.5 mol) of 2-hydroxyethyl acrylate, 1.5 g of dimethylaminoethyl methacrylate and 1.5 g of methylhydroquinone were added to the copolymer solution at 120 ° C. The reaction was continued to obtain a resin having a solid acid value of 130 mg kOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 12,700, and molecular weight distribution (Mw / Mn) was 2.2.

&Lt; Synthesis Example 4 &

426.1 g of propylene glycol monomethyl ether acetate and 176.4 g (1.8 mol) of maleic anhydride were 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 nitrogen in air. After the temperature was raised to 120 ° C., terbutyryl peroxy 2-ethylhexyl carbonate 24.4 was added to a mixture containing 132.0 g (0.6 mole) of dicyclopentanyl methacrylate, 70.8 g (0.6 mole) of vinyltoluene, and 136 g of propylene glycol monomethyl ether acetate. The solution to which g was added was dripped at the flask over 2 hours from the dropping lot, and it stirred further at 120 degreeC for 2 hours, and obtained the precursor of a polymer. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 156.0 g (1.2 mol) of 2-hydroxyethyl methacrylate, 1.5 g of dimethylaminoethyl methacrylate and 1.5 g of methylhydroquinone were added to the copolymer solution, followed by 120 ° C. The reaction was continued at to obtain a resin having a solid acid value of 167 mgkOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 10,300, and molecular weight distribution (Mw / Mn) was 2.4.

&Lt; Synthesis Example 5 &

426.1 g of propylene glycol monomethyl ether acetate and 176.4 g (1.8 mol) of maleic anhydride were 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 nitrogen in air. After heating up to 120 degreeC, the solution which added 24.4 g of terbutyryl peroxy 2-ethylhexylcarbonates to the mixture containing 141.6 g (1.2 mol) of vinyltoluenes and 136 g of propylene glycol monomethyl ether acetates was dripped over 2 hours from the lot. It was dripped at the flask, and further stirred at 120 degreeC for 2 hours, and the precursor of a polymer was obtained. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 156.0 g (1.2 mol) of 2-hydroxyethyl methacrylate, 1.5 g of dimethylaminoethyl methacrylate and 1.5 g of methylhydroquinone were added to the copolymer solution, followed by 120 ° C. The reaction was continued at to obtain a resin having a solid acid value of 187 mg kOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 11,400, and molecular weight distribution (Mw / Mn) was 2.3.

&Lt; Synthesis Example 6 &

426.1 g of propylene glycol monomethyl ether acetate and 176.4 g (1.8 mol) of maleic anhydride were 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 nitrogen in air. After the temperature was raised to 120 ° C., a solution containing 24.4 g of terbutyryl peroxy 2-ethylhexylcarbonate was added dropwise to the mixture containing 201.6 g (1.2 mol) of cyclohexyl acrylate and 136 g of propylene glycol monomethyl ether acetate. It was dripped at the flask over, and stirred for 2 hours at 120 degreeC, and the precursor of a polymer was obtained. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 156.0 g (1.2 mol) of 2-hydroxyethyl methacrylate, 1.5 g of dimethylaminoethyl methacrylate and 1.5 g of methylhydroquinone were added to the copolymer solution, followed by 120 ° C. The reaction was continued at to obtain a resin having a solid acid value of 170 mgkOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 11,000, and molecular weight distribution (Mw / Mn) was 2.4.

&Lt; Synthesis Example 7 &

426.1 g of propylene glycol monomethyl ether acetate and 176.4 g (1.8 mol) of maleic anhydride were 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 nitrogen in air. After heating up to 120 degreeC, the solution which added 24.4 g of terbutyryroxy 2-ethylhexylcarbonates to the mixture containing 70.8 g (0.6 mol) of vinyltoluenes and 136 g of propylene glycol monomethyl ether acetates was dripped over 2 hours from the lot. It was dripped at the flask, and further stirred at 120 degreeC for 2 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, 43.2 g (0.6 mol) of acrylic acid, 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 120 ° C. to give a solid acid value of 110 mg. A resin of kOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 5,800, and molecular weight distribution (Mw / Mn) was 2.5.

&Lt; Synthesis Example 8 &

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. g (0.4 mol), 43.0 g (0.5 mol) of methacrylic acid, monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Kasei Co., Ltd.) 22.0 g (0.10 mol), and 136 g of propylene glycol monomethyl ether acetate The solution which added 3.6 g of azobisisobutyronitrile to the mixture containing was dripped at the flask over 2 hours from the dropping lot, and stirring was continued at 100 degreeC for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 15 g of glycidyl methacrylate [0.1 mol, (20 mol% based on the carboxyl group of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and hydroquinone 0.145 g was poured into the flask, and the reaction was continued at 110 ° C. for 6 hours to obtain a resin having a solid acid value of 102 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 30,000, and molecular weight distribution (Mw / Mn) was 2.1.

Synthesis Example 9

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. The atmosphere in the flask was changed from nitrogen to air, and the temperature was raised to 100 ° C., followed by benzyl methacrylate 105.7. g (0.6 mole), 25.3 g (0.3 mole) of methacrylic acid, monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Kasei Co., Ltd.) 22.0 g (0.10 mole), and 136 g of propylene glycol monomethyl ether acetate A solution in which 3.6 g of azobisisobutyronitrile was added to the mixture was added dropwise to the flask over 2 hours from the dropping lot, followed by further stirring at 100 ° C for 5 hours. A resin having a solid acid value of 120 mgKOH / g Got it. The weight average molecular weight of polystyrene conversion measured by GPC was 24,000, and molecular weight distribution (Mw / Mn) was 2.1.

About the measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) in the synthesis examples 1-9, it carried out on condition of the following using GPC method.

Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial Connection)

Column temperature: 40 ℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection volume: 50 μl

Detector: RI

Sample concentration: 0.6 wt% (solvent = tetrahydrofuran)

Calibration standard: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio of the obtained weight average molecular weight (Mw) and number average molecular weight (Mn) was made into molecular weight distribution (Mw / Mn).

Preparation of coloring photosensitive resin composition

Colored photosensitive resin compositions were prepared according to Examples 1 to 8, and Comparative Examples 1 and 2 using alkali-soluble resins prepared according to Synthesis Examples 1-9. Among these, Examples 1 and 2 used the resin of Synthesis Example 1.

&Lt; Example 1 >

<22.52 parts of Pigment Dispersion M1>, 0.51 parts of VALIFAST Yellow 1101 (manufactured by Orient Chemical Industries, Ltd.), 8.86 parts of Resin of <Synthesis Example 1>, 2.95 parts of KAYARAD DPHA (manufactured by Nippon Kayaku), Irgacure OXE01 (BASF Corporation) Preparation) A colored photosensitive resin composition was prepared by mixing 0.59 parts, ethyl lactate 35.2 parts, propylene glycol monomethyl ether acetate, 11.77 parts, and propylene glycol monomethyl ether 17.6 parts.

<Example 2>

23.03 parts of <pigment dispersion liquid M1>, 8.86 parts of resin of <Synthesis Example 1>, 2.95 parts of KAYARAD DPHA (manufactured by Nippon Kayaku), 0.59 parts of Irgacure OXE01 (manufactured by BASF), 35.2 parts of ethyl lactate, propylene glycol monomethyl ether 11.77 parts of acetate and 17.6 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

<Example 3>

A colored photosensitive resin composition was produced in the same manner as in Example 1 except that the alkali-soluble resin was changed to the resin of <Synthesis Example 2>.

<Example 4>

A colored photosensitive resin composition was produced in the same manner as in Example 1 except that the alkali-soluble resin was changed to the resin of <Synthesis Example 3>.

Example 5

The colored photosensitive resin composition was produced like Example 1 except having changed alkali-soluble resin into the resin of <synthesis example 4>.

<Example 6>

A colored photosensitive resin composition was produced in the same manner as in Example 1 except that the alkali-soluble resin was changed to the resin of <Synthesis Example 5>.

<Example 7>

A colored photosensitive resin composition was produced in the same manner as in Example 1 except that the alkali-soluble resin was changed to the resin of <Synthesis Example 6>.

<Example 8>

A colored photosensitive resin composition was produced in the same manner as in Example 1 except that the alkali-soluble resin was changed to the resin of <Synthesis Example 7>.

Comparative Example 1

A colored photosensitive resin composition was produced in the same manner as in Example 1 except that the alkali-soluble resin was changed to the resin of <Synthesis Example 8>.

Comparative Example 2

A colored photosensitive resin composition was produced in the same manner as in Example 1 except that the alkali-soluble resin was changed to the resin of <Synthesis Example 9>.

<Experimental Example>

Color filters were prepared using the colored photosensitive resin compositions prepared in Examples 1 to 8 and Comparative Examples 1 and 2. That is, the colored photosensitive resin compositions prepared in Examples 1 to 8 and Comparative Examples 1 and 2 were applied on a glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. Subsequently, a test photomask having a pattern in which the transmittance is changed stepwise in a range of 1 to 100% and a line / space pattern of 1 to 50 µm is placed on the thin film, and the UV light is spaced at a distance of 100 µm from the test photomask. Investigate.

At this time, the ultraviolet light source was irradiated with luminous intensity of 100mJ / cm 2 using a 1KW high-pressure mercury lamp containing g, h, and i rays, and no special optical filter was used. The UV-irradiated thin film was developed by soaking in a KOH aqueous solution developing solution of pH 10.5 for 2 minutes. The thin plate coated glass plate was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230 ° C. for 20 minutes to prepare a color filter. The film thickness of the manufactured color filter was 2.0 μm.

The development speed, sensitivity, adhesiveness and surface foreign matter of the color filter using the colored photosensitive resin compositions prepared from Examples 1 to 8 and Comparative Examples 1 and 2 were measured and evaluated, and the results are shown in Table 1 below.

Development speed

At the time of development, the time taken for the non-exposed part to completely dissolve in the developer was measured.

<Sensitivity>

The minimum exposure amount necessary to form a thin film free from tearing after development was measured.

<Adhesiveness>

When the generated pattern was evaluated through an optical microscope, the degree of tearing on the pattern was evaluated as follows.

○: no tearing on the pattern

(Triangle | delta): 1-3 pieces broken in a pattern

×: 4 or more tearing pattern

<Contents Resistance>

The produced color filter was immersed in N-methylpyrrolidone solvent for 30 minutes, and the color change before and after evaluation was compared and evaluated. At this time, the equation to be used is calculated by the following Equation 1 representing the color change in the three-dimensional colorimeter defined by L *, a *, b *, the smaller the color change value, it is possible to manufacture a highly reliable color filter.

[Equation 1]

△ Eab ^* = (△ L ^* ) ² + (△ a ^* ) ² + (△ b ^* ) ² ] ^(1/2)

<Check surface foreign matter>

When the generated pattern was evaluated through an optical microscope, the number of foreign substances of 3 μm or more on the pattern was confirmed as follows.

○: less than 2

△: 2 to 10

×: 10 or more

Example Comparative example One 2 3 4 5 6 7 8 One 2 Developing speed (S) 10 10 23 12 14 12 10 22 43 55 Sensitivity (mJ / ㎠) 10 12 8 12 12 10 14 20 32 38 Adhesion ○ ○ ○ ○ ○ ○ ○ ○ △ X △ Eab * 2.1 2.3 3.4 1.8 1.7 1.9 1.2 3.9 5.3 7.8 Surface ○ ○ ○ ○ ○ ○ ○ ○ X X

As shown in Table 1, in Examples 1 to 8 using an alkali-soluble resin having a structural unit represented by the formula (1), it has excellent sensitivity, excellent adhesion and solvent resistance, and excellent compatibility with colorants including dyes. By the formation of the colored layer it can be seen that the surface exhibits excellent properties for the foreign material.

Particularly, Examples 1 and 3 to 8, which contain both pigments and dyes, exhibit excellent properties even when compared to Example 2 using only pigments, so that the alkali-soluble resins according to the present invention are compatible with pigments or dyes as colorants. It turns out that the coloring photosensitive resin composition of the characteristic was favorable and the characteristic was manufactured.

However, in the case of Comparative Examples 1 and 2 using the coloring photosensitive resin composition using alkali-soluble resin (resin synthesized in Synthesis Examples 8 and 9) not using maleic anhydride which is the compound represented by the formula (1), the sensitivity was low, and the pattern It can be seen that the phase tearing phenomenon is not excellent adhesion. In addition, the color change was large, the solvent resistance was bad, and more than 10 surface foreign substances were generated, indicating poor characteristics as a whole.

Therefore, when the colored photosensitive resin composition containing alkali-soluble resin which has a structural unit represented by General formula (1) according to this invention was used, it turns out that the color filter excellent in various physical properties was manufactured.

The invention is not to be limited by the foregoing embodiments and the accompanying drawings, but should be construed by the appended claims. In addition, it will be apparent to those skilled in the art that various forms of substitution, modification, and alteration are possible within the scope of the present invention without departing from the technical spirit of the present invention.

1 board
2 Teratogenic Coloring Pattern
3 colored layers
3` coloring pattern
10 photomask
11 glass plates
12 shading layer
13 floodlight
20 rays

Claims (12)

As a coloring photosensitive resin composition containing the coloring agent containing a alkali-soluble resin, a pigment, or dye, a photopolymerizable compound, a photoinitiator, and a solvent,
The alkali-soluble resin is a colored photosensitive resin composition comprising a structural unit derived from an acid anhydride (A1) represented by the general formula (1):
<Formula 1>

In formula, R <_1> and R <_2> is respectively independently hydrogen, the aliphatic, or aromatic hydrocarbon which contains or does not contain the hetero atom of C1-C12. The method according to claim 1,
The said alkali-soluble resin is a copolymer of the said acid anhydride (A1) and the compound (A2) which has an unsaturated bond copolymerizable with the said acid anhydride (A1), The coloring photosensitive resin composition characterized by the above-mentioned. The method according to claim 2,
The ratio of the structural unit guide | induced from the said acid anhydride (A1) with respect to the total number of moles of all the structural units of the said alkali-soluble resin is 2 to 80 mol%, The coloring photosensitive resin composition characterized by the above-mentioned. The method according to claim 2,
The ratio of the structural unit derived from the compound (A2) which has an unsaturated bond copolymerizable with the said acid anhydride (A1) with respect to the total mole number of all the structural units of the said alkali-soluble resin is 2 to 95 mol%, The coloring characterized by the above-mentioned. Photosensitive resin composition. The method according to claim 2,
Compound (A2) having an unsaturated bond copolymerizable with the acid anhydride (A1) is an unsaturated carboxylic acid, an unsubstituted or substituted alkyl ester compound of an unsaturated carboxylic acid, an unsaturated carboxylic acid ester compound containing an alicyclic substituent, and a monosaturated carboxylic acid of glycols. It is at least one compound selected from the group consisting of an ester compound, an unsaturated carboxylic acid ester compound including a substituent having an aromatic ring, an aromatic vinyl compound, a carboxylic acid vinyl ester, a vinyl cyanide compound and a maleimide compound. Resin composition. The method according to claim 2,
Compound (A2) which has an unsaturated bond copolymerizable with the said acid anhydride (A1) is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, aminoethyl (meth) acrylate, and cyclopentyl (Meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl ( Meta) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, Pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, pineneyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (Meta) Arc Relate, 3,4-epoxycyclohexylmethyl (meth) acrylate, methylglycidyl (meth) acrylate, oligoethylene glycol monoalkyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) Acrylate, styrene, α-methylstyrene, vinyltoluene, vinyl acetate, vinyl propionate, (meth) acrylonitrile, α-chloroacrylonitrile, N-cyclohexylmaleimide, N-phenylmaleimide, acrylic acid, methacrylic acid And at least one compound selected from the group consisting of crotonic acid, itaconic acid, maleic acid and fumaric acid. The method according to claim 1,
The alkali-soluble resin has a compound (A3) having a functional group bondable with the acid anhydride (A1) in the copolymer of the acid anhydride (A1) and the compound (A2) having an unsaturated bond copolymerizable with the acid anhydride (A1). The colored photosensitive resin composition characterized by the above-mentioned compound. The method of claim 7,
The ratio of the structural unit derived from the compound (A3) which has a functional group couple | bonded with the said acid anhydride (A1) with respect to the number-of-moles of the structural unit of the said acid anhydride (A1) in the said alkali-soluble resin is 2 to 95 mol%. The coloring photosensitive resin composition characterized by the above-mentioned. The method of claim 7,
Compound (A3) having a functional group bondable with the acid anhydride (A1) is hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylic Latex, 4-hydroxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 3- (acryloyloxy) It is at least 1 sort (s) or more compound chosen from the group which consists of 2-hydroxypropyl methacrylate, The coloring photosensitive resin composition characterized by the above-mentioned. The method according to claim 1,
The alkali-soluble resin is a colored photosensitive resin composition, characterized in that the weight average molecular weight in terms of polystyrene is 3,000 to 100,000. The color filter containing the colored layer containing the coloring photosensitive resin composition of any one of Claims 1-10. A liquid crystal display comprising the color filter of claim 11.

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