KR20120044603A - A colored photosensitive resin composition, color filter and liquid crystal display device having the same - Google Patents

Abstract

PURPOSE: Colored photo-sensitive compositions, color filters including the same, and liquid crystal display devices including the same are provided to overcome precipitation problems by improving solubility. CONSTITUTION: Colored photo-sensitive compositions include coloring agents with pigment and dye, alkali soluble resins, photopolymerizable compounds, photopolymerizable initiators, and solvents. The solvents are mixture of two or more compounds. One of the compounds is represented by chemical formula 1. In chemical formula 1, R1 is a C1 to C10 alkyl group, a C2 to C10 alkenyl group, or a benzyl group; and R2 is a hydrogen group or a methyl group. The content of the compound represented by chemical formula 1 is 1 to 50 weight% based on total weight of the solvents.

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.

Color filters are widely used in imaging devices, liquid crystal displays, and the like, and their application ranges are rapidly expanding. The color filter used for a color liquid crystal display device, an image pick-up element, etc. is uniformly apply | coated uniformly the coloring photosensitive resin composition containing the coloring agent corresponding to each color of red, green, and blue on the board | substrate with which the black matrix was patterned by spin coating. After that, the coating film formed by heating and drying (hereinafter sometimes referred to as preliminary firing) is exposed and developed, and if necessary, heat-hardening (hereinafter sometimes referred to as postfiring) is repeated for each color. It is manufactured by forming a pixel of color.

When manufacturing a color filter using the high brightness ratio or the high brightness coloring photosensitive resin composition, a stain arises at the time of vacuum drying, or a surface abnormality arises and a color filter defect frequently occurs. This problem occurs due to further increase in the process time for increasing the manufacturing amount of the color filter. In addition, when manufacturing a color filter with a coloring photosensitive resin composition containing a dye as well as conventional pigments, the dye-containing colored photosensitive resin composition is sensitive to the solubility according to the solvent used, and the problem of precipitation depending on the concentration frequently occurs Doing.

An object of the present invention is to provide a colored photosensitive resin composition which can prevent defects caused by vacuum drying stains during color filter manufacture and which can improve productivity.

It is another object of the present invention to provide a color filter of excellent quality including a color layer formed of the colored photosensitive resin composition.

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

In order to achieve the above object, the present invention comprises a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E) containing a pigment and a dye. The solvent (E) is a mixture of two or more compounds, one of which provides a colored photosensitive resin composition, characterized in that the compound represented by the following formula (1).

<Formula 1>

(In the formula, R1 represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group or benzyl group having 2 to 10 carbon atoms, and R2 represents hydrogen or a methyl group.)

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

In addition, the present invention provides a liquid crystal display device comprising the color filter in order to achieve the above object.

By using the coloring photosensitive resin composition which concerns on said invention, the defect by the vacuum drying stain at the time of color filter manufacture is reduced, and in the case of the coloring photosensitive resin composition containing dye, solubility improves and the problem of precipitation etc. can be solved. have.

1A to 1C are cross-sectional views schematically showing a procedure for manufacturing a color filter using the colored photosensitive resin composition according to the present invention.
2A and 2B illustrate a color filter according to an embodiment of the present invention.

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

The coloring photosensitive resin composition which concerns on this invention consists of a coloring agent (A), alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E). In addition, the coloring photosensitive resin composition may optionally further include an additive (F) as necessary.

Colorant (A)

The said coloring agent (A) contains a pigment and dye.

The pigment may be used an organic pigment or an inorganic pigment generally used in the art, these may be used alone or in combination of two or more.

If necessary, the pigment may be a resin treatment, a surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, a graft treatment on the surface of the pigment with a high molecular compound or the like, an atomization treatment by a sulfate atomization method or the like to remove impurities. Washing treatment with an organic solvent, water, or the like, removing ionic impurities by an ion exchange method, or the like can also be performed.

The pigment may be used a variety of pigments used in inkjet ink, and the like, specifically, water-soluble azo pigment, insoluble azo pigment, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, isoindolin pigment, perylene pigment, Perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, ananthrone pigments, indanthrone pigments, pravantron pigments, pyranthrone pigments, dike Topiro pyrrole pigments and the like.

In addition, metal compounds such as metal oxides and metal complex salts may be used as the inorganic pigment, and specific examples 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, the pigment may be a compound that is specifically classified as a pigment in the color index (Published by The society of Dyers and Colourists), more specifically, a pigment having the following color index (CI) number can 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.

C.I. exemplified above. 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 which the said particle size 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.

As said pigment dispersant, surfactant, such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine type, etc. are mentioned, for example, These can be used individually or in combination of 2 or more types, respectively. Can be.

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 Chemical Co., Ltd.), Florard (manufactured by Sumitomo 3M Inc.), Asahi guard, Suflon (manufactured by Asahi Glass Co., Ltd.), SOLSPERSE ) (Manufactured by Geneva Co., Ltd.), EFKA (manufactured by EFKA Chemicals Co., Ltd.), PB 821 (manufactured by Ajinomoto Co., Ltd.), and the like.

The pigment dispersant is usually used in 1 parts by weight or less with respect to 1 part by weight of the pigment, preferably from 0.05 to 0.5 parts by weight. 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 phthalocyanines. Acid dyes and derivatives thereof can also be selected.

Preferably, the dye may be 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 dye 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;

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;

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;

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 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;

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.

It is preferable that 0.5-80 weight% of content of the dye in the said coloring agent (A) is contained by weight fraction with respect to solid content in a coloring agent (A), 0.5-60 weight% is more preferable, 1-50 weight% is especially preferable. Do. When the content of the dye in the coloring agent (A) is in the above range based on the above criteria, 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.

Content of the said coloring agent (A) is 5 to 70 weight% with respect to solid content in colored photosensitive resin composition, It is good to contain 10 to 50 weight% preferably. When the colorant (A) 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 the residue is unlikely to occur because the omission of the non-pixel portion during development is not reduced. Do.

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.

Alkali-soluble resin (B)

The said alkali-soluble resin (B) melt | dissolves in the solvent of this invention, and functions as a binder resin with respect to the said coloring agent (A).

The alkali-soluble resin (B) can be used without particular limitation as long as it is a resin that can be dissolved in an alkaline developer. Preferably, the copolymer (B-1) or the copolymer of the first monomer (b1) having a carboxyl group and an unsaturated bond and the second monomer (b2) having an unsaturated bond copolymerizable with the first monomer (b1) ( The polymer (B-2) containing the photopolymerizable unsaturated bond obtained by making B-1) react the compound (b3) which has an unsaturated bond and an epoxy group can be used.

Specific examples of the first monomer (b1) having the carboxyl group and the unsaturated bond include unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And anhydrides of the above-mentioned unsaturated dicarboxylic acids can be used. The 1st monomer (b1) illustrated above can be used individually or in combination of 2 types or more, respectively. Moreover, the monomer containing a hydroxyl group and a carboxyl group can also be used together in the same molecule like (alpha)-(hydroxymethyl) acrylic acid. In addition, the copolymer (B-1) may be copolymerized by further including other monomers in addition to the first monomer (b1) and the second monomer (b2).

Specific examples of the second monomer (b2) having an unsaturated bond copolymerizable with the first monomer (b1) include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, and m-methoxy Styrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinyl Aromatic vinyl compounds such as benzyl glycidyl ether; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02,6] decane-8-yl (meth) acrylate, 2-dish Alicyclic (meth) acrylates such as clofentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; N-cyclohexyl maleimide, N-benzyl maleimide, N-phenyl maleimide, No-hydroxyphenyl maleimide, Nm-hydroxyphenyl maleimide, Np-hydroxyphenyl maleimide, No-methylphenyl maleimide, Nm N-substituted maleimide compounds such as -methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; Unsaturated amide compounds such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide; 3- (methacryloyl oxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyl oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. Unsaturated oxetane compounds and the like can be used. (B2) illustrated above can be used individually or in combination of 2 types or more, respectively.

Specific examples of the compound (b3) having the unsaturated bond and the epoxy group further reacted with the copolymer (B-1) of the first monomer (b1) and the second monomer (b2) include glycidyl (meth) acrylate. , 3,4-epoxybutyl (meth) acrylate, 2,3-epoxycyclopentyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate , Methylglycidyl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.02,6] decane-9-yl (meth) acrylate, and the like can be used. (B3) illustrated above can be used individually or in combination of 2 types or more, respectively.

In the copolymer (B-1) of the first monomer (b1) and the second monomer (b2), the ratio of the structural units derived from the first monomer (b1) is the total mole number of the structural units constituting the copolymer. It may be in the range of 2 to 95 mol%, preferably 2 to 70 mol% in terms of mole fraction, and the ratio of the structural unit derived from the second monomer (b2) is 2 to 70 mol%, preferably 2 to 50 mol. Can be%. When the ratio of the structural unit derived from each of said (b1) and (b2) exists in the said range, since it is excellent in developability, solubility, and adhesiveness with a board | substrate, a preferable copolymer can be obtained.

The (b3) may be reacted with 2 to 80 mol%, preferably 2 to 50 mol% with respect to the total number of moles of the structural unit derived from (b1). When the (b3) is reacted in the above range, the crosslinking density is increased, so the sensitivity and developability are excellent.

An example of the manufacturing method of the copolymer (B-1) of said (b1) and (b2) is as follows. To the flask equipped with the stirrer, the thermometer, the reflux cooling tube, the dropping lot and the nitrogen inlet tube, 0.5 to 20 times the solvent was introduced on a weight basis with respect to the total amount of (b1) and (b2). Replace with Then, after heating a solvent to 40-140 degreeC, 0.5-20 times of a solvent and a polymerization initiator with respect to the predetermined amount of said (b1) and (b2) and the total amount of said (b1) and (b2) were made To the total moles of the above (b1) and (b2), a solution (stirred and dissolved under room temperature or heating) added 0.1 to 10 mol% was added dropwise to the flask over 0.1 to 8 hours from a dropping lot, and 40 to 140 ° C. Stir for 1 to 10 hours. In the above process, the solvent may be used in the normal radical polymerization reaction, specifically, 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, Either one or a mixture thereof selected from the group consisting of ethylbenzene, chloroform, dimethyl sulfoxide and the like can be used. The polymerization initiator may be a polymerization initiator commonly used in the art, it is not particularly limited. Specifically, diisopropylbenzenehydroperoxide, di-t-butylperoxide, benzoyl peroxide, t-butylperoxyisopropylcarbonate, t-amylperoxy-2-ethyl hexanoate, t-butylperoxy Organic peroxides such as 2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylbareronitrile), dimethyl 2,2'-azobis (2-methylpropionate) Nitrogen compounds; and the like. These can be used individually or in combination of 2 types or more, respectively. Α-methylstyrene dimer or mercapto compound may be used as the chain transfer agent in order to control the molecular weight in the above process. The α-methylstyrene dimer or mercapto compound may be used in an amount of 0.005 to 5 parts by weight based on the total amount of (b1) and (b2). The polymerization conditions described above may be appropriately adjusted in the input method and the reaction temperature in consideration of the amount of heat generated by the production facility, polymerization, and the like.

An example of the manufacturing method of the copolymer (B-2) obtained by making said (b3) further react with the copolymer (B-1) of said (b1) and (b2) is as follows. (B1) in the copolymer obtained by preparing the copolymer of (b1) and (b2) in the same manner as above, then substituting the atmosphere in the flask with nitrogen for air and copolymerizing the (b1) and (b2). Reaction catalyst of carboxyl group and epoxy group of 0.01 to 5 parts by weight relative to the total amount of (b3), (b1) to (b3) of 2 to 80 mole%, based on the constitutional units derived from (e.g., trisdimethyl aminomethylphenol) And 0.001 to 5 parts by weight of a polymerization inhibitor (for example, hydroquinone) based on the total amount of (b1) to (b3) in a flask to react at 60 to 130 ° C. for 1 to 10 hours to obtain a copolymer (B-1). have. At this time, similarly to the copolymerization conditions described above, the charging method and the reaction temperature may be appropriately adjusted in consideration of the amount of heat generated by the production equipment, polymerization, and the like.

The weight average molecular weight in terms of polystyrene of the alkali-soluble resin (B) may be 3,000 to 100,000, preferably 5,000 to 50,000. When the weight average molecular weight of the said (B) alkali-soluble resin exists in the range of 3,000-100,000, film | membrane reduction is prevented at the time of image development, and the omission property of a pattern part is favorable.

It is preferable that acid value of the said alkali-soluble resin (B) exists in the range of 30-150 (mgKOH / g) based on solid content. If the acid value is less than 30 mgKOH / g, there is a possibility that the developability to the alkaline water is lowered, leaving a residue on the substrate, and if the acid value exceeds 150 mgKOH / g, the possibility of desorption of the pattern is increased.

The alkali-soluble resin (B) may be included in an amount of 5 to 90 parts by weight, preferably 10 to 80 parts by weight, based on the solids in the photosensitive resin composition. When the alkali-soluble resin (B) is included in the above range, solubility in a developing solution is sufficient, so that pattern formation is easy, and the reduction of the film portion of the pixel portion of the exposed portion is prevented at the time of development, so that the missing property of the non-pixel portion is improved. desirable.

Photopolymerization  The compound (C)

Although the said photopolymerizable compound (C) is a compound which can superpose | polymerize by the action of the photoinitiator mentioned later, it will not specifically limit, Preferably it is a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound, or a trifunctional or more than polyfunctional photopolymerizable. Compounds and the like.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl py. And commercially available products include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nipbon Kayaku), and Biscotti 158 (Osaka Yuki Kagaku High School).

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, and the like; 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 Kagakusa).

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, dipentaerythritol hexa (meth) acrylate, etc. are commercially available products such as Aronix M-309, TO-1382 (Doagosei), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPHA-40H (Nipbon Kayaku).

Among the photopolymerizable compounds (C) exemplified above, trifunctional or more than trifunctional (meth) acrylic acid esters and urethane (meth) acrylates are particularly preferable in terms of excellent polymerizability and improving strength.

The photopolymerizable compound (C) illustrated above can be used individually or in combination of 2 types or more, respectively.

It is preferable to contain content of the said photopolymerizable compound (C) 5 to 45 weight% with respect to solid content in colored photosensitive resin composition, and it is especially preferable to contain 7 to 45 weight%. When the said photopolymerizable compound (C) is contained 5 to 45 weight% by said reference | standard, since the intensity | strength and smoothness of a pixel part become favorable, it is preferable.

Photopolymerization Initiator (D)

The photoinitiator (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 tee 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 oxatone compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy Hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 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 -One, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

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, and the like.

Specific examples of the triazine-based 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, 2,4-bis (trichloromethyl ) -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, 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole are preferably used do.

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

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. 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 said 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, a titanocene compound, etc. are mentioned as another photoinitiator.

You may use combining the photoinitiator (D-1) with the said photoinitiator (D). When using a photoinitiator adjuvant (D-1) 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 (D-1), 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-dimethylamino Benzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethyl Aromatic amine compounds, such as amino) 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 and dichloro And aromatic heteroacetic acids such as phenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

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

The amount of the photopolymerization initiator (D) used is 0.1 to 40% by weight, preferably 1 to 30% by weight based on the total amount of the alkali-soluble resin (B) and the photopolymerizable compound (C). When the photoinitiator (D) is in the range of 0.1 to 40% by weight based on the above criteria, the colored photosensitive resin composition is highly sensitive and the exposure time is shortened, so productivity is improved and high resolution can be maintained. Since the intensity | strength of the formed pixel part and the smoothness in the surface of this pixel part become favorable, it is preferable.

In the case of using the photopolymerization initiation aid (D-1), the amount of the photopolymerization initiation aid (D-1) is used in terms of weight fraction based on the total amount of the alkali-soluble resin (B) and the photopolymerizable compound (C). 0.1 to 50% by weight, preferably 1 to 40% by weight. When the usage-amount of the said photoinitiator (D-1) exists in the range of 0.1 to 50 weight% on the said reference | standard, since the sensitivity of a coloring photosensitive resin composition will become high and the productivity of the color filter formed using this composition will improve. desirable.

Solvent (E)

The solvent (E) is a mixture of two or more compounds, one of which is a compound represented by the following formula (1).

<Formula 1>

In the above formula, R1 represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group or benzyl group having 2 to 10 carbon atoms, and R2 represents hydrogen or a methyl group.

The compound represented by Chemical Formula 1 is preferably contained in 1 to 50% by weight, more preferably 5 to 30% by weight based on the total weight of the solvent. When the compound represented by Formula 1 is included in the above range, the coloring photosensitive resin composition may reduce defects due to vacuum drying stains, and in the case of the coloring photosensitive resin composition including dyes, solubility may be improved to solve problems such as precipitation. .

It is preferable that at least 1 sort (s) of the benzoic acid ester whose boiling point is 150 degreeC-330 degreeC is used for the compound represented by the said Formula (1). When the boiling point of the benzoic acid ester is lower than 150 ° C., the solvent is dried during the process due to low boiling point, and thus the process characteristics are decreased. In the case of more than 330 ° C., the residual solvent is not dried during prebake, thereby forming a pattern. There is a drawback to interruption.

Specific examples of the benzoic acid esters usable as the compound represented by Formula 1 include methyl benzoate, ethyl benzoate, propyl benzoate, isopropyl benzoate, butyl benzoate, isobutyl benzoate, isopentyl benzoate and hexyl Benzoate, benzylbenzoate, methylmethylbenzoate, ethylmethylbenzoate, propylmethylbenzoate, isopropylmethylbenzoate, isodecylbenzoate, allylbenzoate, linalylbenzoate. From the standpoint of dispersion stability and the like, in particular, methylbenzoate, ethylbenzoate, propylbenzoate, isopropylbenzoate, butylbenzoate, isobutylbenzoate, isopentylbenzoate, hexylbenzoate, isodecylbenzoate and lees It is preferred that at least one selected from the group consisting of nalylbenzoate and benzylbenzoate is used.

As another kind of solvent mixed with the compound represented by General formula (1), what melt | dissolves or disperse | distributes each component of a composition and does not react with each component is used preferably.

Examples of such other solvents include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates, and propylene. Glycol alkyl ether propionate, aromatic hydrocarbons, ketones, esters and the like.

As an example of these solvents, For example, as alcohol, methanol, ethanol, benzyl alcohol, etc .; As ether, tetrahydrofuran and the like; As glycol ether, Ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, etc .; As ethylene glycol alkyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, etc .; As diethylene glycol monoalkyl ether, Diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, etc .; As diethylene glycol dialkyl ether, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .; As propylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc .; As propylene glycol alkyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc .; As propylene glycol alkyl ether propionate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc .; As an aromatic hydrocarbon, toluene, xylene, etc .; Examples of the ketone include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, and the like; As the ester, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, ethyl 2-hydroxypropionate (ethyl lactate), methyl 2-hydroxy-2-methylpropionate, 2 Ethyl hydroxy-2-methyl propionate, methyl hydroxyacetic acid, ethyl hydroxyacetate, butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate, methyl 3-hydroxypropionate Propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoic acid, methyl methoxyacetate, methoxyacetic acid ethyl, methoxyacetic acid propyl, methoxy butylacetate, ethoxyacetic acid Methyl, ethoxy acetate, ethoxy acetate, ethoxy acetate, methyl propoxy acetate, ethyl acetate, propoxyacet Propyl, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2- Butyl methoxy propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-part Propyl oxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxypropion Butyl, and 3-butoxy-propionic acid methyl, 3-butoxy-ethyl, 3-butoxy propyl propionate, butyl propionate, 3-butoxy respectively.

Among these, alcohols, esters, diethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates, ethylene glycol alkyl ether acetates, and diethylene glycol dialkyl ethers are particularly preferable. Benzyl alcohol, ethyl lactate, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether Acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol diethyl ether are preferable.

In addition, the compound represented by Formula 1 may be further mixed with other high boiling point solvent having a boiling point of 150 ℃ ~ 330 ℃. Generally, a higher boiling point is referred to as a high boiling point solvent based on propylene glycol monomethyl ether acetate (boiling point of 150 ° C).

As the high boiling point solvent which can be mixed, for example, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methyl Pyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, diethyl oxalate, diethyl maleate , γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like.

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. If content of the said solvent (E) is the range of 60 to 90 weight% based on said reference | standard, it coats with application apparatuses, such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes called a die coater), an inkjet, etc. Since coating property becomes favorable at the time of carrying out, it is preferable.

Additive (F)

As the additive (F) 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 the other polymer compound 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, polyurethanes, and the like. 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 bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, noblock type epoxy resin, other aromatic epoxy resin, 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, cyclohexane dicarboxylic acid bis oxetane and the like.

The said 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 said polyhydric carboxylic anhydride, what is marketed can be used as an epoxy resin hardening | curing agent. As a specific example of the said epoxy resin hardening | curing agent, a brand name (Adekahadona EH-700) (made by Adeka Industrial Co., Ltd.), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), a brand name (MH-700) (New Nippon Ewha Co., Ltd.) etc. are mentioned. The hardeners illustrated above can be used individually or in mixture of 2 or more types.

The surfactant may be used to further improve the film formability of the photosensitive resin composition, and a fluorine-based surfactant or a silicone-based surfactant may be preferably used.

The silicone-based 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, manufactured by GE Toshiba And TSF-4452. Examples of the fluorine-based surfactant include Megapieces F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink & Chemicals Co., Ltd. as commercially available products. Surfactant illustrated above can be used individually or in combination of 2 types or more, respectively.

Specific examples of the adhesion promoter 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-mercaptopropyltrimeth And oxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane. The adhesion promoter exemplified above can be used individually or in combination of 2 or more types, 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 weight of solids 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 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 and the like.

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

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

The color filter according to the present invention comprises a color layer formed by applying the coloring photosensitive resin composition according to the present invention on the substrate and exposing and developing 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 cross-sectional views schematically showing the procedure for manufacturing a color filter using the colored photosensitive resin composition 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. Specifically, a color layer 3 made of a colored photosensitive resin composition is formed on the substrate 1 (FIG. 1A), and the formed color layer 3 is irradiated with a predetermined pattern (FIG. 1B), followed by development. (FIG. 1C). There may be a pre-formed colored pattern 2 on the substrate 1, or may be heated after the development.

The substrate 1 is not limited and may be a substrate of a 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), poly carbonate (PC), or the like. That is, the substrate may be a silicon (Si), silicon oxide (SiOx) or 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 color layer 3 which consists of a coloring photosensitive resin composition is formed, Comprising: The color layer 3 consists of solid components of a coloring photosensitive resin composition, and contains few volatile components.

The thickness of the color layer 3 is determined by the coating conditions such as the viscosity of the composition, the concentration of solids, the coating speed, and the like, and when the colored photosensitive resin composition of the present invention is used, the color layer 3 having a thickness of 0.5 to 5 μm is used. ) Can be obtained.

Subsequently, as shown in FIG. 1B, the color layer 3 made of the colored photosensitive resin composition is exposed to light. In order to expose, for example, the color 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. According to the pattern of the light transmitting part 13, the color layer 3 is exposed. The irradiation amount of the light beam 20 is suitably selected according to the coloring photosensitive resin composition used. The portion irradiated with the light beam 20 is much smaller in solubility than the portion not irradiated with the light beam 20, thereby maximizing the difference in solubility between them.

After the exposure operation described above, development is performed 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, aqueous solutions, such as an alkali compound, such as sodium carbonate, sodium hydroxide, potassium hydroxide, potassium carbonate, tetramethylammonium hydroxide, are used.

By the development, the light unradiated area which is not irradiated by the light ray in the color layer is removed. On the contrary, the light irradiation area irradiated by the light rays remains to constitute the coloring pattern 3 '. After development, the layer is washed with ordinary water and dried to obtain a predetermined colored pattern 3 '. Moreover, you may heat-process after drying. The colored pattern 3 'formed by the heat treatment is cured, and the mechanical strength thereof 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.

The color filter formed as described above is as shown in Figs. 2A and 2B. 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 for shielding light, the layer appears black. This colored pattern may exist in the form of a lattice (mosaic) (FIG. 2A) or in the form of a line (FIG. 2B).

On the other hand, the method of forming the colored layer of a color filter using the inkjet head (droplet discharge head) is proposed recently (refer patent document 1: Unexamined-Japanese-Patent No. 2002-372613). In the manufacturing method of the color filter using such an inkjet head, as described in patent document 1, each color is discharged and dried on the board | substrate with which the partition (bank) for preventing the ink of each color is mixed is provided, and drying. The colored layer which consists of colored parts of is formed. In such a method, it is easy to control the discharge position of the droplets of the material for forming the colored layer (the composition for forming the colored layer), and the waste of the composition for forming the colored layer can be reduced, thereby reducing the load on the environment. In addition, manufacturing cost can also be suppressed.

Next, the liquid crystal display of the present invention will be described. The liquid crystal display according to the present invention includes the color filter according to the present invention described above.

The liquid crystal display device includes a configuration known to those skilled in the art, except that the 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.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall 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.

Preparation of Pigment Dispersion

Pigment Dispersion MR

C.I. Pigment Red 254 8.2 parts by weight, C.I. 12.3 parts by weight of Pigment Red 177, 2.5 parts by weight of Azispa PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as a dispersant, a copolymer of methacrylic acid and benzyl methacrylate (methacrylic acid unit and benzyl methacrylate) The ratio with the unit is a molar ratio of 27:73, acid value of 83, polystyrene equivalent weight average molecular weight of 18,000), 10.3 parts by weight, and 66.7 parts by weight of propylene glycol monomethyl ether acetate as a solvent, mixed and dispersed for 8 hours by a bead mill. Pigment dispersions (MR) were prepared.

Pigment Dispersion MG

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 by weight of cyclohexanone The mixture was dispersed and dispersed for 12 hours to prepare a pigment dispersion (MG).

Pigment Dispersion MB

10 parts by weight of CI Pigment Blue (PB15: 6) 15: 6, 4 parts by weight of CI Pigment Violet 23 (PV23), 4 parts by weight of BYK-2000 (trade name) as a dispersant, dipropylene glycol, a DPMA organic solvent. 80 parts by weight of methyl ether acetate and 2 parts by weight of benzyl methacrylate / methacrylic acid (70:30 mol%, styrene-weighted average molecular weight in terms of styrene) of binder resin were mixed and dispersed for 12 hours using a bead mill to disperse the pigment dispersion. (MB) was prepared.

Preparation of coloring photosensitive resin composition

Comparative Example 1

21.74 parts of the above <pigment dispersion liquid MR>, C.I. 1.15 parts of solvent yellow 163, a copolymer of methacrylic acid and benzyl methacrylate (the ratio of the methacrylic acid unit and the benzyl methacrylate unit is 27:73 in molar ratio, the acid value is 83, and the weight average molecular weight in terms of polystyrene is 18,000) 9 parts, 2.95 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co.), 0.59 parts of Irgacure OXE01 (manufactured by BASF), and 64.57 parts of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

Comparative Example 2

In the composition of <Comparative Example 1>, except for CI solvent yellow 163, a colored photosensitive resin composition was prepared in which the remainder was mixed in the same composition.

&Lt; Example 1 >

The colored photosensitive resin composition was produced similarly except having changed the solvent of <Comparative Example 1> into 6.46 parts of methyl benzoate, and 58.11 parts of propylene glycol monomethyl ether acetate.

<Example 2>

The colored photosensitive resin composition was produced similarly except having changed the solvent of <Comparative Example 1> into 12.91 parts of methyl benzoate, and 51.66 parts of propylene glycol monomethyl ether acetate.

<Example 3>

The colored photosensitive resin composition was produced similarly except having changed the solvent of <Comparative Example 1> into 19.37 parts of methyl benzoate, and 45.2 parts of propylene glycol monomethyl ether acetate.

<Example 4>

The colored photosensitive resin composition was produced similarly except having changed the solvent of <Comparative Example 1> into 6.46 parts of ethyl benzoate, and 58.11 parts of propylene glycol monomethyl ether acetate.

Example 5

A colored photosensitive resin composition was produced in the same manner as in Comparative Example 1, except that 12.91 parts of ethylbenzoate and 51.66 parts of propylene glycol monomethyl ether acetate were used.

<Example 6>

The colored photosensitive resin composition was produced similarly except having changed the solvent of <Comparative Example 1> into 19.37 parts of ethyl benzoate and 45.2 parts of propylene glycol monomethyl ether acetate.

<Example 7>

The colored photosensitive resin composition was produced similarly except having changed the solvent of <Comparative Example 1> into 6.46 parts of isopropyl benzoates, and 58.11 parts of propylene glycol monomethyl ether acetate.

<Example 8>

The colored photosensitive resin composition was produced similarly except having changed the solvent of <Comparative Example 1> into 12.91 parts of isopropyl benzoates and 51.66 parts of propylene glycol monomethyl ether acetate.

Example 9

The colored photosensitive resin composition was produced similarly except having changed the solvent of <Comparative Example 1> into 19.37 parts of isopropyl benzoate and 45.2 parts of propylene glycol monomethyl ether acetate.

Comparative Example 3

22.52 parts of said <pigment dispersion liquid MG>, 0.51 part of CI solvent yellow 163, and a copolymer of methacrylic acid and benzyl methacrylate (the ratio of methacrylic acid unit and benzyl methacrylate unit is molar ratio 27:73, and acid value is 83, polystyrene conversion weight average molecular weight is 18,000) resin 8.86 parts, KAYARAD DPHA (manufactured by Nippon Kayaku) 2.95 parts, Irgacure OXE01 (BASF) 0.59 parts, ethyl lactate 35.2 parts, propylene glycol monomethyl ether acetate 11.77 parts And 17.6 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

<Example 10>

A colored photosensitive resin composition was produced in the same manner as the solvent of <Comparative Example 3> except that 12.91 parts of methylbenzoate, 22.29 parts of ethyl lactate, 11.77 parts of propylene glycol monomethyl ether acetate, and 17.6 parts of propylene glycol monomethyl ether were used. It was.

<Example 11>

A colored photosensitive resin composition was produced in the same manner as the solvent of <Comparative Example 3> except that 12.91 parts of ethylbenzoate, 22.29 parts of ethyl lactate, 11.77 parts of propylene glycol monomethyl ether acetate and 17.6 parts of propylene glycol monomethyl ether were used. It was.

<Example 12>

The same colored photosensitive resin composition was used except having changed the solvent of <Comparative Example 3> into 12.91 parts of isopropyl benzoates, 22.29 parts of ethyl lactate, 11.77 parts of propylene glycol monomethyl ether acetate, and 17.6 parts of propylene glycol monomethyl ether. Prepared.

Example 13

The same colored photosensitive resin composition was used except having changed the solvent of <Comparative Example 3> into 12.91 parts of isodecyl benzoate, 22.29 parts of ethyl lactate, 11.77 parts of propylene glycol monomethyl ether acetate, and 17.6 parts of propylene glycol monomethyl ether. Prepared.

<Example 14>

The colored photosensitive resin composition was similarly used except having changed the solvent of <Comparative Example 3> into 12.91 parts of linalyl benzoates, 22.29 parts of ethyl lactate, 11.77 parts of propylene glycol monomethyl ether acetate, and 17.6 parts of propylene glycol monomethyl ether. Prepared.

<Example 15>

The colored photosensitive resin composition was produced similarly except having changed the solvent of <Comparative Example 3> into 12.91 parts of benzyl benzoate, 22.29 parts of ethyl lactate, 11.77 parts of propylene glycol monomethyl ether acetate, and 17.6 parts of propylene glycol monomethyl ether. It was.

<Comparative Example 4>

A colored photosensitive resin composition was produced in the same manner as that in which the solvent of <Comparative Example 3> was changed to 64.57 parts of propylene glycol monomethyl ether acetate alone and used alone.

Comparative Example 5

A colored photosensitive resin composition was produced in the same manner as in Comparative Example 3, except that 45.2 parts of propylene glycol monomethyl ether acetate and 19.37 parts of ethyl-3-ethoxypropionate were used.

Comparative Example 6

A colored photosensitive resin composition was produced in the same manner as in Comparative Example 3, except that 45.2 parts of propylene glycol monomethyl ether acetate and 19.37 parts of propylene glycol monomethyl ether were used.

&Lt; Comparative Example 7 &

22.22 parts by weight of the <pigment dispersion MB>, C.I. 1.18 parts of solvent yellow 163 and 9 parts by weight of benzyl methacrylate / methacrylic acid (70:30 mol%, styrene-weighted average molecular weight 15,000) polymer as the binder resin and the curable monomer dipentaerythritol pentaacryl commonly used Rate 8 parts by weight, 0.5 parts by weight of azobisisobutyronitrile (hereinafter referred to as AIBN) and 0.5 parts by weight of a surfactant (SH8400; manufactured by Toray Silicone) as a thermal initiator were added to 37 parts by weight of the dispersion, followed by diethylene glycol. 45 parts by weight of monoethyl ether acetate was added to prepare a composition.

&Lt; Comparative Example 8 >

20 parts by weight of propylene glycol monomethyl ether acetate and 25 parts by weight of diethylene glycol monoethyl ether acetate were added to the solvent of <Comparative Example 7> to prepare a composition.

<Example 16>

20 parts by weight of methylbenzoate and 25 parts by weight of diethylene glycol monoethyl ether acetate were added to the solvent of <Comparative Example 7> to prepare a composition.

<Example 17>

20 parts by weight of ethylbenzoate and 25 parts by weight of diethylene glycol monoethyl ether acetate were added to the solvent of <Comparative Example 7> to prepare a composition.

&Lt; Example 18 >

20 parts by weight of isopropyl benzoate and 25 parts by weight of diethylene glycol monoethyl ether acetate were added to the solvent of <Comparative Example 7> to prepare a composition.

&Lt; Example 19 >

20 parts by weight of isodecylbenzoate and 25 parts by weight of diethylene glycol monoethyl ether acetate were added to the solvent of <Comparative Example 7> to prepare a composition.

Example 20

20 parts by weight of linalyl benzoate and 25 parts by weight of diethylene glycol monoethyl ether acetate were added to the solvent of <Comparative Example 7> to prepare a composition.

&Lt; Example 21 >

20 parts by weight of benzyl benzoate and 25 parts by weight of diethylene glycol monoethyl ether acetate were added to the solvent of <Comparative Example 7> to prepare a composition.

Experimental Example 1

Color filters were prepared using the colored photosensitive resin compositions prepared in Examples 1 to 15 and Comparative Examples 1 to 6. That is, after applying each of the colored photosensitive resin composition on the glass substrate by spin coating method, and after removing the residual solvent by vacuum drying apparatus to observe the defect at 50 times magnification by using an optical microscope and the results are shown in Table 1 And in Table 2.

<Defects after vacuum drying>

(Double-circle): No defect in 50 magnification optical microscope observation

(Circle): 1-10 defects at the time of 50 magnification optical microscope observation

(Triangle | delta): 11-30 defects at the time of 50 magnification optical microscope observation

×: 30-99 defects at 50 magnification optical microscope observation

××: 100 or more defects at the time of 50x optical microscope observation

Experimental Example 2

After confirming that the colored photosensitive resin composition prepared in Examples 10 to 15 and Comparative Examples 3 to 6 were completely dissolved by stirring for 30 minutes or more, the result was visually observed whether the precipitated component remained in the liquid after standing at room temperature for 2 hours. do.

Precipitation Experiment

The observation result regarding the precipitation component observed by Experimental Example 2 is shown in Table 3 below.

○: no precipitation component

△: precipitation component generation

×: Precipitation component bundle

<Experimental Example 3>

The compositions prepared in Examples 16 to 21 and Comparative Examples 7 and 8 were printed at a volume of 30 pl per ink on a black matrix having a height of 1.5 μm using a inkjet printing apparatus in a clean room at 23 ° C. and a humidity of 50%, Differences in solvents in the prepared ink compositions and the results of dryness evaluation during jetting are summarized. The dryness evaluation is repeated for 30 seconds of standing still after 30 seconds jetting and 30 seconds of still standing after 30 seconds jetting again to evaluate whether the nozzles are clogged due to drying of the ink.

◎: Does not occur for 60 repetitions (60 minutes)

○: does not occur for 50 repetitions (50 minutes)

△: does not occur for 30 repetitions (30 minutes)

×: Nozzle clogging after 10 repetitions (10 minutes)

As shown in Table 4 above, when a composition containing a high boiling point benzoic acid ester compound and a composition containing a low boiling point propylene glycol monomethyl ether acetate as a solvent are included in the composition, the nozzle is clogged when the composition contains a low boiling point solvent. It can be seen that this results in harm.

Claims (8)

It comprises the coloring agent (A) containing a pigment and dye, alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E),
The solvent (E) is a mixture of two or more compounds, one of which is a compound represented by the following general formula (1).
<Formula 1>

(In the formula, R1 represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group or benzyl group having 2 to 10 carbon atoms, and R2 represents hydrogen or a methyl group.) According to claim 1, wherein the compound represented by the formula (1) is methyl benzoate, ethyl benzoate, propyl benzoate, isopropyl benzoate, butyl benzoate, isobutyl benzoate, isopentyl benzoate, hexyl benzoate, benzyl At least one compound selected from the group consisting of benzoate, methylmethylbenzoate, ethylmethylbenzoate, propylmethylbenzoate, isopropylmethylbenzoate, isodecylbenzoate and allylbenzoate and linalylbenzoate Colored photosensitive resin composition to be used. The compound represented by the formula (1) is benzyl alcohol, ethyl lactate, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol Coloring photosensitivity, characterized in that it is mixed with at least one compound selected from the group consisting of ethyl ether acetate, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol diethyl ether Resin composition. The colored photosensitive resin composition according to claim 1, wherein the compound represented by Chemical Formula 1 is contained in an amount of 1 to 50% by weight based on the total weight of the solvent. The said coloring photosensitive resin composition is 5 to 70 weight% of the said coloring agent (A), 5 to 90 weight% of the said alkali-soluble resin (B), and 5 to 45 said photopolymerizable compound (C). A coloring photosensitive resin composition comprising a weight%. The coloring photosensitive resin composition of Claim 1 used to produce a color filter by forming a colored layer by the inkjet discharge system. A color filter comprising a color layer formed by applying the colored photosensitive resin composition according to any one of claims 1 to 6 on a substrate, and being exposed and developed in a predetermined pattern. A liquid crystal display device comprising the color filter according to claim 7.

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