JP2012083753A - Colored photosensitive resin composition, color filter and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition excellent in compatibility with a dye, from which a color filter having higher reliability can be produced.SOLUTION: The colored photosensitive resin composition contains an alkali-soluble resin, a colorant containing a pigment and/or a dye, a photopolymerizable compound, a photopolymerization initiator and a solvent. The alkali-soluble resin includes a repeating unit derived from an acid anhydride (A1) expressed by the formula. In the formula, Rand Reach independently represent a hydrogen atom or an aliphatic or aromatic hydrocarbon group having 1 to 12 carbon atoms and containing or without containing a heteroatom.

Description

  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 a dye and improved reliability. And a liquid crystal display device including the color filter.

  A color filter is incorporated in a color photographing apparatus of an image sensor such as a complementary metal oxide semiconductor (CMOS) or a charge coupled device (CCD) and is actually a color filter. It can be used to obtain images, and is also widely used for imaging elements, plasma display panels (PDP), liquid crystal display devices (LCD), field emission displays (FED), and light emitting displays (LEDs). Its application range is expanding rapidly. In particular, recently, the use for LCDs has further expanded, and accordingly, color filters are recognized as one of the most important parts in reproducing the color tone of LCDs.

  Such a color filter is manufactured by a method of forming a desired colored pattern using a colored photosensitive resin composition containing a colorant. Specifically, a coating layer made of a colored photosensitive resin composition is formed on a substrate, a pattern is formed on the formed coating layer, exposure and development are performed, and a series of processes of heating and thermosetting is repeated. Manufactured by.

  Although pigments have been used as colorants, recently there have been attempts to use dyes that are bright and have excellent heat resistance. When only a dye is used as a colorant, it is preferable because all of the excellent properties of the dye can be realized. However, since the dye is less compatible with the other components of the composition than the pigment, its use is limited. there were. Therefore, although a method using a hybrid type colorant that uses all pigments and dyes as a colorant has been attempted, the problems when using a colorant containing a dye have not been completely solved so far. .

  When a color filter is produced using a colored photosensitive resin composition containing a dye as a colorant, foreign matter is generated when the colored layer is formed due to insufficient compatibility with the materials used. Further, when producing a color filter, there is a problem that the development speed is slow, and the pattern formed during the development process with an alkaline developer frequently peels off due to insufficient sensitivity. Accordingly, there is a demand for development of a colored photosensitive resin composition suitable for a photolithography process that can solve the problems when using a colorant containing a dye or when using a dye alone as a colorant.

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a color filter that is excellent in compatibility with a dye and can be manufactured with improved reliability. It is providing the photosensitive resin composition, the color filter using the same, and a liquid crystal display device provided with the color filter.

  In order to achieve the above object, a colored photosensitive resin composition according to one aspect of the present invention includes an alkali-soluble resin, a colorant containing a pigment and / or a dye, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The alkali-soluble resin has a repeating unit derived from an acid anhydride (A1) represented by the following formula 1.

(Wherein, R ₁ and R ₂ are each independently hydrogen, a C 1-12 aliphatic or aromatic hydrocarbon group containing or not containing a hetero atom).

  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 these copolymers are converted to an acid anhydride (A1). And a compound bonded to the compound (A3) having a functional group capable of bonding to.

  The ratio of the repeating unit derived from the acid anhydride (A1) to the total number of moles of the entire repeating unit of the alkali-soluble resin can be 2 to 80 mol%.

  The ratio of the repeating unit derived from the compound (A2) having an unsaturated bond copolymerizable with the acid anhydride (A1) is 2 to 95 mol% with respect to the total number of moles of the entire repeating unit of the alkali-soluble resin. Can be.

  The ratio of the repeating unit derived from the compound (A3) having a functional group capable of binding to the acid anhydride (A1) is 2 to 95 mol% with respect to the number of moles of the repeating unit in the alkali-soluble resin (A1). Can be.

  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 the unsaturated carboxylic acid, and an unsaturated group having an alicyclic substituent. Carboxylic acid ester compounds, monosaturated carboxylic acid ester compounds of glycols, unsaturated carboxylic acid ester compounds having a substituent containing an aromatic ring, aromatic vinyl compounds, carboxylic acid vinyl esters, vinyl cyanide compounds, and maleimide compounds It can be at least one selected from the group constituted.

  The compound (A2) having an unsaturated bond copolymerizable with the acid anhydride (A1) includes methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, aminoethyl (meth) acrylate, cyclopentyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, Cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl ( Acrylate), norbornyl (meth) acrylate, pinenyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 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 Selected from the group consisting of N-cyclohexylmaleimide, N-phenylmaleimide, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid It is possible to use at least one compound.

  The compound (A3) having a functional group capable of binding to the acid anhydride (A1) includes 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)- At least one selected from the group consisting of 2-hydroxypropyl methacrylate can be used.

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

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

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

The colored photosensitive resin composition according to the present invention is excellent in compatibility with the pigment or dye of the colorant as a constituent of the composition, and has a high development speed and sensitivity and adhesion while containing both the pigment and the dye. Since it is excellent, there is no peeling of the pattern during the development process, and the solvent resistance is excellent.
Moreover, since it is excellent in the chemical resistance with respect to the solvent used on the manufacturing process of the color filter of the colored photosensitive resin composition by this invention, and the safety | security of long-term storage, there exists an effect which improves reliability.

3 is a diagram illustrating a manufacturing procedure of a color filter according to the present invention. 5 is a drawing showing a subsequent procedure for manufacturing a color filter according to the present invention. 5 is a drawing showing a subsequent procedure for manufacturing a color filter according to the present invention. 1 is a perspective view of a color filter according to the present invention. It is a perspective view of the color filter which continues from this invention.

  Embodiments of the present invention will be described below with reference to the accompanying drawings. However, the embodiments of the present invention can be modified in various forms, and the scope of the present invention is not limited to the embodiments described below. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art.

  The colored photosensitive resin composition according to the present invention comprises an alkali-soluble resin (A), a colorant (B) containing a pigment and / or a dye, a photopolymerizable compound (C), and a photopolymerization initiator (D). And solvent (E). Hereinafter, each component contained in the colored photosensitive resin composition of the present invention will be described in more detail.

Alkali-soluble resin (A )
The alkali-soluble resin (A) added as a binder resin to the colored photosensitive resin composition of the present invention generally has reactivity and alkali solubility due to the action of light and heat, and the colorant (B) Acts as a dispersion medium.

  The alkali-soluble resin (A) has a repeating unit derived from an acid anhydride (A1) represented by the following formula 1.

In the formula, R ₁ and R ₂ are each independently hydrogen, an aliphatic or aromatic hydrocarbon group having 1 to 12 carbon atoms, which contains or does not contain a hetero atom.

  The alkali-soluble resin (A) is an unsaturated group-containing resin having a repeating unit obtained by polymerizing the compound of Formula 1 (including copolymerization). That is, the compound of Formula 1 is polymerized alone or together with other compounds to constitute the alkali-soluble resin (A). There are no limitations on the conditions of other compounds 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 can be a copolymer of an acid anhydride (A1) and a compound (A2) having an unsaturated bond copolymerizable with the acid anhydride (A1). Further, the alkali-soluble resin (A) according to the present invention comprises an acid anhydride (A1) and a copolymer of the compound (A2) having an unsaturated bond copolymerizable with the acid anhydride (A1). It can be obtained by binding with a compound (A3) having a functional group capable of binding to A1).

  In one embodiment of the present invention, the 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 alicyclic ring Unsaturated carboxylic acid ester compounds having a substituent, monosaturated carboxylic acid ester compounds of glycols, unsaturated carboxylic acid ester compounds having a substituent containing an aromatic ring, aromatic vinyl compounds, carboxylic acid vinyl esters, cyanide It can be at least one selected from the group consisting of vinyl compounds and maleimide compounds.

  The compound (A2) having an unsaturated bond copolymerizable with the acid anhydride (A1) includes methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, aminoethyl (meth) acrylate, cyclopentyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, Cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl ( Acrylate), norbornyl (meth) acrylate, pinenyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 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, crotonic acid, itaconic acid, maleic acid, and fumaric acid It is possible to use at least one compound barrel.

  In one embodiment of the present invention, a copolymer obtained by copolymerizing (A1) and (A2) (a monomer other than (A1) and (A2) is further included in the present invention. The ratio of the repeating unit derived from each of (A1) and (A2) is the repeating unit derived from the acid anhydride (A1) with respect to the total number of moles of the entire repeating unit of the alkali-soluble resin. The proportion of the repeating unit derived from the compound (A2) having an unsaturated bond copolymerizable with the acid anhydride (A1) is 2 to 95 mol%. Can be.

  That is, when the alkali-soluble resin (A) is a copolymer of (A1) and (A2), the repeating units derived from (A1) and (A2) are 2 to 80 mol% and 2 to 95, respectively. It is preferably contained in the range of mol%. When the alkali-soluble resin (A) is a copolymer of (A1) and (A2), the repeating units derived from (A1) and (A2) are 5 to 70 mol% and 5 to 5, respectively. More preferably, it is contained in the range of 80 mol%. When each repeating unit is within these ranges, a good balance of developability, solubility and heat resistance is obtained, so that a preferable copolymer can be obtained.

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

  The compound (A3) having a functional group capable of binding to the acid anhydride (A1) includes hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4- Selected from the group consisting of hydroxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 3- (acryloyloxy) -2-hydroxypropyl methacrylate Can be used. These may be used alone or in combination of two or more, but are not limited thereto.

  The proportion of the repeating unit derived from the compound (A3) having a functional group capable of binding to the acid anhydride (A1) is 2 to 95 mol% with respect to the number of moles of the repeating unit (A1) in the alkali-soluble resin. Can be. More preferably, it is 10-90 mol%. When the composition ratio of (A3) is within this range, it is preferable because sufficient photocurability and thermosetting can be obtained, sensitivity and pencil hardness are compatible, and reliability is excellent.

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

  In a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a gas introduction tube, 0.5 to 20 times the amount of solvent (E) based on the weight based on the total amount of (A1) and (A2). And the atmosphere in the flask is replaced with nitrogen from air. Then, after raising the temperature of the solvent (E) to 40 to 140 ° C., 0 to 20 times the amount of the solvent (E) and azobisisobutyl on a weight basis with respect to the total amount of (A1) and (A2). A solution in which a polymerization initiator such as ronitrile or t-butylperoxy 2-ethylhexyl carbonate is added in an amount of 0.1 to 10 mol% with respect to the total number of moles of (A1) and (A2) Is dissolved in the flask over 0.1 to 8 hours from the dropping funnel, and further stirred at 40 to 140 ° C. for 1 to 10 hours.

  Further, a part or the whole amount of the polymerization initiator may be charged into the flask, or a part or the whole amount of (A1) and (A2) may be charged into the flask. Moreover, in order to control molecular weight and molecular weight distribution, you may use (alpha) -methylstyrene dimer and a mercapto compound as a chain transfer agent. The amount of α-methylstyrene dimer or mercapto compound used is 0.005 to 5% on a weight basis with respect to the total amount of (A1) and (A2). The polymerization conditions may be adjusted so that the charging method and the reaction temperature are different from the above in consideration of the production equipment and the amount of heat generated by the polymerization.

  In one embodiment of the present invention, the alkali-soluble resin (A) binds the compound (A3) having a functional group capable of binding to the acid anhydride (A1) to the copolymer of (A1) and (A2). In the case of a compound, it can be produced as follows.

  The atmosphere in the flask was replaced from nitrogen to air, and 3 to 95 mol% of (A3) acid anhydride, with respect to the repeating unit derived from the copolymer of (A1) and (A2), As a reaction catalyst for alcohol, for example, dimethylaminoethyl methacrylate is 0.01 to 5% by weight based on the total amount of (A1) to (A3), and as a polymerization inhibitor, for example, hydroquinone (A1 ) To (A3), 0.001 to 5% on a weight basis is charged into the flask and reacted at 60 to 130 ° C. for 1 to 10 hours to obtain a co-weight of (A1) and (A2). The union and (A3) can be reacted. The polymerization conditions may be adjusted so that the charging method and the reaction temperature are different from the above in consideration of the production equipment and the amount of heat generated by the polymerization.

  The alkali-soluble resin (A) can have a polystyrene-equivalent weight average molecular weight of 3,000 to 100,000, and preferably 5,000 to 50,000. When the weight average molecular weight of the alkali-soluble resin (A) is in the range of 3,000 to 100,000, it is preferable because film loss hardly occurs during development and the developability of non-pixel portions tends to be good during development.

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the alkali-soluble resin (A) is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. . If the molecular weight distribution of the alkali-soluble resin (A) is 1.5 to 6.0, it is preferable because the developability is excellent.

  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 solid content of the colored photosensitive resin composition. . When the content of the alkali-soluble resin (A) is 5 to 90% by weight, the solubility in the developer is sufficient, so that a development residue hardly occurs on the non-pixel portion of the substrate. Since the film thickness of the portion hardly occurs, it is preferable because the developability of the non-pixel portion tends to be good.

Colorant (B )
The colorant (B) used in the colored photosensitive resin composition of the present invention can contain a pigment and a dye, respectively, or together.

As the pigment, an organic pigment or an inorganic pigment generally used in the art can be used, and these can be used alone or in combination of two or more.
If necessary, the pigment can be treated with resin, surface treatment with a pigment derivative with an acidic group or basic group introduced, grafting onto the pigment surface with a polymer compound, etc., atomization treatment with impurities such as sulfuric acid atomization or impurities Cleaning treatment with an organic solvent or water for removing water, removal treatment of ionic impurities by an ion exchange method, or the like may be performed.

  Various pigments used for inkjet inks can be used as the pigment, specifically water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments. , Dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavantron pigments, pyranthrone pigments, and diketopyrrolopyrrole pigments. .

  Moreover, as an inorganic pigment, a metal compound such as a metal oxide or a metal complex salt can be used. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony And metal oxides such as carbon black or composite metal oxides.

In particular, as the pigment, compounds specifically classified as pigments by the color index (published by The Society of Dyers and Colorists) can be used, and more specifically, the following color index (C.I. ) Number pigments can be used, but are not necessarily limited to these.
CI 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
CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71
CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264
CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38
CI Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64 and 76
CI Pigment Green 7, 10, 15, 25, 36, 47 and 58
CI Pigment Brown 28
CI Pigment Black 1 and 7 etc.

  Among the exemplified CI pigments (pigments), CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 185, CI 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 CI pigment blue 15: 6, CI pigment green 7, CI pigment green 36 or CI pigment green 58 is preferably used.

  It is preferable to use a pigment dispersion in which the particle diameter is uniformly dispersed. An example of a method for uniformly dispersing the pigment particle diameter is a method of dispersing by adding a pigment dispersant. According to this method, the pigment is in a state where the pigment is uniformly dispersed in the solution. A dispersion is obtained.

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

  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 In addition, there are other trade names such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (POLYFLOW) (manufactured by Kyoeisha Chemical Co., Ltd.), F-TOP (EFTOP) (manufactured by Tochem Products), Mega Fuck. (MEGAFAC) (Dainippon Ink Chemical Co., Ltd.), Florad (Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (Asahi Glass Co., Ltd.), SOLSPERSE ) Zeneca Co., Ltd.), EFKA (manufactured by EFKA Chemical Co., Ltd.), and PB821 (Ajinomoto Co., Ltd.), and the like.

  The pigment dispersant is usually used in an amount of 1 part by weight or less with respect to 1 part by weight of the pigment, and preferably 0.05 to 0.5 part by weight. When the pigment dispersant is used in the above-described content, it is preferable because a pigment having a uniform particle diameter can be obtained.

  The dye is not particularly limited as long as it has solubility in an organic solvent. It is preferable to use a dye that can ensure the solubility in an alkali developer, the heat resistance, the solvent resistance, and the like while having solubility in an organic solvent.

  As the dye, an acid dye having an acid group such as sulfonic acid or carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide of an acid dye, or the like, and a derivative thereof can be used. In addition, azo, xanthene, and phthalocyanine acid dyes and derivatives thereof can also be used.

  Preferably, the dye may be a compound classified as a dye in the Color Index (published by The Society of Dyers and Colorists) or a known dye described in a dyeing note (manufactured by Color Dye).

Specific examples of dyes are CI solvent dyes,
C. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, and other yellow dyes,
C.I. Solvent Red 45, 49, 122, 125, 130 and other red dyes,
C.I. Solvent Orange 2, 7, 11, 15, 26, 56 and other orange dyes,
C. I. Solvent Blue 35, 37, 59, 67 and other blue dyes, and
C. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and other green dyes.

In addition, as CI 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, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251 etc. Yellow dye,
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, 295, 308, 312, 315, 316, 339, 341, 345, Red dyes such as 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426,
CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173, etc. Color dyes,
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, 335, 340 and other blue dyes,
C. I. Acid Violet 6B, 7, 9, 17, 19 and other violet color dyes, and
CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc.

As CI direct dyes,
C.I.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, 136, 138, 141 yellow dyes,
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, Red dyes such as 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250,
CI Direct Orange Orange dyes such as 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107,
C.I.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, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293 How blue dye,
C.I.Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104, etc., and ,
CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc.

In addition, as CI modern dyes,
CI Yellow Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, etc.,
C.I.Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95, and other red dyes,
CI Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48 Orange dye, such as
CI Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84 and other blue dyes,
CI Modern Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58, etc. Dyes and
C. I. Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and the like.

  The content of the dye in the colorant (B) is preferably included in the range of 0.5 to 80% by weight with respect to the solid content in the colorant (B). % By weight is more preferable, and 1 to 50% by weight is particularly preferable. When the content of the dye in the colorant (B) is within this range, it is possible to prevent the problem of reliability deterioration that the dye is squeezed out by the organic solvent after pattern formation, and it is preferable because the sensitivity is excellent.

  The content of the colorant (B) should be contained in the range of 5 to 70% by weight, preferably 10 to 50% by weight, based on the solid content in the colored photosensitive resin composition. When the colorant (B) is contained in the range of 5 to 70% by weight based on the above criteria, the color density of the pixel is sufficient even when a thin film is formed, and the developability of the non-pixel portion during development is not deteriorated. This is preferable because a residue hardly occurs.

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

Photopolymerizable 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 later, but is preferably a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound, or a trifunctional or higher polyfunctional compound. There are functional photopolymerizable compounds.

  Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the like as commercial products. Examples include Aronix M-101 (manufactured by Toa Gosei Co., Ltd.), KAYARAD TC-110S (manufactured by Nippon Kayaku Co., Ltd.), and Biscote 158 (manufactured by Osaka Organic Chemical Industries, Ltd.).

  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, and bisphenol A. Examples thereof include bis (acryloyloxyethyl) ether and 3-methylpentanediol di (meth) acrylate, and commercially available products include Aronix M-210, M-1100, 1200 (manufactured by Toa Gosei Co., Ltd.), KAYARAD HDDA (Japan) Kayaku Co., Ltd.), Biscoat 260 (Osaka Organic Chemical Co., Ltd.), AH-600, AT-600, UA-306H (Kyoeisha Chemical Co., Ltd.), and the like.

  Specific examples of the polyfunctional photopolymerizable compound having three or more functions include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and pentaerythritol tris. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, and dipentaerythritol hexa ( Examples of commercially available products include Aronix M-309, TO-1382 (manufactured by Toa Gosei Co., Ltd.), KAYARAD TMPTA, KAYARAD D. PHA, KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.) and the like.

  Among the exemplified photopolymerizable compounds (C), tri- or higher functional (meth) acrylic acid esters and urethane (meth) acrylates are particularly preferable in that they are excellent in polymerizability and can improve strength. Moreover, the illustrated photopolymerizable compound (C) can be used alone or in combination of two or more.

  The content of the photopolymerizable compound (C) is preferably included in the range of 5 to 45% by weight, particularly 7 to 45% by weight, based on the solid content in the colored photosensitive resin composition. More preferably, it is included in the range. When the photopolymerizable compound (C) is contained in the range of 5 to 45% by weight, it is preferable because the strength and smoothness of the pixel portion are improved.

Photopolymerization initiator (D )
The photopolymerization initiator (D) is not particularly limited as long as the photopolymerizable compound (C) can be polymerized. In particular, the photopolymerization initiator (D) is an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound, and a thioxanthone compound from the viewpoint of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, and the like. It is preferable to use at least one compound selected from the group consisting of compounds.

  Specific examples of acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-Methylpropan-1-one, 1-hydroxycyclohexyl phenyl 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] propan-1-one, and 2- (4-methylbenzyl)- 2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one and the like can be mentioned.

  Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl). ) Benzophenone, 2,4,6-trimethylbenzophenone and the like.

  As a specific example of the triazine compound, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 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 (such as trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl)- 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) -4,4 ′, 5,5′-tetra Examples include phenyl-1,2′-biimidazole, or an imidazole compound in which the phenyl group at the 4,4 ′, 5,5 ′ position is substituted with a carboalkoxy group. Among these, 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 preferably used.

  Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and commercially available products include OXE01 and OXE02 manufactured by BASP.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

  Further, other photopolymerization initiators can be used in combination as long as the effects of the present invention are not impaired. Examples of other photopolymerization initiators include benzoin-based compounds and anthracene-based compounds, and these can be used alone or in combination of two or more.

  Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. .

  In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, or titanocene A compound etc. are mentioned as a photoinitiator.

  The photopolymerization initiator (D) can be used in combination with a photopolymerization initiation auxiliary agent. If a photopolymerization initiator auxiliary is used in combination with the photopolymerization initiator (D), a photosensitive resin composition containing these is preferred because it becomes more sensitive and improves productivity. As the photopolymerization initiation auxiliary agent, for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group is preferably used.

  Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-Ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (common name: Michler's ketone), and 4,4′-bis And aromatic amine compounds such as (diethylamino) benzophenone. As the amine compound, an aromatic amine compound is preferably used.

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

  Specific examples of the organic sulfur compound having a 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, trimethylolpropane tris (3 mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis ( 3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate).

  The amount of the photopolymerization initiator (D) used is 0.1 to 40% by weight based on the solid content with respect to the total amount of the alkali-soluble resin (A) and the photopolymerizable compound (C). It is preferably 1 to 30% by weight. 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 that productivity is improved and high resolution is achieved. This is preferable because the strength of the pixel portion formed using this composition and the smoothness on the surface of the pixel portion are improved.

  Moreover, when using a photopolymerization start adjuvant, the usage-amount of a photopolymerization start adjuvant is a weight part with respect to the total amount of alkali-soluble resin (A) and a photopolymerizable compound (C) on the basis of solid content. The ratio is 0.1 to 50% by weight, preferably 1 to 40% by weight. When the amount of the photopolymerization initiation auxiliary used is in the range of 0.1 to 50% by weight, the sensitivity of the colored photosensitive resin composition is further increased, and the productivity of the color filter formed using this composition is increased. Since it improves, it is preferable.

Solvent (E)
The type of the solvent (E) is not limited as long as it is effective for dispersing or dissolving other components contained in the colored photosensitive resin composition. In particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters or amides are preferable.

  Specific examples of the solvent (E) include 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, and propylene glycol. Such as 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 ether, dipropylene glycol dibutyl ether , Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, propanol, butanol, hexanol, cyclohexanol, Alcohols such as ethylene glycol and glycerol, 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, ethyl 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 mono Examples include esters such as ethyl ether acetate, ethylene carbonate, propylene carbonate, and γ-butyrolactone.

  Among the exemplified solvents, in view of coating property and drying property, preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, or 3- Methyl methoxypropionate can be used.

The exemplified solvents (E) can be used alone or in admixture of two or more.
The content of the solvent (E) is 60 to 90% by weight, preferably 70 to 85% by weight, based on the total amount of the colored photosensitive resin composition containing the solvent (E). When the content of the solvent (E) is in the range of 60 to 90% by weight based on the above criteria, when coating is performed with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (or die coater), and inkjet. This is preferable because the coating property is improved.

The additive additive can be selectively added as necessary, and includes, for example, other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and agglomerates. Examples include inhibitors.

  Specific examples of other polymer compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. Is mentioned.

  Curing agents are used to increase deep cure and mechanical strength. Specific examples of the curing agent include an epoxy compound, a multi-tubular isocyanate compound, a melamine compound, and an oxetane compound.

  Among the curing agents, specific examples of the epoxy compound include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolac type epoxy resin, and other aromatics. Epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, or brominated derivatives of such epoxy resins, epoxy resins and aliphatic, alicyclic or aromatics other than brominated derivatives thereof Examples thereof include epoxy compounds, butadiene (co) polymer epoxidized products, isoprene (co) polymer epoxidized products, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.

  Among the curing agents, specific examples of the oxetane compounds include carbonate bisoxetane, xylene bisoxetane, bisoxetane adipate, bisphthalate terephthalate, and bisoxetane cyclohexanedicarboxylate.

  The curing agent can be used in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators. As the polyvalent carboxylic acid anhydrides, commercially available epoxy resin curing agents are used. Specific examples of the epoxy resin curing agent include a trade name (Adeka Hadna EH-700) (manufactured by Adeka Industries Co., Ltd.), a trade name (Rikasit HH) (manufactured by Shin Nippon Rika Co., Ltd.), and a trade name (MH-700). ) (New Nippon Rika Co., Ltd.). The illustrated curing agents can be used alone or in admixture of two or more.

  The surfactant can be used to further improve the film forming property of the photosensitive resin composition, and a fluorine-based surfactant or a silicon-based surfactant is preferably used.

  Examples of the silicon surfactant include DC3PA, DC7PA, SH11PA, SH21PA, SH8400 manufactured by Toray Dow Corning Silicon Co., Ltd. as commercially available products. Moreover, TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442, etc. of GE Toshiba Silicon Corporation are mentioned. Examples of the fluorosurfactant include Megapis F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink and Chemicals, Inc. as commercially available products. The exemplified surfactants can be used alone or in combination of two or more.

  Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and 3-iso Etc. A sulfonate propyl triethoxy silane. The exemplified adhesion promoters can be used alone or in combination of two or more. The adhesion promoter can be contained in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the solid content of the colored photosensitive resin composition.

  Specific examples of the antioxidant include 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, and the like.

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

  Specific examples of the aggregation inhibitor include sodium polyacrylate.

  The colored photosensitive resin composition of the present invention can be produced, for example, by the following method. The colorant (B) is preliminarily mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle size of the coloring material is about 0.2 μm or less. At this time, if necessary, a pigment dispersant is used, and some or all of the alkali-soluble resin (A) may be blended. In the obtained dispersion, the remainder of the alkali-soluble resin (A), the photopolymerizable compound (C) and the photopolymerization initiator (D), the additive used as necessary, and the solvent (E) added as necessary. It is further added so as to have a predetermined concentration to obtain a desired colored photosensitive resin composition.

  According to another aspect of the present invention, there is provided a color filter including a colored layer having the colored photosensitive resin composition according to the present invention. The color filter according to the present invention comprises a colored layer formed by applying a colored photosensitive resin composition on an upper part of a substrate, and exposing and developing in a predetermined pattern. A partition wall may be further formed between the colored patterns, and a black matrix may be added. In addition, a protective film can be further formed on the color filter.

  1a to 1c are diagrams illustrating a manufacturing procedure of a color filter according to the present invention. When a color filter is produced using the colored photosensitive resin composition according to the present invention, for example, the colored photosensitive resin composition is subjected to pattern treatment to form a colored pattern 3 ′. That is, a color layer 3 made of a colored photosensitive resin composition is formed on the substrate 1 (FIG. 1a), and the color layer 3 thus formed is irradiated with light in a predetermined pattern (FIG. 1b) and then developed. (FIG. 1c). There may be a colored pattern 2 already formed on the substrate 1. A heating process can also be carried out after development.

  The substrate 1 is not limited and may be a substrate of the color filter itself, or may be a place where the color filter is located on a display device or the like. The substrate 1 may be a plastic plate such as a glass plate, a silicon wafer, PES (Poly Ether Sulphone), and PC (Poly Carbonate). That is, the substrate 1 can be silicon (Si), silicon oxide (SiOx), a glass substrate, or a polymer substrate.

  As shown in FIG. 1a, in order to form the colored layer 3 made of the colored photosensitive resin composition on the substrate 1, for example, the colored photosensitive resin composition diluted with a solvent is spun and spin after slitting is performed. Then, after coating on the substrate by a coating method such as slit, roll, spray, or ink jet method, a volatile component such as a solvent is volatilized. Thereby, although the colored layer 3 which consists of a colored photosensitive resin composition is formed, the colored layer 3 consists of a solid component of a colored photosensitive resin composition, and almost no volatile component is contained.

  The thickness of the colored layer 3 is determined by coating conditions such as the viscosity of the composition, the solid content concentration, the coating speed, and the like. When the colored photosensitive resin composition of the present invention is used, the thickness is 0.5. A colored layer 3 of ˜5 μm is 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 g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), etc. are usually used. The light beam 20 passes 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. The light beam 20 is shielded by the light shielding layer 12. The portion of the glass plate 11 where the light shielding layer 12 is not provided is a light projecting portion 13 through which the light beam 20 is transmitted. The colored layer 3 is exposed by such a pattern of the light projecting portion 13. The irradiation amount of the light beam 20 is appropriately selected depending on the colored photosensitive resin composition used. The portion irradiated with the light beam 20 has a lower solubility than the portion not irradiated with the light beam 20, and the difference in solubility between them is maximized.

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

  By the development, the light non-irradiated region that has not been irradiated with the light in the colored layer is removed. On the other hand, the light irradiation area irradiated with the light remains to form the colored pattern 3 ′. After development, it is generally washed with water and dried. In addition, heat treatment can be performed after drying. The colored pattern 3 'formed by the heat treatment is cured, thereby improving the mechanical strength. Thus, since the mechanical strength of colored pattern 3 'can be improved by heat processing, it is preferable to use the colored photosensitive composition containing a hardening | curing agent. The heating temperature is usually 180 ° C. or higher, preferably 200 to 250 ° C.

  As is well known, the color filter is usually a black matrix and pixels of three primary colors of red, green and blue arranged on a substrate, but the colored photosensitive resin of the present invention containing a coloring material corresponding to a certain color. By performing the above operation using the composition, a black matrix or pixel of that color is obtained, and the colored photosensitive resin composition of the present invention containing a coloring material corresponding to the target color for other colors as well The same operation can be performed using the, and the black matrix and the three primary color pixels can be arranged on the substrate. Of course, the colored photosensitive resin composition of the present invention can be applied to only one, two or three of the black matrix and the three primary colors.

  2a and 2b are perspective views of a color filter according to the present invention. In the present invention, the colored pattern means, for example, RGB color pixels 2, 3 ′, 4 ′, black matrix 5, and the like, the color pixels are colored transparent layers, and the black matrix is a layer that blocks light. is there. These color pixels and black matrix are usually formed on the substrate 1 to form a color filter. Since the color pixels 2, 3 ′, 4 ′ are transparent and colored, the light transmitted through these color pixels indicates the color of each color pixel. Since the black matrix 5 is a light shielding layer, it looks black. Such a colored pattern can be present in a plaid (mosaic) (FIG. 2a) or in a line (FIG. 2b).

  Furthermore, another aspect of the present invention provides a liquid crystal display device including the color filter according to the present invention. The liquid crystal display device includes a configuration well known to those skilled in the art in the technical field of the present invention, except that it includes a color filter. That is, all liquid crystal display devices to which the color filter of the present invention can be applied are included in the present invention. As an 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 opposed to each other at a predetermined interval, and a liquid crystal material is poured into the gap portion to form a liquid crystal layer. It is done. There is also a reflective liquid crystal display device in which a reflective layer is provided between a color filter substrate and a colored layer.

  As another example, there is a liquid crystal display device including a TFT (Thin Film Transistor) substrate superimposed on a transparent electrode of a color filter and a backlight fixed at a position where the TFT substrate overlaps the color filter. It is done. The TFT substrate is 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 added in the outer frame, and a number of liquid crystal layers provided for each region of the liquid crystal layer. A pixel electrode, 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 can be provided.

Hereinafter, preferred embodiments will be presented for the understanding of the present invention. However, the following embodiments are merely illustrative of the present invention, and various changes and modifications can be made within the scope and technical spirit of the present invention. It will be apparent to those skilled in the art that such variations and modifications are, of course, within the scope of the claims.
In the following examples and comparative examples, “%” and “parts” indicating the contents are based on weight unless otherwise specified, and the addition amount is a ratio with respect to the whole colored photosensitive resin composition.

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

Production of pigment dispersion <Pigment dispersion M1>
C. I. Pigment Green 36, 16.2 parts by weight, C.I. I. 1.8 parts by weight of Pigment Yellow 150, 4.2 parts by weight of Ajispa PB821 (manufactured by Ajinomoto 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 were used in a bead mill. For 12 hours to prepare a pigment dispersion (M1).

Synthesis of alkali-soluble resin (A) <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 funnel and a nitrogen inlet, and the atmosphere in the flask was air. The mixture was heated to 120 ° C. to a mixture containing 66.0 g (0.3 mol) of dicyclopentanyl methacrylate, 106.2 g (0.9 mol) of vinyl toluene and 136 g of propylene glycol monomethyl ether acetate. The solution added with 24.4 g of t-butylperoxy 2-ethylhexyl carbonate was dropped into the flask over 2 hours from the dropping funnel, and further stirred at 120 ° C. for 2 hours to obtain a polymer precursor. 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 methyl hydroquinone were added to the copolymer solution. Thereafter, the reaction was continued at 120 ° C. to obtain a resin having a solid content acid value of 180 mg kOH / g. The polystyrene equivalent weight average molecular weight measured by GPC was 6,700, and the molecular weight distribution (Mw / Mn) was 2.3.

<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 funnel and a nitrogen inlet, and the atmosphere in the flask was air. The mixture was heated to 120 ° C., and tert-butyl 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. A solution to which 24.4 g of peroxy 2-ethylhexyl carbonate was added was dropped into the flask over 2 hours from the dropping funnel, and further stirred at 120 ° C. for 2 hours to obtain a polymer precursor. 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 methyl hydroquinone were added to the copolymer solution. Thereafter, the reaction was continued at 120 ° C. to obtain a resin having a solid content acid value of 173 mg kOH / g. The polystyrene equivalent weight average molecular weight measured by GPC was 8,900, and the molecular weight distribution (Mw / Mn) was 2.4.

<Synthesis Example 3>
426.1 g of propylene glycol monomethyl ether acetate and 58.8 g (0.6 mol) of maleic anhydride were introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen introduction tube, and the atmosphere in the flask was air. The mixture was heated to 120 ° C. and mixed with a mixture containing 264.0 g (1.2 mol) of dicyclopentanyl methacrylate, 141.6 g (1.2 mol) of vinyl toluene and 136 g of propylene glycol monomethyl ether acetate. The solution added with 24.4 g of t-butylperoxy 2-ethylhexyl carbonate was dropped into the flask over 2 hours from the dropping funnel, and further stirred at 120 ° C. for 2 hours to obtain a polymer precursor. 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 methyl hydroquinone were added to the copolymer solution. Thereafter, the reaction was continued at 120 ° C. to obtain a resin having a solid content acid value of 130 mg kOH / g. The polystyrene-equivalent weight average molecular weight measured by GPC was 12,700, and the molecular weight distribution (Mw / Mn) was 2.2.

<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 funnel and a nitrogen inlet, and the atmosphere in the flask was air. The mixture was heated to 120 ° C. to a mixture containing 132.0 g (0.6 mol) of dicyclopentanyl methacrylate, 70.8 g (0.6 mol) of vinyltoluene and 136 g of propylene glycol monomethyl ether acetate. The solution added with 24.4 g of t-butylperoxy 2-ethylhexyl carbonate was dropped into the flask over 2 hours from the dropping funnel, and further stirred at 120 ° C. for 2 hours to obtain a polymer precursor. 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 methyl hydroquinone were added to the copolymer solution. Thereafter, the reaction was continued at 120 ° C. to obtain a resin having a solid content acid value of 167 mg kOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 10,300, and the molecular weight distribution (Mw / Mn) was 2.4.

<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 funnel and a nitrogen inlet, and the atmosphere in the flask was air. The temperature was raised to 120 ° C., and 24.4 g of t-butylperoxy 2-ethylhexyl carbonate was added to a mixture containing 141.6 g (1.2 mol) of vinyl toluene and 136 g of propylene glycol monomethyl ether acetate. The solution was dropped into the flask over 2 hours from the dropping funnel, and further stirred at 120 ° C. for 2 hours to obtain a polymer precursor. 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 methyl hydroquinone were added to the copolymer solution. Thereafter, the reaction was continued at 120 ° C. to obtain a resin having a solid content acid value of 187 mg kOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 11,400, and the molecular weight distribution (Mw / Mn) was 2.3.

<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 funnel and a nitrogen inlet, and the atmosphere in the flask was air. The mixture was heated to 120 ° C., and 24.4 g of t-butylperoxy 2-ethylhexyl carbonate was added to a mixture containing 201.6 g (1.2 mol) of cyclohexyl acrylate and 136 g of propylene glycol monomethyl ether acetate. The solution was dropped into the flask over 2 hours from the dropping funnel, and further stirred at 120 ° C. for 2 hours to obtain a polymer precursor. 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 methyl hydroquinone were added to the copolymer solution. Thereafter, the reaction was continued at 120 ° C. to obtain a resin having a solid content acid value of 170 mg kOH / g. The polystyrene-reduced weight average molecular weight measured by GPC was 11,000, and the molecular weight distribution (Mw / Mn) was 2.4.

<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 funnel and a nitrogen inlet, and the atmosphere in the flask was air. The mixture was heated to 120 ° C., and 24.4 g of t-butylperoxy 2-ethylhexyl carbonate was added to a mixture containing 70.8 g (0.6 mol) of vinyl toluene and 136 g of propylene glycol monomethyl ether acetate. The obtained solution was dropped into the flask over 2 hours from the dropping funnel, and further stirred at 120 ° C. for 2 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 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 reacted at 120 ° C. Subsequently, a resin having a solid content acid value of 110 mg kOH / g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 5,800, and the molecular weight distribution (Mw / Mn) was 2.5.

<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 funnel, and a nitrogen introduction pipe, the atmosphere in the flask was changed from air to nitrogen, and the temperature was raised to 100 ° C. 70.5 g (0.4 mol), methacrylic acid 43.0 g (0.5 mol), monomethacrylate having a tricyclodecane skeleton (manufactured by Hitachi Chemical Co., Ltd., FA-513M) 22.0 g (0.10 mol) A solution containing 3.6 g of propylene glycol monomethyl ether acetate and 3.6 g of azobisisobutyronitrile was added dropwise to the flask over 2 hours from the dropping funnel, and stirring was further continued at 100 ° C. for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, 15 g of glycidyl methacrylate [0.1 mol, (20 mol% based on the carboxy group of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone was charged into the flask and the reaction was continued at 110 ° C. for 6 hours to obtain a resin having a solid content acid value of 102 mg KOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 30,000, and the 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 funnel, and a nitrogen introduction tube, and the atmosphere in the flask was changed from air to nitrogen. 105.7 g (0.6 mol), 25.3 g (0.3 mol) of methacrylic acid, 22.0 g (0.10 mol) of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) and A solution obtained by adding 3.6 g of azobisisobutyronitrile to a mixture containing 136 g of propylene glycol monomethyl ether acetate was dropped into the flask over 2 hours from the dropping funnel, and further stirred at 100 ° C. for 5 hours. Yielded a resin with an A of 120 mg KOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 24,000, and the molecular weight distribution (Mw / Mn) was 2.1.

The weight average molecular weight (Mw) and number average molecular weight (Mn) in Synthesis Examples 1 to 9 were measured using the GPC method under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG4000HXL + TSK-GELG2000HXL (series connection)
Column temperature: 40 ° C
Mobile phase solvent: Tetrahydrofuran flow rate: 1.0 ml / min Injection volume: 50ul
Detector: RI
Measurement sample concentration: 0.6% by weight (solvent = tetrahydrofuran)
Calibration reference materials: 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).

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

<Example 1>
<Pigment dispersion M1> 22.52 parts, VALIFAST Yellow 1101 (manufactured by Orient Chemical Co., Ltd.) 0.51 parts, <Synthesis Example 1> 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, propylene glycol monomethyl ether 17.6 parts mixed, colored photosensitive resin composition Manufactured.

<Example 2>
<Pigment dispersion M1> 23.03 parts, <Synthesis Example 1> 8.86 parts of resin, KAYARAD DPHA (manufactured by Nippon Kayaku) 2.95 parts, Irgacure OXE01 (manufactured by BASF) 0.59 parts, ethyl lactate 35.2 parts, 11.77 parts of propylene glycol monomethyl ether acetate, and 17.6 parts of propylene glycol monomethyl ether were mixed to produce 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>
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 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>.

<Test example>
Color filters were produced using the colored photosensitive resin compositions produced in Examples 1 to 8 and Comparative Examples 1 and 2. That is, after the colored photosensitive resin compositions produced in Examples 1 to 8 and Comparative Examples 1 and 2 were applied on a glass substrate by a spin coating method, they were placed on a heating plate at a temperature of 100 ° C. A thin film was formed by maintaining for 3 minutes. 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 μm to 50 μm is placed on the thin film so that the distance from the test photomask is 100 μm. And irradiated with ultraviolet rays.

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

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

<Development speed>
At the time of development, the time taken for the non-exposed part to be completely dissolved in the developer was measured.

<Sensitivity>
After the development, the minimum exposure amount necessary to form a thin film having no chipping or peeling of the pattern was measured.

<Adhesion>
When the generated pattern was evaluated with an optical microscope, the evaluation was performed based on the degree of chipping or peeling of the pattern as follows.
○: No chipping or peeling of the pattern Δ: One to three chippings or peeling of the pattern X: Four or more chippings or peeling of the pattern

<Solvent resistance>
The produced color filter was immersed in N-methylpyrrolidone solvent for 30 minutes, and the color change before and after the evaluation was compared and evaluated. At this time, the formula used is calculated by the following mathematical formula 1 showing the color change in the three-dimensional colorimeter defined as L *, a *, b *, and the smaller the color change value, the more reliable the color. Filter manufacture is possible.

<Confirmation of surface foreign matter>
When the generated pattern was evaluated with an optical microscope, the number of foreign matters of 3 μm or more was confirmed on the pattern as follows.
○: Less than 2 Δ: 2 to 10 ×: 10 or more

As shown in Table 1, in the case of Examples 1 to 8 using the alkali-soluble resin having the repeating unit represented by the above formula 1, the colorant contains not only excellent sensitivity, adhesion and solvent resistance but also a dye. Therefore, it can be confirmed that when the colored layer is formed, it exhibits excellent characteristics with respect to the surface foreign matter.
In particular, in Examples 1 and 3 to 8 containing all pigments and dyes, both showed excellent characteristics as compared with Example 2 using only the pigment, and the alkali-soluble resin according to the present invention is a colorant. Since the compatibility with a certain pigment or dye is good, it can be seen that a colored photosensitive resin composition having excellent characteristics was produced.
However, in the case of Comparative Examples 1 and 2 using a colored photosensitive resin composition containing an alkali-soluble resin (resin synthesized in Synthesis Examples 8 and 9) that did not use maleic anhydride which is a compound represented by Formula 1 It can be seen that the film has low sensitivity and lack of adhesion due to occurrence of chipping or peeling of the pattern. Further, since the color change value was large, the solvent resistance was poor, and 10 or more surface foreign matters were generated, indicating an overall poor characteristic.
Therefore, it can be seen that when a colored photosensitive resin composition containing an alkali-soluble resin having a repeating unit of Formula 1 is used according to the present invention, a color filter excellent in various physical properties can be produced.

  The present invention is not limited by the above-described embodiments and the accompanying drawings, but should be interpreted by the appended claims. In addition, those skilled in the art have the knowledge that various forms can be replaced, modified and changed without departing from the technical idea of the present invention described in the claims. It is self explanatory.

1: Substrate 2: Pre-formed colored pattern 3: Colored layer 3 ′: Colored pattern 10: Photomask 11: Glass plate 12: Light shielding layer 13: Light projecting part 20: Light beam

Claims (12)

A colored photosensitive resin composition comprising a colorant containing an alkali-soluble resin, a pigment and / or a dye, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
The alkali-soluble resin has a repeating unit derived from an acid anhydride (A1) represented by the following formula 1, and is a colored photosensitive resin composition:

(Wherein, R ₁ and R ₂ are each independently hydrogen, a C 1-12 aliphatic or aromatic hydrocarbon group containing or not containing a hetero atom).   The alkali-soluble resin is a copolymer of the acid anhydride (A1) and a compound (A2) having an unsaturated bond copolymerizable with the acid anhydride (A1). The colored photosensitive resin composition as described.   The ratio of the repeating unit derived from the acid anhydride (A1) is 2 to 80 mol% with respect to the total number of moles of the entire repeating unit of the alkali-soluble resin. Colored photosensitive resin composition.   The ratio of the repeating unit derived from the compound (A2) having an unsaturated bond copolymerizable with the acid anhydride (A1) is 2 to 95 mol with respect to the total number of moles of the entire repeating unit of the alkali-soluble resin. The colored photosensitive resin composition according to claim 2 or 3, wherein the colored photosensitive resin composition is%.   The 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 group having an alicyclic substituent. Carboxylic acid ester compounds, monosaturated carboxylic acid ester compounds of glycols, unsaturated carboxylic acid ester compounds having a substituent containing an aromatic ring, aromatic vinyl compounds, carboxylic acid vinyl esters, vinyl cyanide compounds, and maleimide compounds It is at least 1 sort (s) of compound chosen from the group comprised, The colored photosensitive resin composition in any one of Claims 2-4 characterized by the above-mentioned.   The compound (A2) having an unsaturated bond copolymerizable with the acid anhydride (A1) includes methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, aminoethyl (meth) acrylate, cyclopentyl ( (Meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate , Cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamanty (Meth) acrylate, norbornyl (meth) acrylate, pinenyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, methylglycidyl (meta ) Acrylate, oligoethylene glycol monoalkyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) acrylate, styrene, α-methylstyrene, vinyl toluene, vinyl acetate, vinyl propionate, (meth) acrylonitrile, α-chloro A group consisting of acrylonitrile, N-cyclohexylmaleimide, N-phenylmaleimide, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid The colored photosensitive resin composition according to any one of claims 2-5, characterized in that the al least one compound selected.   The alkali-soluble resin is bonded to the acid anhydride (A1) and the copolymer of the compound (A2) having an unsaturated bond copolymerizable with the acid anhydride (A1) and the acid anhydride (A1). The colored photosensitive resin composition according to claim 1, wherein the compound is a compound in which a compound (A3) having a possible functional group is bound.   In the alkali-soluble resin, the repeating unit derived from the compound (A3) having a functional group capable of binding to the acid anhydride (A1) with respect to the number of moles of the repeating unit of the acid anhydride (A1). The colored photosensitive resin composition according to claim 7, wherein the ratio is from 2 to 95 mol%.   The compound (A3) having a functional group capable of binding to the acid anhydride (A1) is hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, A group consisting of 4-hydroxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 3- (acryloyloxy) -2-hydroxypropyl methacrylate The colored photosensitive resin composition according to claim 7, wherein the colored photosensitive resin composition is at least one compound selected from the group consisting of:   The colored photosensitive resin composition according to any one of claims 1 to 9, wherein the alkali-soluble resin has a polystyrene-equivalent weight average molecular weight of 3,000 to 100,000.   The color filter containing the colored layer containing the colored photosensitive resin composition in any one of Claims 1 thru | or 10.   A liquid crystal display device comprising the color filter according to claim 11.

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