TW201405246A - Photosensitive resin composition, color filter, liquid crystal display device, and imaging element - Google Patents

Abstract

The present invention provides a colored photosensitive resin composition, a color filter made of the colored photosensitive resin composition, and a liquid crystal display element or an imaging element comprising the color filter. The present invention is characterized by comprising: (A) at least one pigment and at least one dye, at least one of the pigment or the dye being a blue series colorant; (B) an alkali soluble resin having acid value of 30-150 mgKOH/g; (C) a photo-polymerizable compound; (D) a photo-polymerization initiator comprising the photo-polymerization initiating agent represented by formula 1; (E) an anti-oxidant in which a molecule contains both a phenolic anti-oxidation functional group and a phosphorus anti-oxidation functional group or contains both a phenolic anti-oxidation functional group and a sulfur anti-oxidation functional group; and (F) a solvent.

Description

Photosensitive resin composition, color filter, liquid crystal display device, and image pickup element

The present invention relates to a colored photosensitive resin composition, a colored pattern formed of the composition, a color filter including the colored pattern, and a liquid crystal display device and an image pickup element including the color filter.

Color filters are widely used in imaging elements, liquid crystal display devices, etc., and their application range is rapidly expanding. A color filter used in a color liquid crystal display device, an image pickup element, or the like is generally manufactured by uniformly applying a coloring agent containing colors corresponding to red, green, and blue colors by spin coating on a substrate on which a black matrix pattern is formed. The photosensitive resin composition is colored, and then dried by heating (hereinafter sometimes referred to as pre-baking) to form a coating film, and the coating film is exposed and developed, and if necessary, heat-cured (hereinafter sometimes referred to as secondary baking), The above operations are repeated for each color to form pixels of respective colors.

Recently, it has been strongly demanded to reflect the improvement in the quality of an image pickup device, a liquid crystal display device, and the like, and to increase the brightness of the display panel. Therefore, studies for increasing the luminance (Y value) of each of the colored photosensitive compositions of blue, red or green are performed in various directions. However, in particular, regarding the coloring photosensitive composition which provides a blue pixel, since the pigment which can be used is limited to copper phthalocyanine blue, the method of improving brightness is also shown. In addition, the yellowing in the secondary baking step of the photopolymerization initiator and the resin component contained in the coloring photosensitive composition is also a factor for lowering the brightness of the blue color filter.

In this case, Korean Patent Publication No. 10-2009-0041338 discloses a radiation-sensitive resin composition for a blue color filter, which comprises: (A) a coloring agent containing a blue coloring agent; Alkali-soluble resin; (C) polyfunctional monomer; (D) selected One or more photopolymerization initiators in the group consisting of a compound represented by the chemical formula 3, an oxime ester compound, and a biimidazole compound; and (E) selected from the group consisting of a phenolic antioxidant, a phosphorus antioxidant, and a sulfur-based antioxidant The total content of the one or more antioxidants in the group (E) is from 1 to 100 parts by weight based on 100 parts by weight of the total of the component (D).

However, it is considered that although the above-mentioned radiation-sensitive resin composition can select a photopolymerization initiator in a wide range, it cannot be increased to a level equivalent to the brightness of the blue pixel.

Patent Document 1: Korean Patent Publication No. 10-2009-0041338

The present invention has been made to solve the above problems of the prior art, and an object of the invention is to provide a blue pixel which is excellent in sensitivity and adhesion, does not cause pattern short circuit in a developing process, has high brightness, and has excellent contrast and light transmittance. The colored photosensitive resin composition.

The present invention provides a colored photosensitive resin composition comprising: (A) a colorant comprising one or more pigments and one or more dyes, one or more of the pigments or dyes being a blue series; (B) an acid value of 30 to 150 mgKOH (g) a photopolymerizable compound; (D) a photopolymerization initiator comprising a photopolymerization initiator represented by the following Chemical Formula 1; (E) an antioxidant having a phenolic antioxidant in one molecule a functional group and a phosphorus-based antioxidant functional group, or both a phenolic antioxidant functional group and a sulfur-based antioxidant functional group; and (F) a solvent, [Chemical Formula 1]

In the formula, R ₁ is a compound of the following Chemical Formula 2, R ₂ is a C1 to C8 alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, and R ₃ is a diphenyl sulfide group, [Chemical Formula 2] -R ₄ -R ₅

In the formula, R ₄ is a C1 to C4 alkylene group, and R ₅ is a C3 to C8 alkyl group or a C3 to C8 cycloalkyl group.

Further, the present invention provides a color filter comprising a color pattern formed by exposing and developing the colored photosensitive resin composition after forming a predetermined pattern.

Further, the present invention also provides a liquid crystal display element and an image pickup element including the aforementioned color filter.

The colored photosensitive resin composition of the present invention is excellent in sensitivity and adhesion, and does not cause pattern short-circuit in the development process, is excellent in brightness, and is excellent in contrast and light transmittance. Therefore, the colored photosensitive resin composition of the present invention can be used very usefully for producing a color filter.

The present invention relates to a colored photosensitive resin composition comprising: (A) a coloring agent comprising one or more pigments and one or more dyes, one or more of the pigments or dyes being a blue series; (B) an acid value of 30 to 150 mgKOH (g) a photopolymerizable compound; (D) a photopolymerization initiator comprising a photopolymerization initiator represented by the following Chemical Formula 1; (E) an antioxidant having a phenolic antioxidant in one molecule a functional group and a phosphorus-based antioxidant functional group, or both a phenolic antioxidant functional group and a sulfur-based antioxidant functional group; and (F) a solvent,

In the formula, R ₁ is a compound of the following Chemical Formula 2, R ₂ is a C1 to C8 alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, and R ₃ is a diphenyl sulfide group, [Chemical Formula 2] -R ₄ -R ₅

In the formula, R ₄ is a C1 to C4 alkylene group, and R ₅ is a C3 to C8 alkyl group or a C3 to C8 cycloalkyl group.

In the above formula, R ₂ is preferably phenyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl The group is more preferably a phenyl group, a methyl group or an ethyl group.

R ₅ may be n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, cyclopropyl, cyclobutyl, cyclopentyl Or cyclohexyl, cycloheptyl or cyclooctyl, more preferably cyclopropyl, cyclopentyl or cyclohexyl.

Hereinafter, the colored photosensitive resin composition of the present invention will be described in detail in accordance with each constituent component.

(A) colorant

The coloring agent (A) described above contains one or more pigments and one or more dyes, and one or more of the foregoing pigments or dyes are in the blue series.

Pigment (a1)

As the aforementioned pigment, an organic pigment or an inorganic pigment which is generally used in the field can be used. As the pigment, various pigments used in printing inks, inkjet inks, and the like can be used, and specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, and isoindolinone. Pigments, isoindoline pigments, anthraquinone pigments, anthrone pigments, dioxazine pigments, anthraquinone pigments, diterpene pigments, pyrimidine pigments, anthrones pigments, indanthrone pigments, flavans A ketone pigment, a ketone pigment, a diketopyrrolopyrrole pigment, and the like.

Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex compounds, and specific examples thereof include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, lanthanum, and carbon. An oxide such as black or a composite metal oxide or the like. The pigments of the blue, violet, and magenta series are preferable. In particular, as the organic pigment and the inorganic pigment, specifically, a compound classified as a pigment under the color rendering index (published by The Society of Dyers and Colourists) may be mentioned. In the case of CI Pigment Red, CI Pigment Violet, and CI Pigment Blue, more specifically, pigments having the following color rendering index (CI) numbers are listed, but are not necessarily limited thereto, and they can be used alone or in combination. Use two or more types.

CI Pigment Red 57:1, 81, 122, 174, 184, 202 CI Pigment Violet 1, 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

In the above-exemplified C.I. pigment, a pigment selected from the group consisting of C.I. Pigment Red 122, C.I. Pigment Violet 23, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:6 can also be suitably used.

The pigment is preferably a pigment dispersion liquid whose particle diameter is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of the pigment is a method of dispersing the pigment dispersant (a3), and a pigment dispersion in a state in which the pigment is uniformly dispersed in a solution can be obtained according to the method. liquid.

Specific examples of the pigment dispersant include a cationic system and an anion A surfactant such as a daughter, a nonionic, an amphoteric, a polyester or a polyamine may be used alone or in combination of two or more.

The content of the pigment (a1) is from 20 to 90% by weight, preferably from 30 to 70% by weight, based on the total weight of the solid content in the colorant. When the content of the pigment is in the range of 20 to 90% by weight based on the above-mentioned basis, the viscosity is low, the storage stability is excellent, the dispersion efficiency is high, and the contrast is effectively improved, which is preferable.

Pigment dispersant (a3)

The aforementioned pigment dispersant (a3) is added for the deflocculation and stability maintenance of the pigment, and a pigment dispersant which is generally used in the field can be used without limitation. It is preferable to include an acrylate-based dispersant (hereinafter referred to as an acrylic dispersant) containing BMA (butyl methacrylate) or DMAEMA (N,N-dimethylaminoethyl methacrylate). In this case, the acrylic dispersant is preferably a dispersant produced by the activity control method proposed in the Korean Patent Publication No. 2004-0014311, and a commercially available product of the acrylate-based dispersant produced by the above-described activity control method is exemplified. DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, etc.

The acrylic dispersants exemplified above may be used singly or in combination of two or more.

In addition to the aforementioned acrylic dispersant, the above dispersant (a3) can also use other resin-based pigment dispersants. Examples of the other resin-based pigment dispersant include a conventional resin-based pigment dispersant, particularly a polycarboxylate represented by polyurethane or polyacrylate, an unsaturated polyamine, a polycarboxylic acid, and a polycarboxylate. Acid (partial) amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polyoxyalkylene oxides, long chain polyaminoguanamine phosphates, hydroxyl-containing polycarboxylic acid esters, and their a modified product, or a guanamine formed by the reaction of a polyester having a free carboxyl group and a poly(lower alkyleneimine) or an oily dispersant such as these salts; (meth)acrylic acid-styrene a water-soluble resin or a water-soluble polymer compound such as a copolymer, a (meth)acrylic acid-(meth)acrylate copolymer, a styrene-maleic acid copolymer, a polyvinyl alcohol or a polyvinylpyrrolidone; a polyester; Polyacrylate; addition product of ethylene oxide/propylene oxide and phosphate ester. In the commercial product of the resin-based dispersant, examples of the cationic resin-dispersing agent include BYK (Compick) Chemical Company's trade names: DISPER BYK-160, DISPER BYK-161, and DISPER BYK-162. DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF's trade names: EFKA-44, EFKA-46, EFKA-47, EFKA- 48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Lubirzol's trade name: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Chuanyan Fine Chemicals Co., Ltd. (HINOACT) T-6000, HINOACTT-7000, HINOACTT-8000; Ajinomoto company's trade name: (AJISPUR) PB-821, AJISPURPB-822, AJISPURPB-823; Gongrongshe Chemical Company's trade name: (FLORENE) DOPA-17HF, FLORENEDOPA-15BHF, FLORENEDOPA-33, FLORENEDOPA-44, etc. In addition to the acrylic dispersant described above, other resin-based pigment dispersants may be used singly or in combination of two or more kinds, or may be used together with an acrylic dispersant.

The amount of the dispersant (a3) to be used is in the range of 5 to 60 parts by weight, more preferably 15 to 50 parts by weight, per 100 parts by weight of the solid content of the pigment (a1) to be used. When the content of the dispersant (a3) exceeds 60 parts by weight, the viscosity is increased, and when the content is less than 5 parts by weight, problems such as difficulty in atomization of the pigment or gelation after dispersion are caused.

Dye (a2)

The dye can be used without limitation as long as it has solubility in an organic solvent. Preferably, a dye having solubility in an organic solvent and ensuring reliability against solubility, heat resistance, solvent resistance, and the like of an alkali developer is preferably used.

As the dye, an acid group selected from a group consisting of a sulfonic acid or a carboxylic acid can be used. An acid dye, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide of an acid dye, or the like, and a dye of the derivative thereof, in addition to the azo-based, xanthene-based, phthalocyanine-based acid dyes, and the like Derivatives. As the color, a dye of a blue, purple, and deep red series is preferable, and a compound classified as a dye in a color rendering index (published by The Society of Dyers and Colourists), or a conventional dye described in a dyeing note (dyeing company) There are red, blue and purple dyes.

In the specific example of the aforementioned dye, as the CI solvent dye, there are red dyes such as CI solvent red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179; CI solvent blue 5, 35, 36 , blue dyes such as 37, 44, 59, 67, 70; violet dyes such as CI solvent violet 8, 9, 13, 14, 36, 37, 47, 49; and CI solvent dyes are preferably excellent in solubility in organic solvents. CI Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; CI Solvent Blue 35, 36, 44, 45, 70; CI Solvent Violet 13; among them, CI Solvent Red 8, 122, 132 are more preferred.

Further, examples of the CI acid dye include: 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, Red dyes such as 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426; 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, etc. blue dye; CI acid violet 6B, 7, 9 , 17, 19, 66 and other purple dyes.

Among the acid dyes, C.I. Acid Red 92 which is excellent in solubility in an organic solvent; C.I. Acid Blue 80, 90; C.I. Acid Violet 66 is preferable.

Further, as the CI direct dye, CI direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, Red dyes such as 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; 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, 250, 251, 252, 256, 257, Blue dyes such as 259, 260, 268, 274, 275, 293; CI direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95 , 96, 103, 104 and other purple dyes.

For example, CI mordant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, Red dyes such as 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; CI mordant 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 mordant violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47 , 48, 53, 58 and other purple dyes.

These dyes can be used singly or in combination of two or more.

The content of the dye in the coloring agent is preferably 0.5 to 80% by weight, more preferably 0.5 to 60% by weight based on the total weight of the solid content in the coloring agent. The weight % is particularly preferably from 1 to 50% by weight. When the content of the dye in the coloring agent is included in the above range, it is possible to prevent the problem that the reliability of elution of the dye by the organic solvent is lowered after the pattern is formed, and the sensitivity is excellent, which is preferable.

The content of the coloring agent is preferably 5 to 60% by weight, and more preferably 10 to 45% by weight, based on the total weight of the solid content of the colored photosensitive resin composition. In the case where the coloring agent is contained in the above range, even if a film is formed, the color density of the pixel is sufficient, and the defect of the non-pixel portion at the time of development does not decrease, so that generation of residue can be suppressed, which is preferable.

In the present invention, the total weight of the solid content in the colored photosensitive resin composition refers to the total weight of the components remaining after the solvent is removed from the colored photosensitive resin composition.

(B) alkali soluble resin

It is produced by copolymerizing an ethylenically unsaturated monomer (b1) having a carboxyl group as an essential component in order to be soluble in the alkaline developing solution used in the developing treatment step at the time of pattern formation.

Further, in order to ensure compatibility with the dye (a2) and storage stability of the colored photosensitive resin composition, the acid value of the alkali-soluble resin is 30 to 150 mgKOH/g. When the acid value of the alkali-soluble resin is less than 30 mgKOH/g, it is difficult to ensure a sufficient development speed of the colored photosensitive resin composition, and when the acid value exceeds 150 mgKOH/g, the adhesion to the substrate is lowered to easily occur. The short circuit of the pattern causes a problem of compatibility with the dye, and the dye deposition in the colored photosensitive resin composition or the storage stability of the colored photosensitive resin composition is lowered, and the viscosity is liable to increase.

Specific examples of the ethylenically unsaturated monomer (b1) having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; and dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid. An acid anhydride of a dicarboxylic acid; a mono(meth)acrylate such as a ω-carboxypolycaprolactone mono(meth)acrylate having a carboxyl group and a hydroxyl group at both terminals, preferably an acrylic acid or a methyl group; acrylic acid.

In order to provide a hydroxyl group to the alkali-soluble resin, it can be produced as follows: The ethylenically unsaturated monomer (b1) is copolymerized with an ethylenically unsaturated monomer (b2) having a hydroxyl group; a copolymer of an ethylenically unsaturated monomer (b1) having a carboxyl group and a compound having a glycidyl group (b3) Additional reaction. Further, it can also be produced by additionally reacting a copolymer of an ethylenically unsaturated monomer (b1) having a carboxyl group and an ethylenically unsaturated monomer (b2) having a hydroxyl group with a compound (b3) having a glycidyl group.

Specific examples of the ethylenically unsaturated monomer (b2) having a hydroxyl group include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, and acrylic acid-2. The -hydroxypropyl ester or the like is preferably 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate.

Specific examples of the compound (b3) having a glycidyl group include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, and glycidyl group. Butyrate, glycidyl methyl ether, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, benzyl glycidyl ether, glycidyl-4-tert-butyl Benzoate, glycidyl stearate, aryl glycidyl ether, glycidyl methacrylate, etc., preferably butyl glycidyl ether, aryl glycidyl ether, glycidyl methacrylate The compound (b3) having a glycidyl group can be used singly or in combination of two or more.

Further, the unsaturated monomer (b4) which can be copolymerized at the time of production of the alkali-soluble resin can be exemplified as follows, but is not necessarily limited thereto.

Specific examples of the polymerizable monomer (b4) having a copolymerizable unsaturated bond include styrene, vinyl toluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, and m-methoxy Styrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, meta-vinyl An aromatic vinyl compound such as benzyl glycidyl ether or p-vinylbenzyl glycidyl ether; N-cyclohexylmaleimide, N-benzyl maleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-pair Hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N- N-substituted maleimide compounds such as o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide ; (methyl) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylate (meth)acrylic acid alkyl esters such as butyl ester, sec-butyl (meth) acrylate, 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-dicyclopentyloxyethyl (meth)acrylate Cycloaliphatic (meth) acrylates such as isobornyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid Hydroxyethyl (meth)acrylate such as 4-hydroxybutyl ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate or N-hydroxyethyl acrylamide (aryl) (meth) acrylate such as phenyl (meth) acrylate or benzyl (meth) acrylate; 3-(methacryloxymethyl) oxetane, 3-(methyl Propylene oxime methyl)-3-ethyloxetane, 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacrylofluorene oxide Methyl)-2-phenyloxetane, 2-(methacryloxymethyl)oxetane, 2-(methacryloxymethyl)-4-trifluoro An unsaturated oxetane compound such as methyloxetane or the like.

The monomers exemplified in the above (b4) can be used alone or in combination of two or more.

The content of the alkali-soluble resin is in the range of 10 to 80% by weight, preferably 10 to 70% by weight, based on the total weight of the solid content in the photosensitive resin composition. When the content of the alkali-soluble resin is from 10 to 80% by weight based on the above criteria, the solubility in the developer is sufficient, and the pattern is easily formed. It is preferable to prevent the film of the pixel portion of the exposure portion from being reduced and the defect of the non-pixel portion to be good.

(C) Photopolymerizable compound

The photopolymerizable compound is a compound which can be polymerized by a photopolymerization initiator, and a monofunctional monomer, a difunctional monomer or a polyfunctional monomer can be used. Preferably, a bifunctional or higher polyfunctional monomer can be used.

As specific examples of the aforementioned monofunctional monomer, there are nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl The acrylate or N-vinylpyrrolidone or the like is not limited thereto.

Specific examples of the aforementioned difunctional monomer include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and three. Ethylene glycol di(meth)acrylate, bis(acryloyloxyethyl)ether or 3-methylpentanediol di(meth)acrylate of bisphenol A, but is not limited thereto.

Specific examples of the aforementioned polyfunctional monomer include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, and propoxylated trimethylolpropane. Tris(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate The propoxylated dipentaerythritol hexa(meth)acrylate or dipentaerythritol hexa(meth)acrylate is not limited thereto.

The photopolymerizable compound is preferably contained in an amount of 5 to 45% by weight, and more preferably 7 to 45% by weight, based on the total weight of the solid content of the colored photosensitive resin composition. When the photopolymerizable compound is contained in the above range, the strength and smoothness of the pixel portion are good, which is preferable.

(D) Photopolymerization initiator

The photopolymerization initiator contains the photopolymerization initiator (d1) represented by the following Chemical Formula 1: [Chemical Formula 1]

In the formula, R ₁ is a compound of the following Chemical Formula 2, R ₂ is a C1 to C8 alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, and R ₃ is a diphenyl sulfide group, [Chemical Formula 2]-R ₄ -R ₅

In the formula, R ₄ is a C1 to C4 alkylene group, and R ₅ is a C3 to C8 alkyl group or a C3 to C8 cycloalkyl group.

The photopolymerization initiator (d1) having the structure of the above Chemical Formula 1 prevents deterioration in sensitivity and light transmittance due to the dye, and exhibits effective photopolymerization characteristics for the colored photosensitive resin composition containing the dye as a colorant.

In the present invention, the photopolymerization initiator (d1) represented by the above formula (1) is preferably used in an amount of 10 to 100 parts by weight based on the total weight of the solid content of the photopolymerization initiator in order to exhibit characteristics as described above.

In addition, a photopolymerization initiator (d2) other than the photopolymerization initiator (d1) may be used in combination as long as the effects of the present invention are not impaired. Typically, one or more compounds selected from the group consisting of an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a biimidazole-based compound, an anthraquinone compound, and a thioxanthone-based compound are preferably used.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and benzoin dimethyl ketal. , 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4) -methylthiophenyl)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2 -hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)- 1-(4-morpholinophenyl)butan-1-one and the like.

Examples of the benzophenone-based compound include benzophenone, methyl ortho-benzoylbenzoate, 4-phenylbenzophenone, and 4-benzylidene-4'-methyldiphenylsulfide. Ether, 3,3',4,4'-tetrakis(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, 2,4. - bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-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)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan) -2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl) Vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3, 5-triazine and the like.

Specific examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-double (2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5' -tetrakis(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole, 2, 2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole or phenyl group at the 4,4',5,5' position An imidazole compound or the like after replacement with an alkoxycarbonyl group. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorobenzene) is preferably used. -4,4',5,5'-tetraphenylbiimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1 , 2'-biimidazole.

Specific examples of the ruthenium compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and the like, and are commercially available products, and are typically OXE01 and OXE02 of BASF Corporation.

Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxy group. Thioxanthone and the like.

In addition, the photopolymerization initiator may further contain a photopolymerization initiation aid (d3) in order to increase the sensitivity of the coloring photosensitive resin composition of the present invention. The colored photosensitive resin composition according to the present invention contains a photopolymerization initiation aid (d3), making the sensitivity higher, thereby improving productivity.

In the above (d3), 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.

As the amine compound, an aromatic amine compound is preferably used. Specifically, an aliphatic amine compound such as triethanolamine, methyldiethanolamine or triisopropanolamine, methyl 4-dimethylaminobenzoate or 4-di can be used. Ethyl methylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N- Dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as: Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and the like.

The carboxylic acid compound is preferably an aromatic heterocyclic acetic acid, and specific examples thereof include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, and methylethylphenylthioacetic acid. Dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthio Acetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyloxy)butane, and 1,3,5-tri ( 3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), Pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), and the like.

The photopolymerization initiator may be contained in an amount of 0.1 to 40 parts by weight, based on 100 parts by weight of the (B) alkali-soluble resin and the photopolymerizable compound (C) contained in the colored photosensitive resin composition of the present invention, and preferably contains 1 to 1 part by weight. 30 parts by weight. When the photopolymerization initiator (D) is contained in the above range, the photosensitive resin composition is highly sensitive, and the exposure time is shortened, so that productivity is improved and high resolution can be maintained, which is preferable. Further, when the composition under the above conditions is used, the strength and surface smoothness of the formed pixel portion become good.

Further, in the case of the photopolymerization initiation auxiliary (d3), the photopolymerization initiation The auxiliary agent (d3) may be contained in an amount of 10 to 100 parts by weight, preferably 20 to 100 parts by weight, per 100 parts by weight of the photopolymerization initiator based on the solid content. When the photopolymerization initiation aid (d3) is included in the above range, it is possible to prevent a decrease in sensitivity and a pattern short circuit in the conventional process.

(E) Antioxidants

The aforementioned antioxidant must have both a phenolic antioxidant functional group and a phosphorus-based antioxidant functional group in one molecule, or both a phenolic antioxidant functional group and a sulfur-based antioxidant functional group. When a phenol-based antioxidant and a phosphorus-based antioxidant or a phenol-based antioxidant and a sulfur-based antioxidant are used at the same time, it is difficult to expect an improvement in light transmittance in a blue colored photosensitive resin composition containing a dye, and sensitivity is generated. It is difficult to form a pattern by exposure, and pattern short-circuiting is likely to occur. As an antioxidant having a phenolic antioxidant functional group and a phosphorus-based antioxidant functional group, there are IRGANOX 1425 (manufactured by BASF Corporation), Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.), and the like, and have both a phenolic antioxidant functional group and a sulfur system. Antioxidant functional group antioxidants include IRGANOX 1035 (manufactured by BASF Corporation), IRGANOX 1081 (manufactured by BASF Corporation), IRGANOX 1726 (manufactured by BASF Corporation), and the like.

As an antioxidant having a phenolic antioxidant functional group and a phosphorus-based antioxidant functional group, there are IRGANOX 1425 (manufactured by BASF Corporation), Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.), and the like, and have both a phenolic antioxidant functional group and a sulfur system. Antioxidant functional group antioxidants include IRGANOX 1035 (manufactured by BASF Corporation), IRGANOX 1081 (manufactured by BASF Corporation), IRGANOX 1726 (manufactured by BASF Corporation), and the like. The antioxidant may be contained in an amount of 1 to 100 parts by weight, preferably 2 to 50 parts by weight, per 100 parts by weight of the photopolymerization initiator based on the solid content. When the antioxidant is contained in the above range, it is preferable to increase the light transmittance of the colored photosensitive resin composition without lowering the sensitivity. When the amount is less than 1 part by weight, it is difficult to expect an improvement in light transmittance. When the amount is more than 100 parts by weight, the sensitivity due to the dye cannot be overcome, the sensitivity is not improved, and the pattern short circuit is likely to occur in the development step.

(F) solvent

The solvent (F) is a solvent used in a usual photosensitive resin composition, and it is particularly preferable to use an ether, an aromatic hydrocarbon, or a ketone, as long as the other components contained in the colored photosensitive resin composition are effectively dissolved. Classes, alcohols, esters or guanamines.

Specific examples of the solvent (F) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dipropyl ether, diethylene glycol dibutyl ether; methyl cellosolve acetate, ethyl fiber Ethylene glycol alkyl ether acetate such as acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether acetate, butyl methoxyacetate, amyl methoxyacetate Alkylene glycol alkyl ether acetates; aromatic hydrocarbons such as benzene, toluene, xylene, and trimethylbenzene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone Classes; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate a cyclic ester such as γ-butyrolactone.

The solvent (F) is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C from the viewpoint of coatability and drying property, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, or a ring can be used. Hexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

The solvent (F) of the above-mentioned example can be used singly or in combination of two or more kinds, and may be contained in an amount of 60 to 90% by weight, preferably 70 to 85% by weight based on the total weight of the colored photosensitive resin composition of the present invention. . When the solvent (F) is included in the above range, a roll coater, a spin coater, a slit spin coater, or a slit coater (sometimes referred to as a groove coating) is used. When the coating device such as an inkjet type or the like is applied, an effect of improving the coating property can be obtained.

(G) additive

The colored photosensitive resin composition of the present invention is not damaged except for the aforementioned components. Additives such as fillers, other polymer compounds, curing agents, pigment dispersants, adhesion promoters, ultraviolet absorbers, deflocculating agents, and the like can be simultaneously used within the scope of the object of the present invention in accordance with the needs of those skilled in the art.

Specific examples of the filler include glass, cerium oxide, aluminum oxide, and the like, but are not limited thereto.

Specific examples of the other polymer compound include a curable resin such as an epoxy resin or a maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, or polyfluoroalkyl acrylate. A thermoplastic resin such as polyester or polyurethane, but is not limited thereto.

The curing agent is used for improving deep curing and mechanical strength. Specifically, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, or the like can be used, but is not limited thereto. Specific examples of the epoxy compound include a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a hydrogenated bisphenol F type epoxy resin, and a novolac type ring. Oxygen resin, other aromatic epoxy resin, alicyclic epoxy resin, glycidyl ester resin, glycidylamine resin or brominated derivatives of these epoxy resins, epoxy resins and brominated derivatives thereof Other aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co)polymer epoxides, isoprene (co)polymer epoxides, glycidyl (meth)acrylates ( Copolymer), triglycidyl isocyanurate, etc., but is not limited thereto. With respect to the aforementioned oxetane compound, specifically, carbonate dioxetane, xylene dioxetane, adipic acid dioxetane, and dioxa terephthalate can be used. Although it is cyclobutane, cyclohexane dicarboxylic acid dioxetane, etc., it is not limited to this.

The curing agent can simultaneously use a curing auxiliary compound capable of simultaneously ring-opening polymerization of an epoxy group or an oxetane skeleton of an oxetane compound with a curing agent. As the curing auxiliary compound, a polyvalent carboxylic acid, a polycarboxylic acid anhydride, an acid generator, or the like can be used. As the polyvalent carboxylic acid anhydride, a compound commercially available as an epoxy resin curing agent can be used. Cured as previously commercially available epoxy resin For example, the product name (ADEKA curing agent EH-700) (made by ADEKA Industries Co., Ltd., the product name (RIKACID HH) (manufactured by Shin Nippon Chemical Co., Ltd.), and the trade name (MH-700) (new) Made by Nippon Chemical Co., Ltd.).

The curing agent or the like of the foregoing examples can be used alone or in combination of two or more.

A commercially available surfactant can be used as the pigment dispersant, and specifically, a surfactant selected from the group consisting of organic lanthanide, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants can be used. Individual in the group or a mixture thereof. More specifically, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters can be used. In addition to the above, the product name KP (Shin-Etsu Chemical Co., Ltd.), (POLYFLOW) (Kyoeisha Chemical Co., Ltd.), (EFTOP)( Co., Ltd.) (MEGAFAC) (DAINIPPON INK AND CHEMICALS, INCORPORATED (株式会社)), (Flourad) (Sumitomo 3M Co., Ltd.), (Asahi guard), Surflon (Surflon) (above, Asahi Glass Co., Ltd.), (SOLSPERSE) (Lubrisol), EFKA (EFKA Chemical Co., Ltd.), PB821 (Ajinomoto Co., Ltd.), Disperbyk-series (BYK-chemi), and the like.

With regard to the aforementioned adhesion promoter, specifically, it is possible to use a single or a mixture thereof selected from the group consisting of an adhesion promoter: vinyl trimethoxy decane, vinyl triethoxy decane, vinyl three (2) -methoxyethoxy)decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxy Baseline, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4 -Epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane 3-mercaptopropyltrimethoxydecane, 3-isocyanatepropyltrimethoxydecane, and 3-isocyanatepropyltriethoxydecane. The adhesion promoter is solid relative to the colored photosensitive resin composition The total weight of the body component may be 0.01 to 10% by weight, and preferably 0.05 to 2% by weight.

Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone. But it is not limited to this.

As the deflocculant, specifically, sodium polyacrylate or the like can be used, but is not limited thereto.

In the present invention, the additive (G) may be contained in an amount of 0.01 to 15% by weight based on the total weight of the solid content in the colored photosensitive resin composition.

Hereinafter, a method for producing the colored photosensitive resin composition of the present invention will be described by way of example.

First, the pigment (a1) in the coloring agent (A) is mixed with the solvent (F), and dispersed by using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, a part or all of the pigment dispersant (a3) and (B) the alkali-soluble resin or the (a2) dye may be mixed, dissolved or dispersed together with the solvent (F) as needed.

Further, the dye (a2), (B) the balance of the alkali-soluble resin, (C) the photopolymerizable compound, (D) the photopolymerization initiator, and (E) the antioxidant are further added to the mixed liquid mixture, and if necessary, further The colored photosensitive resin composition of the present invention can be produced by adding the (G) additive and the (F) solvent to form a predetermined concentration.

Hereinafter, the present invention will be described in more detail based on the examples, however, the embodiments of the invention disclosed below are merely examples, and the scope of the invention is not limited by the embodiments. The scope of the present invention is intended to be embraced by the scope of the claims In addition, in the following Examples and Comparative Examples, "%" and "parts" indicating the content refer to the weight basis unless otherwise specified.

Production Example 1: Production of Pigment Dispersion Composition (M1)

12.0 parts by weight of pigment CI Pigment Blue 15:6, 4.0 parts by weight of pigment dispersant DISPERBYK-2001 (manufactured by BYK Corporation), 44 parts by weight of propylene glycol methyl ether acetate as a solvent, and 40 parts by weight of propylene glycol methyl ether The bead mill was mixed for 12 hours, and it was dispersed to produce a pigment dispersion M1.

Production Example 2: Production of alkali-soluble resin

120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 13.0 parts of acrylic acid, 10 parts of A were placed in a flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping funnel, and a nitrogen introduction tube. The benzyl acrylate, 57.0 parts of 4-methylstyrene, 20 parts of methyl methacrylate, and 3 parts of n-dodecyl mercaptan were replaced with nitrogen. Then, while the temperature of the reaction liquid was raised to 110 ° C while stirring, the reaction was allowed to proceed for 6 hours. The solid content of the alkali-soluble resin thus synthesized had an acid value of 100.2 mgKOH/g, and the weight average molecular weight Mw measured by GPC was about 15,110.

Production Example 3: Production of alkali-soluble resin

120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 3.5 parts of acrylic acid, 10 parts of A were placed in a flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping funnel and a nitrogen introduction tube. The benzyl acrylate, 66.5 parts of 4-methylstyrene, 20 parts of methyl methacrylate, and 3 parts of n-dodecyl mercaptan were replaced with nitrogen. Then, while the temperature of the reaction liquid was raised to 110 ° C while stirring, the reaction was allowed to proceed for 6 hours. The solid content of the alkali-soluble resin thus synthesized was 26.5 mgKOH/g, and the weight average molecular weight Mw measured by GPC was about 16070.

Production Example 4: Production of alkali-soluble resin

120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 22.5 parts of acrylic acid, 10 parts of A were placed in a flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping funnel and a nitrogen introduction tube. The benzyl acrylate, 47.5 parts of 4-methylstyrene, 20 parts of methyl methacrylate, and 3 parts of n-dodecyl mercaptan were replaced with nitrogen. Then, while the temperature of the reaction liquid was raised to 110 ° C while stirring, the reaction was allowed to proceed for 6 hours. The solid content of the alkali-soluble resin thus synthesized was 172.3 mgKOH/g, and the weight average molecular weight Mw measured by GPC was about 14850.

Example 1: Production of Colored Photosensitive Resin Composition

22.5 parts by weight of the above-mentioned pigment dispersion composition M1, dye VALIFAST BLUE 2620 (product of Orient Chemical Industries Co., Ltd.) 0.3 parts by weight, and 16.5 parts by weight of the resin of Production Example 2, KAYARAD DPHA (Nippon Chemical Co., Ltd.) 5.0 parts by weight of Irgacure 907 (manufactured by BASF Corporation), 0.7 parts by weight of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having a structure of the following Chemical Formula 3, and 0.2 parts by weight of an antioxidant Irganox 1035 (manufactured by BASF Corporation). 20.5 parts by weight of propylene glycol monomethyl ether acetate and 34.0 parts by weight of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

Example 2: Production of colored photosensitive resin composition

22.5 parts by weight of the above-mentioned pigment dispersion composition M1, VALIFAST BLUE 2620 (product of Orient Chemical Industries Co., Ltd.) 0.3 parts by weight, 16.5 parts by weight of the resin of Production Example 2, and KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 5.0 weight 0.3 parts by weight of Irgacure 907 (manufactured by BASF Corporation), 0.7 parts by weight of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having the structure of the above Chemical Formula 3, 0.2 parts by weight of antioxidant Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.), and propylene glycol 20.5 parts by weight of methyl ether acetate and 34.0 parts by weight of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

Comparative Example 1: Production of colored photosensitive resin composition

22.5 parts by weight of the above-mentioned pigment dispersion composition M1, VALIFAST BLUE 2620 (product of Orient Chemical Industries Co., Ltd.) 0.3 parts by weight, 16.5 parts by weight of the resin of Production Example 2, and KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 5.0 weight 0.3 parts by weight of Irgacure 907 (manufactured by BASF Corporation), 0.7 parts by weight of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having a structure of the above Chemical Formula 3, 20.5 parts by weight of propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether 34.0 parts by weight The colored photosensitive resin composition was mixed and produced.

Comparative Example 2: Production of colored photosensitive resin composition

22.5 parts by weight of the above-mentioned pigment dispersion composition M1, VALIFAST BLUE 2620 (product of Orient Chemical Industries Co., Ltd.) 0.3 parts by weight, 16.5 parts by weight of the resin of Production Example 2, and KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 5.0 weight 0.3 parts by weight of Irgacure 907 (manufactured by BASF Corporation), 0.7 parts by weight of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having the structure of the above Chemical Formula 3, 0.2 parts by weight of phenolic antioxidant IRGANOX 3114 (manufactured by BASF Corporation), propylene glycol monomethyl 20.5 parts by weight of phenyl ether acetate and 34.0 parts by weight of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

Comparative Example 3: Production of colored photosensitive resin composition

22.5 parts by weight of the above-mentioned pigment dispersion composition M1, VALIFAST BLUE 2620 (product of Orient Chemical Industries Co., Ltd.) 0.3 parts by weight, 16.5 parts by weight of the resin of Production Example 2, and KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 5.0 weight 0.3 parts by weight of Irgacure 907 (manufactured by BASF Corporation), 0.7 parts by weight of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having a structure of the above Chemical Formula 3, and 0.2 parts by weight of a phosphorus-based antioxidant IRGAFOS 168 (manufactured by BASF Corporation), propylene glycol monomethyl 20.5 parts by weight of phenyl ether acetate and 34.0 parts by weight of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

Comparative Example 4: Production of colored photosensitive resin composition

22.5 parts by weight of the above-mentioned pigment dispersion composition M1, VALIFAST BLUE 2620 (product of Orient Chemical Industries Co., Ltd.) 0.3 parts by weight, 16.5 parts by weight of the resin of Production Example 2, and KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 5.0 weight 0.3 parts by weight of Irgacure 907 (manufactured by BASF Corporation), 0.7 parts by weight of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having the structure of the above Chemical Formula 3, 0.2 parts by weight of IRGANOX 3114 (manufactured by BASF Corporation), and IRGAFOS 168 (manufactured by BASF Corporation) 0.2 A part by weight, 20.5 parts by weight of propylene glycol monomethyl ether acetate, and 34.0 parts by weight of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

Comparative Example 5: Production of colored photosensitive resin composition

22.5 parts by weight of the above-mentioned pigment dispersion composition M1, VALIFAST BLUE 2620 (product of Orient Chemical Industries Co., Ltd.) 0.3 parts by weight, 16.5 parts by weight of the resin of Production Example 2, and KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 5.0 weight 0.3 parts by weight of Irgacure 907 (manufactured by BASF Corporation), 0.7 parts by weight of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having a structure of the above Chemical Formula 3, and 0.2 parts by weight of a sulfur-based antioxidant STAB AO-412S (manufactured by Adeka Co., Ltd.). 20.5 parts by weight of propylene glycol monomethyl ether acetate and 34.0 parts by weight of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

Comparative Example 6: Production of colored photosensitive resin composition

22.5 parts by weight of the above-mentioned pigment dispersion composition M1, VALIFAST BLUE 2620 (product of Orient Chemical Industries Co., Ltd.) 0.3 parts by weight, 16.5 parts by weight of the resin of Production Example 2, and KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 5.0 weight 0.3 parts by weight of Irgacure 907 (manufactured by BASF Corporation), 0.7 parts by weight of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having the structure of the above Chemical Formula 3, 0.2 parts by weight of IRGANOX 3114 (manufactured by BASF Corporation), STAB AO-412S (ADEKA Corporation) 0.2 parts by weight, 20.5 parts by weight of propylene glycol monomethyl ether acetate, and 34.0 parts by weight of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

Comparative Example 7: Production of colored photosensitive resin composition

22.5 parts by weight of the above-mentioned pigment dispersion composition M1, VALIFAST BLUE 2620 (product of Orient Chemical Industries Co., Ltd.) 0.3 parts by weight, 16.5 parts by weight of the resin of Production Example 2, and KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 5.0 weight 0.3 parts by weight of Irgacure 907 (manufactured by BASF Corporation), 0.7 parts by weight of Irgacure OXE02 (manufactured by BASF Corporation) of the following <Chemical Formula 4>, 0.2 parts by weight of antioxidant Irganox 1035 (manufactured by BASF Corporation), propylene glycol monomethyl ether acetate 20.5 parts by weight of an ester and 34.0 parts by weight of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

Comparative Example 8: Production of colored photosensitive resin composition

22.5 parts by weight of the above-mentioned pigment dispersion composition M1, VALIFAST BLUE 2620 (product of Orient Chemical Industries Co., Ltd.) 0.3 parts by weight, 16.5 parts by weight of the resin of Production Example 2, and KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 5.0 weight 0.3 parts by weight of Irgacure 907 (manufactured by BASF Corporation), 0.7 parts by weight of Irgacure OXE02 (manufactured by BASF Corporation) of the above-mentioned <Chemical Formula 4>, 0.2 parts by weight of an antioxidant Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.), and propylene glycol monomethyl ether 20.5 parts by weight of acetate and 34.0 parts by weight of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

Comparative Example 9: Production of colored photosensitive resin composition

22.5 parts by weight of the above-mentioned pigment dispersion composition M1, VALIFAST BLUE 2620 (product of Orient Chemical Industries Co., Ltd.) 0.3 parts by weight, 16.5 parts by weight of the resin of Production Example 3, and KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 5.0 weight 0.3 parts by weight of Irgacure 907 (manufactured by BASF Corporation), 0.7 parts by weight of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having the structure of the above Chemical Formula 3, and 0.2 parts by weight of antioxidant Irganox 1035 (manufactured by BASF Corporation), propylene glycol monomethyl ether 20.5 parts by weight of acetate and 34.0 parts by weight of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

Comparative Example 10: Production of colored photosensitive resin composition

22.5 parts by weight of the aforementioned pigment dispersion composition M1, VALIFAST 0.3 parts by weight of BLUE 2620 (product of Orient Chemical Industries Co., Ltd.), 16.5 parts by weight of the resin of Production Example 4, 5.0 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), and 0.3 parts by weight of Irgacure 907 (manufactured by BASF Corporation). 0.7 parts by weight of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having a structure of the above Chemical Formula 3, 0.2 parts by weight of an antioxidant Irganox 1035 (manufactured by BASF Corporation), 20.5 parts by weight of propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether 34.0. The colored photosensitive resin composition was produced by mixing in parts by weight.

Comparative Example 11: Production of colored photosensitive resin composition

22.5 parts by weight of the pigment dispersion composition M1, 16.5 parts by weight of the resin of Production Example 4, 5.0 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), and 0.3 parts by weight of Irgacure 907 (manufactured by BASF Corporation), and having the aforementioned Chemical Formula 3 0.7 parts by weight of TR-PBG-305 (manufactured by TRONLY Co., Ltd.), 0.2 parts by weight of antioxidant Irganox 1035 (manufactured by BASF Corporation), 20.5 parts by weight of propylene glycol monomethyl ether acetate, and 34.0 parts by weight of propylene glycol monomethyl ether. A colored photosensitive resin composition was produced.

Test Example 1: Measurement of development speed, adhesion, and line width of a pattern

The color filter was produced using the colored photosensitive resin compositions manufactured in the foregoing Examples 1 to 2 and Comparative Examples 1 to 11.

Specifically, the colored photosensitive resin composition was applied to a 2 square inch glass substrate ("EAGLE XG" manufactured by Corning Co., Ltd.) by a spin coating method, and then placed on a hot plate at 100 ° C. The temperature was maintained for 3 minutes to form a film. Next, a test photomask having a pattern in which the light transmittance is changed in a range of 1 to 100% and a line width/space pattern of 1 μm to 50 μm is placed on the film, and the interval from the test photomask is placed. It was set to 100 μm and irradiated with ultraviolet rays. At this time, the ultraviolet light source was irradiated with an illumination of 100 mJ/cm ² using a 1 KW high-pressure mercury lamp including all of g, h, and i rays, and no special filter was used. The film irradiated with the above ultraviolet rays was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 2 minutes to be developed. The glass plate coated with the above-mentioned film was washed with distilled water, dried with nitrogen, and heated in a heating oven at 200 ° C for 25 minutes to produce a color filter.

The film thickness of the above-described color filter was 2.0 μm.

<adhesion>

The resulting pattern was observed by an optical microscope and evaluated according to the following criteria and shown in Tables 1 and 2 below.

○: There is no peeling on the pattern

△: 1 to 3 peelings on the pattern

×: There are 4 or more peeling off on the pattern.

<development speed>

The time required for the non-exposed portion to completely dissolve in the developer at the time of development was measured.

Test Example 2: Determination of color and contrast

The color chromaticity and the contrast were measured using a color filter manufactured in the same manner as in the above <Test Example 1 except that the test photomask was not used.

<Chroma and Contrast>

The color chromaticity and the contrast were measured using a color filter manufactured in the same manner as in the above <Test Example 1 except that the test photomask was not used.

In the case of contrast, the substrate of the color filter is sandwiched between two deflection plates, and is illuminated by a fluorescent lamp (wavelength 380 to 780 nm) from the rear side, and a CS-2000 luminance meter (KONICA MINOLTA) is used. The maximum value and the minimum value of the light intensity transmitted by rotating the front side deflecting plate are measured, and the contrast obtained by dividing the maximum value by the minimum value is calculated. In the case of the light transmittance, a colorimeter (manufactured by Olympus Corporation) is used. , OSP-200) was measured.

The results of the above Test Example 1 and Test Example 2 are shown in Tables 1 to 2 below.

As is apparent from the above Table 1, in the case of Examples 1 to 2 of the colored photosensitive resin composition of the present invention, the adhesion and development speed were compared with those of the colored photosensitive resin compositions of Comparative Examples 1 to 11. , contrast and light transmittance show excellent results.

Claims (8)

A colored photosensitive resin composition comprising: (A) a colorant comprising one or more pigments and one or more dyes, one or more of the pigments or dyes being a blue series; (B) an acid value of 30 ~150 mgKOH/g alkali-soluble resin; (C) photopolymerizable compound; (D) photopolymerization initiator comprising a photopolymerization initiator represented by the following Chemical Formula 1; (E) an antioxidant, having a phenol system in one molecule An antioxidant functional group and a phosphorus-based antioxidant functional group, or both a phenolic antioxidant functional group and a sulfur-based antioxidant functional group; and (F) a solvent, In the formula, R ₁ is a compound of the following Chemical Formula 2, R ₂ is a C1 to C8 alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, and R ₃ is a diphenyl sulfide group, [Chemical Formula 2]-R ₄ -R ₅ wherein R ₄ is a C1 to C4 alkylene group, and R ₅ is a C3 to C8 alkyl group or a C3 to C8 cycloalkyl group. The colored photosensitive resin composition according to the first aspect of the invention, wherein the colored photosensitive resin composition contains 5 to 60 by weight based on the total weight of the solid content contained in the colored photosensitive resin composition. % by weight of (A) colorant, 10 to 80% by weight of (B) alkali-soluble resin, and 5 to 45% by weight of (C) photopolymerizable compound, with (B) alkali-soluble resin and (C) light 100 parts by weight of the polymerizable compound In the range of 0.1 to 40 parts by weight of the (D) photopolymerization initiator, based on 100 parts by weight of the (D) photopolymerization initiator, 1 to 100 parts by weight of (E) antioxidant is used for coloring. The solvent is contained in an amount of 60 to 90% by weight based on the total weight of the resin composition. The colored photosensitive resin composition according to claim 1, wherein the antioxidant having both a phenolic antioxidant functional group and a phosphorus-based antioxidant functional group in one molecule is selected from the group consisting of IRGANOX 1425 (manufactured by BASF Corporation) and Sumilizer GP. (Group manufactured by Sumitomo Chemical Co., Ltd.), an antioxidant having both a phenolic antioxidant functional group and a sulfur-based antioxidant functional group in a molecule selected from the group consisting of IRGANOX 1035 (manufactured by BASF Corporation), IRGANOX 1081 (manufactured by BASF Corporation), and IRGANOX 1726 A group consisting of (made by BASF). The colored photosensitive resin composition according to claim 1, wherein R2 is a phenyl group, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a t-butyl group, or the like. N-pentyl, n-hexyl, n-heptyl or n-octyl, R5 is n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl Base, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. The coloring photosensitive resin composition according to the first aspect of the invention, wherein the (D) photopolymerization initiator is a compound represented by the following Chemical Formula 3: A color filter comprising a color pattern, wherein the colored photosensitive resin composition according to any one of claims 1 to 5 is formed into a predetermined pattern, and then exposed and developed. form. A liquid crystal display device comprising the color filter of claim 6 of the patent application. An image pickup element comprising the color filter described in claim 6 of the patent application.