KR20220122896A - A red photosensitive resin composition, a color filter and a display device using the same - Google Patents

Abstract

The present invention relates to a red photosensitive resin composition containing a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, an ultraviolet absorber, a polyfunctional thiol compound and a solvent, a color filter prepared using the same, and a display device including the color filter. The colorant includes red colorant. The ultraviolet absorber satisfies the condition that i) when the maximum absorption wavelength in the wavelength range of 270 nm to less than 330 nm is λmax1, and the maximum absorption wavelength in the wavelength range of 330 nm to less than 400 nm is λmax2, absorbance at λmax1/absorbance at λmax2>0.8, and that the absorbance at a wavelength of 365 nm is 0.3 or less when the absorbance of the maximum absorption wavelength (λmax) in the entire wavelength range is normalized to 1. The present invention can improve chemical resistance, undercut characteristics and adhesion of the color filter.

Description

Red photosensitive resin composition, color filter and display device manufactured using the same

The present invention relates to a red photosensitive resin composition, a color filter manufactured using the same, and a display device including the color filter.

A color filter is widely used in various display devices such as an imaging device, a liquid crystal display (LCD), and an organic light emitting diode (OLED), and its application range is rapidly expanding.

A color filter used in a display device consists of a coloring pattern of three colors of red, green, and blue, or three kinds of yellow, magenta, and cyan. It consists of a coloring pattern of color.

The coloring pattern of each of the color filters is generally formed using a colored photosensitive resin composition including a colorant such as a pigment and/or dye, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The coloring pattern processing using the colored photosensitive resin composition is generally performed by a lithography process.

Recently, the market demand for a high-quality display having a high resolution is increasing, and accordingly, the color filter pattern size is being miniaturized. have.

However, when the content of the colorant is increased, not only the manufacturing cost is improved, but also the curing does not proceed sufficiently when the pattern is formed with the colored photosensitive resin composition, so that the chemical resistance, undercut characteristics and adhesion of the color filter are lowered. Problems may arise.

In this regard, Korean Patent Application Laid-Open No. 10-2012-0007031 discloses a coloring composition including an ultra-fine pigment for high color concentration of a pixel, but the above-mentioned publication does not provide an alternative to the above-described problem.

Republic of Korea Patent Publication No. 10-2012-0007031

The present invention is to improve the problems of the prior art described above, a red photosensitive resin composition capable of improving the chemical resistance, undercut characteristics and adhesion of a color filter by sufficiently curing during pattern formation, and manufactured using the same An object of the present invention is to provide a color filter and a display device.

However, the problem to be solved by the present application is not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

In order to achieve the above object, the present invention includes a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, an ultraviolet absorber, a polyfunctional thiol compound and a solvent, the colorant includes a red colorant, and the ultraviolet absorber is i ) When the maximum absorption wavelength in the wavelength range of 270 nm or more and less than 330 nm is λmax1, and the maximum absorption wavelength in the wavelength range of 330 nm or more and less than 400 nm is λmax2, absorbance at λmax1 / absorbance at λmax2 > 0.8 and ii) When the absorbance of the maximum absorption wavelength (λmax) in the entire wavelength range is normalized to 1, the absorbance at a wavelength of 390 nm satisfies the condition of 0.2 or less, to provide a red photosensitive resin composition.

In addition, the present invention provides a color filter comprising a colored pattern made of the red photosensitive resin composition.

In addition, the present invention provides a display device including the color filter.

The red photosensitive resin composition of the present invention contains an ultraviolet absorber that satisfies specific conditions and a polyfunctional thiol compound, so that the color pattern can be sufficiently cured during the manufacture of a color filter, and accordingly, the color filter has chemical resistance, undercut characteristics, and It has the effect of being able to improve adhesiveness.

The present invention relates to a red photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, an ultraviolet absorber, a polyfunctional thiol compound and a solvent, a color filter prepared using the same, and a display comprising the color filter It relates to an apparatus, wherein the colorant includes a red colorant, and the ultraviolet absorber satisfies the following conditions i) and ii).

i) When the maximum absorption wavelength in the wavelength range of 270 nm or more and less than 330 nm is λmax1 and the maximum absorption wavelength in the wavelength range of 330 nm or more and less than 400 nm is λmax2, absorbance at λmax1 / absorbance at λmax2 > 0.8 ; and

ii) When the absorbance of the maximum absorption wavelength (λmax) in the entire wavelength range is normalized to 1, the absorbance at the wavelength of 365 nm is 0.3 or less

The red photosensitive resin composition of the present invention can sufficiently harden the coloring pattern even when an ultraviolet light source containing only the i-line is used in the exposure process when the color filter is manufactured.

The ultraviolet light source containing only the i-line may be an ultraviolet light source having a half width of 4 nm or more and 15 nm or less, and an LED light source including only the i-line ultraviolet light may be used. Here, "half width" means the width (nm) of the spectrum curve at the point of 50% transmittance of the highest transmittance wavelength in the central wavelength.

Hereinafter, the red photosensitive resin composition of the present invention will be described in detail.

< Red photosensitive resin composition >

The red photosensitive resin composition of the present invention includes (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photoinitiator, (E) an ultraviolet absorber, (F) a polyfunctional thiol compound, and (G) ) may contain a solvent, and may further include other additives.

(A) Colorant

The colorant (A) according to the present invention is characterized in that it contains (a1) a red colorant.

In addition, if necessary, at least one pigment (a2), at least one dye (a4), or a mixture thereof may be further included.

(a1) red colorant

As the red colorant, a red organic pigment, a red inorganic pigment, or a red dye generally used in the art may be used, and these may be used alone or in combination of two or more.

Examples of the red organic pigment and the green inorganic pigment include compounds classified as red pigments in the color index (published by The Society of Dyers and Colorists), and more specifically, C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264. However, it is not necessarily limited to these.

The red pigment may be subjected to resin treatment, surface treatment using a pigment derivative introduced with acidic or basic groups, etc. as necessary, graft treatment of the pigment surface with a polymer compound, atomization treatment by sulfuric acid atomization method, etc., organic for removing impurities A cleaning treatment with a solvent, water, or the like or a treatment for removing ionic impurities by an ion exchange method or the like may be performed.

The red dye may be used without limitation as long as it has solubility in organic solvents. Preferably, it is preferable to use a dye that has solubility in organic solvents and can secure reliability such as solubility in alkali developer, heat resistance, and solvent resistance.

As the red 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 compound of an acid dye, and derivatives thereof may be used. In addition, azo-based, xanthene-based, Phthalocyanine-based acid dyes and derivatives thereof may also be selected. The red dye may include a compound classified as a dye in the color index (published by The Society of Dyers and Colorists) or a known red dye described in a dyeing note (color dye).

As a specific example of the red dye,

C.I. solvent red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179, and the like;

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

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

C.I. Modanto Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 , 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95 red dyes may be mentioned, but are not necessarily limited thereto.

Each of the red dyes may be used alone or in combination of two or more.

As the red colorant, in terms of transmittance and contrast ratio, C.I. It is preferred to include Pigment Red 177, 179, 242 and 254.

The content of the red colorant in the colorant is included in an amount of 50 to 100% by weight based on 100% by weight of the solid content of the colorant, preferably 55 to 95% by weight, and more preferably 60 to 90% by weight. When the red colorant is included within the content range, it is preferable in terms of reliability and fairness.

(a2) pigment

As the pigment that may be further included in addition to the red colorant, organic or inorganic pigments generally used in the art may be used, and these may be used alone or in combination of two or more.

In particular, the organic and inorganic pigments include compounds classified as pigments in the color index (published by The Society of Dyers and Colorists), and more specifically, the color index (C.I.) number of pigments, but are not necessarily limited thereto.

C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185;

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

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

C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 16, 21, 28, 60, 64 and 76;

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

C.I Pigment Brown 28;

C.I Pigment Black 1 and 7;

When the red photosensitive resin composition of the present application includes the pigment (a2), the content of the pigment (a2) may be 5 to 60% by weight, preferably 10 to 45% by weight, based on the total weight of the solid content of the colorant. When the pigment is included within the above range, the color density of the pixel is sufficient even when the thin film is formed, and the omission property of the non-pixel portion does not decrease during development, so that no residue is generated.

(a3) pigment dispersant

As the pigment, it is preferable to use a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. Examples of the method for uniformly dispersing the particle diameter of the pigment include a method of dispersing treatment by containing a pigment dispersant, and according to the method, a pigment dispersion in a state in which the pigment is uniformly dispersed in a solution can be obtained.

The pigment dispersant is added to deagglomerate and maintain stability of the pigment, and may be used without limitation in the art, and specific examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, Surfactants, such as polyester type and polyamine type, etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively.

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

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

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymer, sorbitan fatty acid ester, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, etc. are mentioned.

In addition, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines are mentioned. have.

In addition, the pigment dispersant preferably includes an acrylate-based dispersant (hereinafter, acrylate-based dispersant) including butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA). Commercially available products of the acrylate-based dispersant include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070 or DISPER BYK-2150, and the acrylate-based dispersant may be used alone or in combination of two or more. can

As the pigment dispersant, a pigment dispersant of a resin type other than the acrylate-based dispersant may be used. The pigment dispersants of the other resin types include known resin type pigment dispersants, in particular polyurethane, polycarboxylic acid esters typified by polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids (partially) amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl-containing polycarboxylic acids and modified products thereof, or free ) oily dispersants such as amides or salts thereof formed by the reaction of a polyester having a carboxyl group with poly (lower alkyleneimine); water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; modified polyacrylates; adducts of ethylene oxide/propylene oxide; and phosphate esters.

As a commercially available product of the above-mentioned other resin type pigment dispersant, as a cationic resin dispersant, for example, BYK (Big) Chemi Corporation's trade names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF 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; Trade names from Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Kawaken Fine Chemicals' trade names: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Trade names of Ajinomoto Corporation: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Trade names of Kyoeisha Chemical Corporation: FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, fluorene DOPA-44, etc. are mentioned.

In addition to the acrylate-based dispersant, other resin-type pigment dispersants may be used alone or in combination of two or more, or may be used in combination with an acrylate-based dispersant.

The pigment dispersant may be included in an amount of 5 to 60 wt%, preferably 15 to 50 wt%, based on 100 wt% of the solid content of the pigment. When the pigment dispersant is included within the above range, it is possible to maintain an appropriate viscosity level that is easy to prepare the red photosensitive resin composition, and it is preferable because the gelation process is easy after atomization and dispersion of the pigment.

(a4) dye

The dye that may be further included in addition to the red colorant may be used without limitation as long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye that has solubility in organic solvents and can secure reliability such as solubility in alkali developer, heat resistance, and solvent resistance.

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 compound of an acid dye, and derivatives thereof may be used. In addition, azo-based, xanthene-based, phthalocyanine Acid dyes and derivatives thereof may also be selected. Preferably, the dye is a compound classified as a dye in the color index (published by The Society of Dyers and Colorists) or a known dye described in the dyeing note (color dye).

As a specific example of the dye, C.I. As a solvent dye,

C.I. yellow dyes such as solvent yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163;

C.I. orange dyes such as solvent orange 2, 7, 11, 15, 26, 41, 45, 56, 62;

C.I. blue dyes such as solvent blue 5, 35, 36, 37, 44, 59, 67, and 70;

C.I. violet dyes such as solvent violet 8, 9, 13, 14, 36, 37, 47, 49;

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

Also, C.I. As an acid dye,

C.I. 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. ;

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

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

Violet dyes such as C.I. Acid Violet 6B, 7, 9, 17, 19, 66;

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

Also as a C.I. direct dye,

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 and other yellow dyes;

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

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 blue dye;

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

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

Also, C.I. As a modanto dye,

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

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

C.I. modanto blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, blue dyes such as 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;

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

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

Each of the above dyes may be used alone or in combination of two or more.

When the red photosensitive resin composition of the present application includes the dye (a4), the content of the dye (a4) is included in an amount of 0.5 to 80% by weight based on 100% by weight of the solid content of the colorant, preferably 0.5 to 60% by weight, 1 to 50% by weight is more preferred. When the dye is included in the above content range, it is possible to prevent a problem of reliability degradation in which the dye is eluted by the organic solvent after pattern formation, and the sensitivity is increased, which is preferable.

The content of the colorant may be 5 to 60% by weight, preferably 10 to 50% by weight, more preferably 15 to 45% by weight based on the total weight of the solid content in the red photosensitive resin composition. When the colorant is included within the above range, it is preferable that the color concentration of the pixel is sufficient when the thin film is formed, and the omission property of the non-pixel portion does not decrease during development, so that it is difficult to generate a residue.

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

(B) alkali-soluble resin

The alkali-soluble resin is a component that imparts solubility to an alkali developer used in the developing process when forming a pattern, and the alkali-soluble resin of the present invention includes an ethylenically unsaturated monomer (b1) having a carboxyl group. have.

(b1) an ethylenically unsaturated monomer having a carboxyl group

Specific examples of the ethylenically unsaturated monomer having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids; Polymer mono(meth)acrylates having a carboxyl group and a hydroxyl group at both terminals, such as ω-carboxypolycaprolactone mono(meth)acrylate, etc. are mentioned, and acrylic acid and methacrylic acid are preferable.

The said alkali-soluble resin can be manufactured by copolymerizing the said ethylenically unsaturated monomer which has the said carboxyl group, and the ethylenically unsaturated monomer (b2) which has a hydroxyl group. Alternatively, the alkali-soluble resin can be prepared by copolymerizing the copolymer of the ethylenically unsaturated monomer having a carboxyl group and the compound (b3) having a glycidyl group. Alternatively, the alkali-soluble resin can be produced by copolymerizing the ethylenically unsaturated monomer having the carboxyl group, the ethylenically unsaturated monomer having the hydroxyl group, and the compound having the glycidyl group.

(b2) an ethylenically unsaturated monomer having a hydroxyl group

Specific examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy- 3-phenoxypropyl (meth)acrylate, N-hydroxyethyl acrylamide, etc., and 2-hydroxyethyl (meth)acrylate is preferable, and two or more types may be used in combination.

(b3) a compound having a glycidyl group

Specific examples of the compound having a glycidyl group include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl ether, ethyl glycidyl ether, Dil ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, aryl glycidyl ether, glycidyl methacrylate Cidyl ester, etc., butyl glycidyl ether, aryl glycidyl ether, and methacrylic acid glycidyl ester are preferable, and two or more types may be used in combination.

The alkali-soluble resin may be prepared by copolymerizing the unsaturated monomer (b4).

(b4) unsaturated monomers

Each of the unsaturated monomers may be used alone or in combination of two or more, and the examples are not limited thereto.

Styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinyl aromatic vinyl compounds such as benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether;

N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m -N-substituted maleimide compounds, such as methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, and N-p-methoxyphenylmaleimide;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth)acrylates such as sec-butyl (meth)acrylate and t-butyl (meth)acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl (meth) acrylate, 2- alicyclic (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate and isobornyl (meth)acrylate;

aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate;

3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane; 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. of unsaturated oxetane compounds.

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

In addition, in order to secure the developability of the red photosensitive resin composition, the alkali-soluble resin has an acid value of 10-200 mgKOH/g, preferably 10-150 mgKOH/g. When the acid value of the alkali-soluble resin satisfies the above range, it is preferable that the red photosensitive resin composition can secure a sufficient development speed, improve adhesion to the substrate, and prevent short circuit of the pattern.

The alkali-soluble resin of the present invention may have a weight average molecular weight (Mw) of 3,000 to 30,000, preferably 5,000 to 25,000. In addition, the molecular weight distribution of the alkali-soluble resin of the present invention, that is, the weight average molecular weight relative to the number average molecular weight (weight average molecular weight (Mw) / number average molecular weight (Mn)) may be 1.5 to 6.0, preferably 1.8 to 4.0, , When the alkali-soluble resin satisfies the ranges of the weight average molecular weight and molecular weight distribution, there is an advantage of excellent developability.

The content of the alkali-soluble resin may be 10 to 80% by weight, preferably 10 to 70% by weight, based on the total weight of the solid content of the red photosensitive resin composition. When the alkali-soluble resin is included within the above range, it is preferable because the solubility in the developer is sufficient to facilitate pattern formation, and the film reduction of the pixel portion of the exposed portion is prevented during development, and the omission of the non-pixel portion is improved. do.

(C) photopolymerizable compound

The said photopolymerizable compound is a compound which can superpose|polymerize by the action|action of the photoinitiator mentioned later, and a monofunctional monomer, a bifunctional monomer, other polyfunctional monomer, etc. are mentioned.

Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl p Rollidone etc. are mentioned. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. , bis(acryloyloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like. Specific examples of the other polyfunctional monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and di Pentaerythritol hexa(meth)acrylate etc. are mentioned. Among these, the polyfunctional monomer more than bifunctional is used preferably.

The photopolymerizable compound may be included in an amount of 5 to 50% by weight, preferably 7 to 45% by weight, based on the total weight of the solid content of the red photosensitive resin composition of the present invention. When the photopolymerizable compound is contained within the above range, it is preferable because the strength and smoothness of the pixel portion tend to be good.

(D) photoinitiator

The photopolymerization initiator is characterized in that it comprises a compound represented by the following formula (2).

[Formula 2]

In Formula 2, A is carbon or nitrogen, and R ₃ to R ₁₀ may each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, Formula 3 below, COR ₁₈ or NO ₂ .

R ₁₈ may be an aryl group having 6 to 20 carbon atoms that is unsubstituted or substituted with one or more substituents selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms.

[Formula 3]

In Formula 3, R ₁₆ is hydrogen, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a naphthyl group, R ₁₇ is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, wherein X may be CO or a direct connection .

Alternatively, in Formula 2, A is carbon or nitrogen, and R ₃ and R ₄ , R ₄ and R ₅ , R ₅ and R ₆ , R ₇ and R ₈ , R ₈ and R ₉ , or R ₉ and R At least one pair of ₁₀ may be represented by Formula 4 below.

[Formula 4]

In Formula 4, R ₁₁ to R ₁₄ may each independently be hydrogen, a substituted or unsubstituted C 1 to C 20 alkyl group, or a substituted or unsubstituted phenyl group.

Alternatively, in Formula 2, A is carbon or nitrogen, and R ₁₅ is a substituted or unsubstituted C1-C20 alkyl group, C2-C12 alkenyl group, C4-8 cycloalkenyl group, C2-C20 It may be an alkynyl group of 12, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, or a naphthyl group.

The photopolymerization initiator may include, in addition to the compound represented by Formula 2, a photopolymerization initiator generally used in this field in an amount of 5 to 40 wt% based on the total weight of the photopolymerization initiator. The generally used photoinitiator includes, for example, a triazine-based compound, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, and an oxime-based compound.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, and 2-(3',4'-dime Toxy styryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxy naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2 -(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl-4,6-bis(trichloromethyl)-s-triazine, 2- Piphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichlorobetyl)-6-styryl-s-triazine, 2-(naphtho 1-yl)-4,6- Bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-trichloromethyl ( piperonyl)-6-triazine, 2,4-trichloromethyl(4'-methoxy styryl)-6-triazine, and the like.

Specific examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyltrichloroacetophenone , p-t-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane -1-one and the like.

Examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethyl amino)benzophenone, 4,4'- Bis(diethyl amino) benzophenone, 4,4'- dimethylamino benzophenone, 4,4'- dichloro benzophenone, 3,3'- dimethyl- 2-methoxybenzophenone, etc. are mentioned.

The thioxanthone-based compound includes thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thi Oxanthone, 2-chlorothioxanthone, etc. are mentioned.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyldimethyl ketal.

Examples of the oxime-based compound include 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione and 1-(o-acetyloxime)-1-[9-ethyl- 6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone etc. are mentioned.

In addition to those exemplified above, carbazole-based compounds, diketone-based compounds, sulfonium borate-based compounds, diazo-based compounds, and biimidazole-based compounds may also be used as the photopolymerization initiator.

The content of the photoinitiator in the red photosensitive resin composition of the present invention may be 0.1 to 10 wt%, preferably 3 to 8 wt%, based on the total solid weight of the red photosensitive resin composition of the present invention. When the photopolymerization initiator is included within the above range, photopolymerization occurs sufficiently during exposure in the pattern forming process, and a decrease in transmittance due to the unreacted initiator remaining after photopolymerization may not occur, so it is preferable.

(E) UV absorbers

The red photosensitive resin composition of the present invention includes a UV absorber, and the UV absorber satisfies at least one of the following conditions i) and ii), and preferably satisfies both of the following conditions i) and ii). characterized in that

i) When the maximum absorption wavelength in the wavelength range of 270 nm or more and less than 330 nm is λmax1 and the maximum absorption wavelength in the wavelength range of 330 nm or more and less than 400 nm is λmax2, absorbance at λmax1 / absorbance at λmax2 > 0.8 ; and

ii) When the absorbance of the maximum absorption wavelength (λmax) in the entire wavelength range is normalized to 1, the absorbance at the wavelength of 365 nm is 0.3 or less

The normalization refers to normalization by dividing a spectrum value for each wavelength by a value at the maximum absorption wavelength (λmax).

When the UV absorber satisfies the conditions of i) and ii), it is advantageous to the pattern margin according to the type of exposure machine and the change in the UV wavelength because the change in pattern characteristics according to the change of the illuminance and exposure amount is small, and the pattern undercut, adhesion and There is an advantage that the coating film surface roughness characteristics can be improved.

Regarding condition i), in terms of pattern film curing degree, flatness and reliability, it is preferable that the absorbance at λmax1 / absorbance at λmax2 > 0.9, and the absorbance at λmax1 / absorbance at λmax2 > 1.1 is more desirable.

Further, in relation to condition i), from the viewpoint of pattern undercut and adhesion, λmax1 is more preferably within a wavelength range of 290 to 330 nm.

In addition, the ultraviolet absorber may further satisfy the following conditions iii) in addition to the conditions of i) and ii).

iii) When the absorbance of the maximum absorption wavelength (λmax) in the entire wavelength range is normalized to 1, the absorbance at 380 nm wavelength is 0.2 or less

When the ultraviolet absorber further satisfies the condition of iii) in addition to the conditions of i) and ii), it is advantageous in terms of post-process reliability.

The ultraviolet absorber may include at least one selected from a hindered amine-based compound, a benzophenone-based compound, a benzotriazole-based compound, and a triazine-based compound.

As the hindered amine compound, for example, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)- 4-hydroxyphenyl]methyl]butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, and poly[[6-[(1,1,3,3-) Tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2) , 6,6-tetramethyl-4-piperidyl) imino]] and the like.

As the benzophenone-based compound, for example, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxyhenzophenone, 2,4-dihydroxybenzo and phenone, 2-hydroxy-4-methoxybenzophenone, and 2,2',4,4'-tetrahydroxybenzophenone.

Examples of the benzotriazole-based compound include octyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate; 2-ethylhexyl 3-(3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl)propionate, [3-[3-(2H- Benzotriazol-2-yl)-5-(1,1-methylethyl)-4-hydroxyphenyl]-1-oxopropyl]-w-[3-[3-(2H-benzotriazole-2- yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]poly(oxy-1,2-ethanediyl), (3-(3-(2H-benzo Triazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl)-1-oxopropyl)-hydroxypoly(oxo-1,2-ethanediyl), 2-( 3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, 2-(2H-benzotriazol-2-yl)-4,6-ditertpentylphenol, 3 -(2H-benzotriazolyl)-5-(1,1-dimethylethyl)-4-hydroxy-benzinpropionic acid octyl ester, 2-(2H-benzotriazol-2-yl)-4,6-bis( 1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetra methylbutyl)phenol; and the like.

Examples of the triazine-based compound include 2-(4,6-dimethyl-1,3,5-triazin-2-yl)-5-((hexyl)oxy)-phenol, 2-(4- (2-hydroxy-3-tridecyloxypropyl)oxy)-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(4 -(2-hydroxy-3-didecyloxypropyl)oxy)-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2- (2-hydroxy-4-(3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy)phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3, 5-triazine, 2,2'[6-(2,4-dibutoxyphenyl)-1,3,5-triazine-2,4-diyl]bis(5-butoxyphenol), 6- methylheptyl 2-{4-[4,6-di(4-biphenylyl)-1,3,5-triazin-2-yl]-3-hydroxyphenoxy}propanoate; and the like. .

The ultraviolet absorber may be included in an amount of 0.1 to 7% by weight, preferably 1 to 5% by weight, based on the total weight of the solid content of the red photosensitive resin composition of the present invention. When the ultraviolet absorber is included within the above range, there is an advantage that pattern fairness and reliability can be improved at the same time.

(F) polyfunctional thiol compound

The polyfunctional thiol compound is a compound having two or more thiol (-SH) groups in the same molecule, and includes a primary thiol or secondary thiol compound having 2 to 5 functional groups. The polyfunctional thiol compound may serve to prevent staining on the surface of the coating film, and to improve chemical resistance, surface roughness, and residual film rate of the coating film.

The polyfunctional thiol compound may preferably include at least one selected from compounds represented by the following Chemical Formulas 1-1 to 1-5.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

In Formulas 1-1 to 1-5,

R ¹ and R ² are each independently a hydrogen atom or a methyl group,

m is an integer of 1-12.

The polyfunctional thiol compound is 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2 ,4,6(1H,3H,5H)-trione, trimethylolpropanetris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutylate), pentaerythritoltetrakis(3-mer captopropionate) and dipentaerythritol hexakis (3-mercaptopropionate).

The polyfunctional thiol compound may be included in an amount of 0.1 to 5 wt%, preferably 1 to 4 wt%, based on the total solid weight of the red photosensitive resin composition of the present invention. When the polyfunctional thiol compound is included within the above range, there is an advantage in storage stability.

(G) solvent

As long as the solvent is effective in dissolving other components included in the red photosensitive resin composition according to the present invention, the solvent used in the conventional colored photosensitive resin composition may be used without particular limitation, and in particular, ethers, aromatic hydrocarbons, and ketones. , alcohols, esters or amides are preferable.

The solvent is specifically ethylene glycol monoalkyl ethers such as 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 dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monomethyl ether acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene, methyl ethyl ketone , acetone, methyl amyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, 3-ethyl ethoxypropionate, 3- Esters, such as methyl methoxypropionate, and cyclic esters, such as (gamma)-butyrolactone, etc. are mentioned.

The solvent is preferably an organic solvent having a boiling point of 100° C. to 200° C. in terms of coatability and drying properties, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butalak. Tate, 3-ethoxy ethyl propionate, 3-methoxy methyl propionate, etc. can be used.

Each of the above solvents may be used alone or in combination of two or more.

The solvent may be included in an amount of 60 to 95% by weight, preferably 70 to 90% by weight, based on the total weight of the red photosensitive resin composition. When the solvent is included within the above content range, the effect of improving the applicability when applied with an application device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), an inkjet, etc. It is preferable to provide

(H) additives

The red photosensitive resin composition according to the present invention may further include additives as necessary, and as a specific example, at least one selected from a dispersant, a wetting agent, a silane coupling agent, a sensitizer, and an anti-aggregation agent may be used.

A commercially available surfactant may be used as the dispersant, and the surfactant may include a silicone-based surfactant, a fluorine-based surfactant, a silicone-based surfactant having a fluorine atom, and mixtures thereof. Examples of the silicone-based surfactant include a surfactant having a siloxane bond. Commercially available products include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone 29SHPA, Toray Silicone SH30PA, polyether-modified silicone oil SH8400 (manufactured by Toray Silicone Co., Ltd.), KP321 , KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Silicon), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicon), etc. can be heard

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Specifically, Prolinate (trade name) FC430, Prolinate FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapack (brand name) F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, Megapack F183, Megapack R30 (manufactured by Dainippon Ink Chemical Co., Ltd.), ftop (brand name) EF301, ftop EF303, ftop EF351, ftop EF352 (manufactured by Shin-Akitakasei Co., Ltd.), Seo Pron (brand name) S381, Suflon S382, Suflon SC101, Suflon SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemicals, Inc.), BM-1000, BM-1100 (product) Name: manufactured by BMChemie) and the like.

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specific examples include Megapack (brand name) R08, Megapack BL20, Megapack F475, Megapack F477, Megapack F443 (manufactured by Dainippon Ink Chemical Co., Ltd.).

The wetting agent may include, for example, glycerin, diethylene glycol, and ethylene glycol, and may include at least one selected from among them.

Examples of the silane coupling agent include aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. Commercially available products include SH6062 and SZ6030 (Toray-Dow). Corning Silicon co., Ltd.), KBE903, KBM803 (manufactured by Shin-Etsu silicone co., Ltd.), and the like.

Examples of the sensitizer include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'- Biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxylate, titanocene compound, etc. are mentioned.

Examples of the aggregation inhibitor include sodium polyacrylate.

< Color filter >

One embodiment of the present invention relates to a color filter formed using the above-described red photosensitive resin composition. A color filter according to an embodiment of the present invention is characterized in that it includes a colored pattern formed by applying the above-described red photosensitive resin composition on a substrate, and exposing and developing the red photosensitive resin composition in a predetermined pattern.

Hereinafter, a pattern forming method using the red photosensitive resin composition of the present invention will be described in detail.

First, after apply|coating a red photosensitive resin composition to a base material, volatile components, such as a solvent, are removed by heat-drying, and a smooth coating film is obtained.

As a coating method, it can carry out, for example by the spin coating method, the cast coating method, the roll coating method, the slit-and-spin coating method, or the slit coating method. After application, heat drying (prebaking) or drying under reduced pressure is heated to volatilize volatile components such as solvents. Here, the heating temperature is usually 70 to 200°C, preferably 80 to 130°C. The thickness of the coating film after heat drying is usually about 1 to 8 µm. In this way, the obtained coating film is irradiated with an ultraviolet-ray through the mask for forming the target pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper so that parallel rays are uniformly irradiated to the entire exposed portion and the mask and the substrate are accurately aligned. When irradiated with ultraviolet rays, the portion irradiated with ultraviolet rays is cured.

As the ultraviolet rays, g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), etc. can be used, and in terms of suppressing line width from expanding, i-line ultraviolet rays are used. It is preferable to use i-line ultraviolet rays having a half width of 4 to 15 nm.

The irradiation amount of ultraviolet rays may be appropriately selected according to need, and the present invention is not limited thereto. When the cured coating film is brought into contact with a developer to dissolve the unexposed portion and developed, a desired pattern shape can be formed.

As the developing method, any of a liquid addition method, a dipping method, and a spray method may be used. Moreover, you may incline a board|substrate at an arbitrary angle at the time of development. The developing solution is usually an aqueous solution containing an alkaline compound and a surfactant. Any of an inorganic and organic alkaline compound may be sufficient as the said alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate , sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia, and the like. Further, specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine, etc. are mentioned.

These inorganic and organic alkaline compounds can be used individually or in combination of 2 or more types, respectively. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10 mass%, more preferably 0.03 to 5 mass%.

The surfactant in the alkaline developer may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymer, sorbitan fatty acid ester, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, etc. are mentioned.

Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, dodecylbenzenesulfonic acid Alkylaryl sulfonates, such as sodium and sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or quaternary ammonium salts. These surfactants can be used individually or in combination of 2 or more types, respectively.

The concentration of the surfactant in the developer is usually 0.01 to 10 mass%, preferably 0.05 to 8 mass%, and more preferably 0.1 to 5 mass%. After image development, it washes with water and can also post-baking for 10 to 60 minutes at 150-230 degreeC as needed.

< Display device >

One embodiment of the present invention relates to a display device including the above-described color filter.

The color filter of the present invention is not only a general liquid crystal display device (LCD), but also various display devices such as an electroluminescence display device (EL), a plasma display device (PDP), a field emission display device (FED), and an organic light emitting device (OLED). can be applied to

The display device of the present invention includes a configuration known in the art, except for having the above-described color filter.

A display device according to an embodiment of the present invention provides a color including a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles in addition to the color filter described above. A filter may be additionally provided. In such a case, the emission light of the light source applied to the image display device is not particularly limited, but a light source emitting blue light may be preferably used in terms of superior color reproducibility.

The display device according to an exemplary embodiment of the present invention may further include a color filter including only two color pattern layers among a red pattern layer, a green pattern layer, and a blue pattern layer in addition to the above-described color filter. In such a case, the color filter further includes a transparent pattern layer that does not contain quantum dot particles. When only two types of color pattern layers are provided, a light source emitting light of a wavelength indicating the remaining colors not included may be used. For example, when only the red pattern layer and the green pattern layer are included, a light source emitting blue light may be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer transmits the blue light as it is to display blue color.

Hereinafter, the present invention will be described in more detail based on examples, but the embodiments of the present invention disclosed below are merely illustrative, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and furthermore includes all modifications within the meaning and scope equivalent to those recorded in the claims. In addition, in the following examples and comparative examples, "%" and "part" indicating the content are based on mass unless otherwise specified.

<Reference Example: Spectral analysis by wavelength of UV absorber>

At 0.001 wt% (in PGMEA), the absorption spectrum of the ultraviolet absorber was analyzed for each wavelength, and the absorbance of the main wavelength is shown in Table 1 below. In addition, the absorption spectrum of the ultraviolet absorber is a value obtained by normalizing the absorbance of the maximum absorption wavelength (λmax) in the entire wavelength range to 1, that is, a value normalized by dividing the spectrum value for each wavelength by the value at the maximum absorption wavelength. It is shown together in Table 1 below.

Wavelength
(nm) Absorbance of UV absorbers Normalized Absorbance of UV Absorbers E-1 E-2 E-3 E-4 E-5 E-1 E-2 E-3 E-4 E-5 250 0.27 0.48 0.92 0.29 0.16 0.24 0.17 0.48 0.18 0.15 255 0.31 0.43 1.01 0.19 0.10 0.28 0.16 0.53 0.12 0.10 270 0.68 0.53 1.78 0.25 0.14 0.60 0.19 0.93 0.15 0.14 280 1.00 0.91 1.85 0.49 0.29 0.88 0.33 0.97 0.30 0.28 330 0.57 2.56 0.83 1.20 0.66 0.50 0.93 0.43 0.73 0.64 360 0.21 0.63 0.43 1.26 0.99 0.18 0.23 0.23 0.77 0.97 365 0.11 0.38 0.27 0.91 0.90 0.10 0.14 0.14 0.56 0.88 380 0.01 0.06 0.04 0.15 0.33 0.01 0.02 0.02 0.09 0.32 390 0.00 0.01 0.01 0.03 0.08 0.00 0.00 0.00 0.02 0.08 400 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.01 410 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

- E-1: Tinuvin 400

- E-2: Tinuvin 479

- E-3: ADK STAB LA-46

- E-4: Tinuvin 460

- E-5: Tinuvin 477

Referring to Table 1 above, the maximum absorption wavelength (λmax1) in the wavelength range of 270 nm or more and less than 330 nm of each UV absorber and the maximum absorption wavelength (λmax2) in the wavelength range of 330 nm or more and less than 400 nm of each UV absorber was confirmed and shown in Table 2 below. In addition, the absorbance ratio (A)/(B) was calculated from the absorbance (A) at λmax1 and the absorbance (B) at λmax2 and shown in Table 2 below. In addition, when the absorbance of the maximum absorption wavelength (λmax) in the entire wavelength range was normalized to 1, the absorbance at a wavelength of 365 nm was confirmed and shown in Table 2 below.

E-1 E-2 E-3 E-4 E-5 λmax1 (nm) 288 320 275 299 303 λmax2 (nm) 335 330 340 347 355 Absorbance at λmax1 (A) 1.00 1.00 1.00 0.55 0.65 Absorbance at λmax2 (B) 0.51 0.93 0.47 1.00 1.00 (A)/(B) 1.9 1.1 2.1 0.5 0.6 Normalized absorbance at 365 nm wavelength 0.10 0.14 0.14 0.56 0.89

Referring to Table 2, the UV absorbers of E-1 to E-3 have a value of (A)/(B) greater than 0.8, λmax1 is within a wavelength range of 270 to 330 nm, and a maximum absorption wavelength in the entire wavelength range When the absorbance of (λmax) is normalized to 1, it can be confirmed that the absorbance at a wavelength of 365 nm is 0.3 or less.

On the other hand, it can be seen that the UV absorbers of E-4 and E-5 have a value of (A)/(B) smaller than 0.8, and a normalized absorbance at a wavelength of 365 nm exceeds 0.3.

In order to evaluate the performance of the color filter prepared using the red photosensitive resin composition including the ultraviolet absorber having the values of (A)/(B) and the normalized absorbance satisfying a specific value, the following experiment was performed. carried out.

<Example>

Preparation Example 1: Preparation of Pigment Dispersion A-1

As a pigment, C.I. 40 parts by weight of Pigment Red 254, 24 parts by weight of BYK2001 (Dispervic: manufactured by BYK, 46% by weight of solid content) as a dispersant, and 136 parts by weight of propylene glycol methyl ether acetate as a solvent. was mixed and dispersed for 12 hours to prepare a pigment dispersion A-1 (solid content 32%).

Preparation Example 2: Preparation of Pigment Dispersion A-2

As a pigment, C.I. 40 parts by weight of Pigment Red 177, 24 parts by weight of BYK2001 (Dispervic: manufactured by BYK, solid content: 46% by weight) as a dispersant, and 136 parts by weight of propylene glycol methyl ether acetate as a solvent. was mixed and dispersed for 12 hours to prepare a pigment dispersion A-2 (solid content 32%).

Preparation Example 3: Preparation of Pigment Dispersion A-3

As a pigment, C.I. 40 parts by weight of Pigment Red 179, 24 parts by weight of BYK2001 (Dispervic: manufactured by BYK Co., Ltd., solid content 46% by weight) as a dispersant, and 136 parts by weight of propylene glycol methyl ether acetate as a solvent. was mixed and dispersed for 12 hours to prepare a pigment dispersion A-3 (solid content 32%).

Preparation Example 4: Preparation of Pigment Dispersion A-4

As a pigment, C.I. 40 parts by weight of Pigment Red 242, 24 parts by weight of BYK2001 (Dispervic: manufactured by BYK Co., Ltd., solid content 46% by weight) as a dispersant, and 136 parts by weight of propylene glycol methyl ether acetate as a solvent. was mixed and dispersed for 12 hours to prepare a pigment dispersion A-4 (solid content 32%).

Examples 1 to 12 and Comparative Examples 1 to 20: Preparation of a red photosensitive resin composition

Red photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 20 were prepared according to the compositions of Tables 3 and 4 below.

(weight%) Example One 2 3 4 5 6 7 8 9 10 11 12 pigment dispersion A-1 27 - - - 27 - - - 27 - - - A-2 - 27 - - - 27 - - - 27 - - A-3 - - 27 - - - 27 - - - 27 - A-4 - - - 27 - - - 27 - - - 27 Alkali-soluble resin B 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 photopolymerizable compound C 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 photopolymerization initiator D 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 UV absorber E-1 0.3 0.3 0.3 0.3 - - - - - - - - E-2 - - - - 0.3 0.3 0.3 0.3 - - - - E-3 - - - - - - - - 0.3 0.3 0.3 0.3 E-4 - - - - - - - - - - - - E-5 - - - - - - - - - - - - polyfunctional thiol compound F 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 solvent G 62.2 62.2 62.2 62.2 62.2 62.2 62.2 62.2 62.2 62.2 62.2 62.2

(weight%) comparative example One 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 pigment dispersion A-1 27 - - - 27 - - - 27 - - - 27 - - - 27 - - - A-2 - 27 - - - 27 - - - 27 - - - 27 - - - 27 - - A-3 - - 27 - - - 27 - - - 27 - - - 27 - - - 27 - A-4 - - - 27 - - - 27 - - - 27 - - - 27 - - - 27 Alkali-soluble resin B 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 photopolymerizable compound C 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 photopolymerization initiator D 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 UV absorber E-1 0.3 0.3 0.3 0.3 - - - - - - - - - - - - - - - - E-2 - - - - 0.3 0.3 0.3 0.3 - - - - - - - - - - - - E-3 - - - - - - - - 0.3 0.3 0.3 0.3 - - - - - - - - E-4 - - - - - - - - - - - - 0.3 0.3 0.3 0.3 - - - - E-5 - - - - - - - - - - - - - - - - 0.3 0.3 0.3 0.3 polyfunctional thiol compound F - - - - - - - - - - - - 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 solvent G 62.2 62.2 62.2 62.2 62.2 62.2 62.2 62.2 62.2 62.2 62.2 62.2 62.2 62.2 62.2 62.2 62.2 62.2 62.2 62.2

Components used in the Examples and Comparative Examples are as follows.

- A-1 to A-4: Pigment dispersions A-1 to A-4 according to Preparation Examples 1 to 4

- B: SPCY-1L (acrylic resin, manufactured by Showa Denko)

- C: dipentaerythritol triacrylate (DPHA, manufactured by Nippon Kayak)

- D: Irgacure OXE-01 (manufactured by Basf)

- E-1: Tinuvin 400

- E-2: Tinuvin 479

- E-3: ADK STAB LA-46

- E-4: Tinuvin 460

- E-5: Tinuvin 477

- F: pentaerythritol tetrakis (3-mercaptopropionate)

- G: propylene glycol methyl ether acetate

Experimental example

<Manufacture of color filter>

A color filter was prepared using the red photosensitive resin composition prepared according to Examples and Comparative Examples. First, the red photosensitive resin compositions of Examples and Comparative Examples were applied on a glass substrate by spin coating, placed on a heating plate, and maintained at a temperature of 80° C. for 3 minutes to form a color layer thin film. Then, a test photomask having a line/space pattern of 1 to 50 µm was placed on the test photomask, and the distance from the test photomask was set to 50 µm, and ultraviolet rays were irradiated. At this time, a pattern coating film irradiated with an illuminance of 50 mJ/cm 2 was prepared using an LED lamp including only an i-line (half width at half maximum) as the UV light source, and the color layer thin film irradiated with UV light was applied to a KOH aqueous solution developing solution of pH 10.5. It was developed by immersion for 2 minutes. A color filter was manufactured by washing the glass substrate on which the developed color layer thin film was formed using distilled water, drying it in a nitrogen gas atmosphere, and heating it in a heating oven at 80° C. for 1 hour to thermoset.

1. Chemical resistance evaluation

After immersing the color filter prepared using the red photosensitive resin composition according to the above Examples and Comparative Examples in PGMEA solvent at 50° C. for 5 minutes, the film thickness before and after evaluation was measured, and the change in film thickness (%) was calculated by the following formula was calculated according to Chemical resistance was evaluated according to the following criteria, and the results are shown in Table 5 below.

[Film thickness change (%) = film thickness after immersion in PGMEA / initial film thickness * 100]

<Chemical resistance evaluation criteria>

◎: 80% or more

△: 70% or more and less than 80%

×: less than 70%

2. Evaluation of undercut properties

The undercut was measured by observing the cross-sectional shape of the color filter pattern prepared using the red photosensitive resin composition according to Examples and Comparative Examples with SEM. The undercut characteristics were evaluated according to the following criteria, and the results are shown in Table 5 below.

[Undercut (㎛) = Line width at the top of the pattern - Line width at the bottom of the pattern]

<Undercut Evaluation Criteria>

◎: 1.5um or less

○: More than 1.5um and less than 2.0um

△: more than 2.0um and less than 3.5um

×: more than 3.5um

3. Adhesion evaluation

For the pattern of 50 um * 50 um size of the color filter prepared using the red photosensitive resin composition according to the Examples and Comparative Examples, the number of torn patterns was checked and the adhesion was evaluated according to the following criteria, and the results were It is shown in Table 5 below.

<Adhesiveness evaluation criteria>

◎: No tearing of pattern

○: 1 to 5 patterns torn

△: 6 to 10 patterns torn

×: 11 or more patterns torn

4. Surface roughness evaluation

An arithmetic mean roughness (Ra) value was measured for the surface shape of the color filter prepared using the colored photosensitive resin composition according to Examples and Comparative Examples through AFM. The surface roughness was evaluated according to the following criteria, and the results are shown in Table 5 below.

<Surface Roughness Evaluation Criteria>

◎: Ra 3 or less

△: more than Ra 3 and less than or equal to 5

×: more than Ra 5

5. Remaining film rate evaluation

In the manufacturing process of the color filter using the colored photosensitive resin composition according to the Examples and Comparative Examples, the film thickness before and after thermal curing was measured, and the remaining film ratio (%) was calculated according to the following equation. The remaining film rate was evaluated according to the following criteria, and the results are shown in Table 5 below.

[Residual film rate (%) = Film thickness after heat curing / Film thickness before heat curing * 100]

<Remaining film rate evaluation criteria>

◎: 97% or more

△: 92% or more and less than 97%

×: less than 92%

chemical resistance undercut adhesion surface roughness remaining film rate Example 1 ◎ ◎ ◎ ◎ ◎ Example 2 ◎ ◎ ◎ ◎ ◎ Example 3 ◎ ◎ ◎ ◎ ◎ Example 4 ◎ ◎ ◎ ◎ ◎ Example 5 ◎ ◎ ◎ ◎ ◎ Example 6 ◎ ◎ ◎ ◎ ◎ Example 7 ◎ ◎ ◎ ◎ ◎ Example 8 ◎ ◎ ◎ ◎ ◎ Example 9 ◎ ◎ ◎ ◎ ◎ Example 10 ◎ ◎ ◎ ◎ ◎ Example 11 ◎ ◎ ◎ ◎ ◎ Example 12 ◎ ◎ ◎ ◎ ◎ Comparative Example 1 △ ◎ ◎ △ △ Comparative Example 2 x ◎ ◎ x x Comparative Example 3 x ◎ ◎ x x Comparative Example 4 △ ◎ ◎ △ △ Comparative Example 5 △ ◎ ◎ △ △ Comparative Example 6 x ◎ ◎ x x Comparative Example 7 x ◎ ◎ x x Comparative Example 8 △ ◎ ◎ △ △ Comparative Example 9 △ ◎ ◎ △ △ Comparative Example 10 x ◎ ◎ x x Comparative Example 11 x ◎ ◎ x x Comparative Example 12 △ ◎ ◎ △ △ Comparative Example 13 ◎ △ △ ◎ ◎ Comparative Example 14 ◎ x x ◎ ◎ Comparative Example 15 ◎ x x ◎ ◎ Comparative Example 16 ◎ △ △ ◎ ◎ Comparative Example 17 ◎ △ △ ◎ ◎ Comparative Example 18 ◎ x x ◎ ◎ Comparative Example 19 ◎ x x ◎ ◎ Comparative Example 20 ◎ △ △ ◎ ◎

Referring to the results of Table 5, the color filter prepared using the colored photosensitive resin composition of Examples 1 to 12 of the present application, including the polyfunctional thiol compound and the ultraviolet absorber satisfying the conditions of i) to iii), is resistant to It can be seen that the chemical properties, undercutting, adhesion, surface roughness, and remaining film ratio are all excellent.

On the other hand, the color filter prepared using the colored photosensitive resin composition of Comparative Examples 1 to 20 using no polyfunctional thiol compound or an ultraviolet absorber that does not satisfy all of the conditions of i) to iii) has chemical resistance , it can be seen that undercut, adhesion, surface roughness, and/or residual film rate characteristics are significantly reduced.

Claims (8)

a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, a polyfunctional thiol compound, and a solvent;
The colorant includes a red colorant,
The ultraviolet absorber satisfies the following conditions i) and ii), a red photosensitive resin composition:
i) When the maximum absorption wavelength in the wavelength range of 270 nm or more and less than 330 nm is λmax1 and the maximum absorption wavelength in the wavelength range of 330 nm or more and less than 400 nm is λmax2, absorbance at λmax1 / absorbance at λmax2 >0.8; and
ii) When the absorbance of the maximum absorption wavelength (λmax) in the entire wavelength range is normalized to 1, the absorbance at a wavelength of 365 nm is 0.3 or less. The method according to claim 1,
The ultraviolet absorber, a red photosensitive resin composition comprising at least one selected from a hindered amine-based compound, a benzophenone-based compound, a benzotriazole-based compound, and a triazine-based compound. The method according to claim 1,
The polyfunctional thiol compound is a red photosensitive resin composition comprising at least one selected from compounds represented by the following Chemical Formulas 1-1 to 1-5.
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

(In Formulas 1-1 to 1-5,
R ¹ and R ² are each independently a hydrogen atom or a methyl group,
m is an integer of 1 to 12.) 4. The method of claim 3,
The polyfunctional thiol compound is 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2 ,4,6(1H,3H,5H)-trione, trimethylolpropanetris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutylate), pentaerythritoltetrakis(3-mer A red photosensitive resin composition comprising at least one selected from captopropionate) and dipentaerythritol hexakis (3-mercaptopropionate). The method according to claim 1,
The red colorant comprises at least one selected from CI Pigment Red 177, CI Pigment Red 179, CI Pigment Red 242, and CI Pigment Red 254, a red photosensitive resin composition. The method according to claim 1,
With respect to the total weight of solids in the red photosensitive resin composition,
5 to 60% by weight of the colorant;
10 to 80% by weight of the alkali-soluble resin;
5 to 50% by weight of the photopolymerizable compound;
0.1 to 10% by weight of the photopolymerization initiator;
0.1 to 7% by weight of the ultraviolet absorber;
1 to 4% by weight of the polyfunctional thiol compound; and
With respect to the total weight of the red photosensitive resin composition, comprising 60 to 95% by weight of the solvent, the red photosensitive resin composition. A color filter comprising a colored pattern made of the red photosensitive resin composition of any one of claims 1 to 6. A display device comprising the color filter according to claim 7.