KR20140118196A - Colored photosensitive resin composition - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition and, more specifically, to a colored photosensitive resin composition which includes a coloring agent, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the solvent includes a first solvent and a second solvent having lower boiling point and higher polarity than the first solvent; and the binder resin includes a first resin and a second resin having higher polarity than the first resin to be moved to the surface with the second solvent when the second solvent is evaporated, to have excellent brightness and transmittance to manufacture a color filter fully forming a color to be presented, and having excellent quality.

Description

COLORED PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a colored photosensitive resin composition.

Color filters are widely used in imaging elements, liquid crystal display devices, and the like, and their application range is rapidly expanding. A color filter used in a color liquid crystal display device, an image pickup device, or the like is a device in which a colored photosensitive resin composition containing a green coloring agent corresponding to each color of red, green and blue on a substrate on which a black matrix is patterned is uniformly After coating, the polar material cured layer formed by heating and drying (hereinafter, may be referred to as preliminary firing) may be exposed and developed, and if necessary, further heat curing (hereinafter also referred to as post-firing) To form pixels of each color.

2. Description of the Related Art Recently, color filters for liquid crystal displays (LCDs) have gradually become large-sized liquid crystal displays, and high-quality image quality is continuously required. In recent years, a liquid crystal display device including a color filter for a note PC and a mobile has been required to have higher color purity and high transmittance. As a material for such a color filter, CI pigment 242, which is a pigment used for a red pixel, Japanese Unexamined Patent Application Publication No. 11-14824 discloses a technique for use, and Japanese Unexamined Patent Publication (Kokai) No. 2002-14463 discloses a colored photosensitive resin composition that has excellent transmittance and does not leave a residue on a substrate after development. However, these technologies also have limitations in showing high brightness and high throughput characteristics.

Japanese Patent Application Laid-Open No. 11-14824 Japanese Patent Application Laid-Open No. 2002-14463

It is an object of the present invention to provide a colored photosensitive resin composition capable of producing a color filter excellent in luminance and transmittance.

1. A colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent; Wherein the solvent comprises a first solvent and a second solvent having a lower boiling point and a higher polarity than the first solvent and the binder resin can move to the surface together with the second solvent upon evaporation of the first resin and the second solvent The second resin having a higher polarity than the first resin.

2. The colored photosensitive resin composition according to 1 above, wherein the photopolymerizable compound comprises a first photopolymerizable compound having a different polarity and a second photopolymerizable compound.

3. The colored photosensitive resin composition according to 1 above, wherein the first solvent has a higher content in the composition than the second solvent.

4. The colored photosensitive resin composition according to 1 above, further comprising a leveling agent.

5. A color filter made of a colored photosensitive resin composition according to any one of the above 1 to 4.

6. The color filter of claim 5, wherein the color filter comprises a substrate, a color layer formed on the substrate, and a polar material cured layer formed on the color layer.

7. A liquid crystal display device comprising the color filter of 5 above.

The colored photosensitive resin composition of the present invention is excellent in brightness and transmittance, can sufficiently express the color to be expressed, and can produce a color filter excellent in quality.

1 schematically shows a process of forming a polar material cured layer when a color filter is manufactured using the colored photosensitive resin composition of the present invention.
Fig. 2 shows the refractive index difference and transmittance between the color filter formed of the composition of Comparative Example 1 and the color filter of the color filter formed of the composition of Example 1. Fig.
Fig. 3 is a scanning electron microscope (SEM) showing the formation of a new polar material cured layer in a color filter formed of the colored photosensitive resin composition of Example 1. Fig.

The present invention includes a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent; Wherein the solvent comprises a first solvent and a second solvent having a lower boiling point and a higher polarity than the first solvent and the binder resin can move to the surface together with the second solvent upon evaporation of the first resin and the second solvent A second resin having a higher polarity than that of the first resin so as to provide a color filter having excellent brightness and transmittance and capable of sufficiently expressing hues and having excellent quality.

Hereinafter, the present invention will be described in detail with reference to the drawings.

1 schematically shows a process of forming a polar material cured layer when a color filter is produced using the colored photosensitive resin composition of the present invention. Referring to this, when the color filter is prepared with the colored photosensitive resin composition of the present invention, the second solvent having a low boiling point evaporates before the first solvent during the drying process after coating the composition. At this time, since the polarity of the second solvent is larger than that of the first solvent, a part of the resin having a larger polarity is also moved to the surface of the coated composition, and after a color filter manufacturing process such as exposure and development, A polar material cured layer is formed.

The polarized material cured layer serves to reduce the difference in refractive index between the color layer and the medium on the upper side of the polar material cured layer. Fig. 2 shows the relationship between the color filter formed of the composition of Comparative Example 1 and the color filter formed of the composition of Example 1 of the present invention The refractive index difference and transmittance between the media of the color filter are shown, and in Fig. 3, a polar material cured layer is shown in the color filter according to an embodiment of the present invention. The light emitted from the light source passes through the glass and color layer to the air. The refractive index of the color layer is 1.7, and the refractive index of air is 1.0. Therefore, since the refractive index difference is large, the light is reflected and the final transmittance is decreased. However, in the color filter according to the present invention, the polar material cured layer is formed on the color layer, and the refractive index of the polar material cured layer is 1.5, so that the difference in refractive index with air is reduced, thereby lowering the reflectance and ultimately improving the ultimate transmittance.

The colored photosensitive resin composition of the present invention includes a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

<Colorant>

The colorant may be a pigment, a dye or a mixture thereof.

The pigment may be an organic pigment, an inorganic pigment or a mixture thereof, which are commonly used in the art.

The organic pigment is not particularly limited and may be a pigment used for printing ink, inkjet ink, etc. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, Anthanthrone pigments, indanthrone pigments, pravanthrone pigments, anthraquinone pigments, anthraquinone pigments, anthanthrone pigments, anthanthrone pigments, indanthrone pigments, indanthrone pigments, Pyranthrone pigments, diketopyrrolopyrrole pigments, and the like. These may be used alone or in combination of two or more.

The inorganic pigment is not particularly limited and may be a metal compound such as a metal oxide or a metal complex salt and specifically includes a group consisting of iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black &Lt; / RTI &gt; These may be used alone or in combination of two or more.

Organic pigments and inorganic pigments are compounds classified as pigments in the color index (The Society of Dyers and Colourists), and specifically 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 Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264; C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38; C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64 and 76; C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58; C.I. Pigment Brown 28; C.I. Pigment Black 1 and 7, and the like, preferably C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 122, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 3, Pigment Blue 15: 6, C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. Pigment Green 58, and the like. These may be used alone or in combination of two or more.

The dye is not particularly limited as long as it has solubility in an organic solvent and can ensure reliability such as solubility in an alkali developing solution, heat resistance, solvent resistance, etc., for example, an acid dye having an acid group such as a sulfonic acid or a carboxylic acid; Salts of acidic dyes and nitrogen-containing compounds; Sulfonamide forms of acidic dyes and derivatives thereof; Azo dyes, xanthan dyes, phthalocyanine dyes, and derivatives thereof.

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

The dye is not particularly limited, and for example, C.I. As solvent dyes, 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. Red dyes such as Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179; 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 and the like. In view of excellent solubility in organic solvents, Solvent Yellow 14, 16, 21, 56, 151, 79, 93; C.I. Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; C.I. Solvent Orange 41, 45, 62; C.I. Solvent Blue 35, 36, 44, 45, 70; C.I. Solvent violet 13, and C.I. Solvent Yellow 21, 79; C.I. Solvent Red 8, 122, 132; C.I. Solvent Orange 45, 62 or the like is more preferable.

Also, C.I. CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, Yellow dye; CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 , 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349 Red dyes such as 382, 383, 394, 401, 412, 417, 418, 422, 426; Orange dyes such as C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, , 335, 340 and the like; Violet dyes such as C.I. Acid Violet 6B, 7, 9, 17, 19, 66 and the like; Green dyes such as CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106 and 109, Preferably CI Acid Yellow 42; C.I. Acid Red 92; C. I. Acid Blue 80, 90; C.I. Acid Violet 66; C.I. Acid Green 27, and the like.

As CI direct dyes, CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102 , 108, 109, 129, 136, 138, 141 and the like; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; Orange dyes such as C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293; 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,

Also, C.I. Yellow dyes such as C.I. Modatto Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65 as modaneto dyes; CI Modal 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 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; CI Modanato Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, dyes; CI Modanito Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 43, 44, 48, 49, 53, 61, 74, 77, 83, and 84; Violet colored dyes such as C.I. Modanth 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. Modatto Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43,

These dyes may be used alone or in combination of two or more.

The content of the colorant is not particularly limited and may be in the range of 5 to 60% by weight, preferably in the range of 10 to 45% by weight, based on the solid content of the colored photosensitive resin composition. When the content of the colorant is within the above range, the color density of the pixel is sufficient, and the non-curing portion of the non-cured portion is not deteriorated during development.

The colorant is added to the composition in the form of a dispersion for uniform mixing in the composition. The dispersion may be prepared by further including a dispersant and a solvent used in the composition in addition to the colorant.

The dispersant is added for maintaining deagglomeration and stability of the pigment, and any of those generally used in the art can be used without limitation. Preferably an acrylate-based dispersant comprising BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate); Polycarboxylic acid esters; Unsaturated polyamides; Polycarboxylic acids; (Partial) amine salts of polycarboxylic acids; Ammonium salts of polycarboxylic acids; Alkylamine salts of polycarboxylic acids; Polysiloxanes; Long chain polyaminoamide phosphate salts; Esters of hydroxyl group-containing polycarboxylic acids and their modification products; An amide formed by the reaction of a polyester having a free carboxyl group with a poly (lower alkyleneimine) or a salt thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide; Phosphate esters and the like. These may be used alone or in combination of two or more.

DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK- DISPER BYK-182, DISPER BYK-184, DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150 (BYK KEMISA); EFKA-44, EFKA-44, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA- 4400, EFKA-4406, EFKA-4510, EFKA-4800 (BASF); SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 (Lubirzol); Hinoact T-6000, Hinoact T-7000, Hinoact T-8000 (Kawaken Fine Chemicals); AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 (Ajinomoto); FLORENE DOPA-17HF, Florene DOPA-15BHF, Florene DOPA-33 and Florene DOPA-44 (Kyoeisha Chemical Co., Ltd.). These may be used alone or in combination of two or more.

The content of the dispersing agent is not particularly limited and may be, for example, 5 to 60 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the pigment based on the solid content. When the content of the dispersing agent is within the above range, the pigment can be finely atomized and the coloring agent dispersion can have an appropriate viscosity.

<Binder Resin>

The binder resin according to the present invention includes a first resin and a second resin having different polarities.

In the present invention, the second resin is a resin having a polarity higher than that of the first resin, and the second resin moves to the surface of the coated composition together with the evaporation of the second solvent to form a polar material- The resin is used for color layer formation. In this respect, the larger the difference in polarity between the second resin and the first resin, the better, and more preferably, the first resin may be substantially non-polar or apolar. In such a case, the polar material cured layer generation promoting effect can be maximized.

The first and second resins according to the present invention are not particularly limited as long as they have different polarities from each other, and examples thereof include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, 2-acryloxyethylhydrogenphthalate, Acrylate, isobutyl acrylate, t-butyl acrylate, lauryl acrylate, glycidyl acrylate, alkyl acrylate, stearyl acrylate, cyclohexyl acrylate, Acrylate, isobornyl acrylate, benzyl acrylate, 2-hydroxy acrylate, trimethoxy butyl acrylate, ethyl carbitol acrylate, phenoxy ethyl acrylate, 4-hydroxybutyl acrylate, phenoxypolyethylene glycol Acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxypropyl Acrylate and their methacrylate; Acrylates including halogen compounds such as 3-fluoroethyl acrylate and 4-fluoropropyl acrylate, and methacrylates thereof; Acrylates including siloxane groups such as triethylsiloxy ethyl acrylate and methacrylates thereof; And olefins having an aromatic group such as styrene, 4-methoxystyrene, and the like.

Some of the binder resins according to the present invention may be included in the dispersion of the colorant and may also serve as a dispersion medium (dispersion resin) of the colorant.

The dispersion resin assists in the action of the dispersion medium of the colorant, and makes it possible to produce a dispersion in which the colorant is more uniformly dispersed.

When a part of the binder resin serves as a dispersing resin, the first and second resins may be polymerized by including a compound having a carboxyl group and an unsaturated bond.

The kind of the compound having a carboxylic acid group and an unsaturated bond is not particularly limited, and examples thereof 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 thereof; mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate, and the like, preferably acrylic acid, methacrylic acid and the like. These may be used alone or in combination of two or more.

The first and second resins may be polymerized in addition to the compound having an unsaturated bond with the carboxyl group, further comprising a monomer commonly used in the art. Methylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, aromatic vinyl compounds such as p-vinylbenzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether or p-vinyl benzyl glycidyl ether; Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate or t-butyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate or isobornyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate or benzyl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide-based compounds such as methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide; Unsaturated amide compounds such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide; 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. Unsaturated oxetane compounds; 1,5-hexadiene-3-ol, and the like. These may be used alone or in combination of two or more.

The content of the binder resin may be 10 to 80% by weight, preferably 10 to 70% by weight, based on the solid content of the total amount of the colored photosensitive resin composition. When the content of the binder resin is within the above range, solubility in a developing solution is sufficient, pattern formation is easy, and reduction of the film portion of the pixel portion of the exposed portion is prevented at the time of development, and the missing property of the non-pixel portion is improved.

< Photopolymerization  Compound &gt;

The photopolymerizable compound according to the present invention is a component for enhancing the strength of the pattern.

The photopolymerizable compound according to the present invention is not particularly limited and may be, for example, a monofunctional monomer compound. Specific examples of the monofunctional compounds such as nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Monomers; (Meth) acrylates such as 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di 3-methylpentanediol di (meth) acrylate, 3- (acryloyloxy) -2-hydroxypropyl methacrylate, 2-hydroxy-1,3-dimethacryloxypropane, Bifunctional monomers such as 2-hydroxy-1-acryloxy-3-methacryloxypropane; Trifunctional monomers such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate; Tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate; Pentafunctional monomers such as dipentaerythritol penta (meth) acrylate; And hexafunctional monomers such as dipentaerythritol hexa (meth) acrylate. These may be used alone or in combination of two or more.

The photopolymerizable compound may preferably be a bifunctional or higher functional monomer and, more preferably, a pentafunctional or higher functional monomer in view of enhancement of pattern strength and improvement in smoothness.

Commercially available photopolymerizable compounds include Aronix M-210, M-1100, 1200, M-309, TO-1382 (Toagosei); KAYARAD HDDA, KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPHA-40H (Nippon Kayaku); Viscot 260 (Osaka Yuki Kagaku High School); AH-600, AT-600 and UA-306H (Kyoeisha Chemical Co., Ltd.).

The photopolymerizable compound according to the present invention may comprise a first photopolymerizable compound and a second photopolymerizable compound having different polarities, if necessary.

In the present invention, the second photopolymerizable compound is a photopolymerizable compound having a polarity higher than that of the first photopolymerizable compound, and the second photopolymerizable compound moves to the surface of the coated composition together with the evaporation of the second solvent, A material hardening layer is formed and the first photopolymerizable compound is used for color layer formation. Preferably, the larger the difference in polarity between the second photopolymerizable compound and the first photopolymerizable compound, the better. In such a case, the polar material cured layer generation promoting effect can be maximized.

The content of the photopolymerizable compound is not particularly limited and may be, for example, from 5 to 45% by weight, preferably from 7 to 45% by weight, based on the solid content of the total amount of the colored photosensitive resin composition. When the content of the photopolymerizable compound is within the above range, the strength and smoothness of the pixel portion can be good.

< Light curing Initiator >

The photopolymerization initiator according to the present invention is not particularly limited as long as it is capable of polymerizing the photopolymerizable compound, and examples thereof include acetophenone, benzophenone, triazine, biimidazole, oxime, Based compounds and the like. These may be used alone or in combination of two or more.

The acetophenone compound is not particularly limited and includes, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan- ] Propane-1-one, and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

The benzophenone compound is not particularly limited, and examples thereof include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'- methyldiphenylsulfide, 3,3 ' -Tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

The triazine compound is not particularly limited, and examples thereof include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4- Methyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2 , 2,4-bis (trichloromethyl) -6- [2- (5-methylpiperazin-1-yl) Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- (Trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

The imidazole-based compound is not particularly limited, and examples thereof include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4' Phenyl) imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2- Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4,4', 5,5 'position is substituted with a carboalkoxy group , And preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl ) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4,5,5'-tetraphenyl- Imidazole and the like.

The oxime-based compound is not particularly limited, and may be, for example, o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one. OXE01 and OXE02 of BASF Co. are commercially available.

The thioxanthone compound is not particularly limited and includes, for example, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Oakstone, and the like.

The photopolymerization initiator according to the present invention may further comprise a benzoin compound, an anthracene compound, etc. in addition to the above compound.

The benzoin compound is not particularly limited, and examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

The anthracene-based compound is not particularly limited and includes, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene or 2-ethyl-9,10- Anthracene and the like.

Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclyoxylic acid A methyl or a titanocene compound may be used in combination as a photopolymerization initiator.

The content of the photopolymerization initiator is not particularly limited and may be, for example, 0.1 to 40% by weight, and preferably 1 to 30% by weight based on the total amount of the binder resin and the photopolymerizable compound based on the solid content. When the content of the photopolymerization initiator is within the above range, the colored photosensitive resin composition becomes highly sensitive and the exposure time is shortened, so that productivity is improved and high resolution can be maintained, and the strength of the formed pixel portion and the smoothness on the surface of the pixel portion can be improved have.

< Light curing  Initiation supplements>

The colored photosensitive resin composition of the present invention may further include a photopolymerization initiation auxiliary agent for improving the sensitivity.

The photopolymerization initiation auxiliary is not particularly limited, and examples thereof include an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group. These may be used alone or in combination of two or more.

The amine compound is not particularly limited, and examples thereof include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, Aromatic amine compounds such as 4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone.

The carboxylic acid compound is not particularly limited and includes, for example, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, And aromatic heteroacetic acids such as phenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The organic sulfur compound having a thiol group is not particularly limited and examples thereof include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (1H, 3H, 5H) -triene, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis Phonate), and the like.

The content of the photopolymerization initiator is not particularly limited and may be, for example, from 0.1 to 40% by weight, preferably from 1 to 30% by weight, based on the total amount of the binder resin and the photopolymerizable compound based on the solid content . When the content of the photopolymerization initiator is within the above range, the sensitivity of the colored photosensitive resin composition is further improved and the productivity can be improved.

<Solvent>

The solvent includes a first solvent and a second solvent having a lower boiling point and a higher polarity than the first solvent. As described above, the second solvent evaporates before the first solvent in the drying process during the manufacture of the color filter, and moves the first resin having a high polarity to the surface of the coated composition to form the polar material cured layer.

The first solvent and the second solvent are not particularly limited within the range satisfying the above conditions, and examples thereof include ethers, aromatic hydrocarbons, ketones, alcohols and esters. These may be used alone or in combination of two or more. For example, 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 dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether Ethers such as acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; And esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and? -Butyrolactone. Of these, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, Ethyl lactate, butalactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

The solvent is preferably an organic solvent having a boiling point of 100 占 폚 to 200 占 폚 in view of coatability and dryness.

The content ratio of the first solvent to the second solvent is not particularly limited, but preferably the content of the first solvent is higher in the composition than that of the second solvent. More specifically, it may be contained in a ratio of 1: 0.2 to 0.6, preferably 1: 0.3 to 0.5. When the content ratio of the first solvent and the second solvent is within the above range, the polar material cured layer and the color layer are formed with appropriate thickness, and the effect of improving the luminance and the transmittance can be maximized.

The content of the solvent is not particularly limited and includes, for example, a solvent contained in the colorant dispersion. The total content of the solvent may be 60 to 90% by weight of the total weight of the colored photosensitive resin composition, preferably 70 to 85% %. &Lt; / RTI &gt; When the content of the solvent is within the above range, the coating property may be good.

<Additives>

The colored photosensitive resin composition of the present invention may further include at least one additive selected from the group consisting of other polymer compounds, a curing agent, a leveling agent, an adhesion promoter, an antioxidant, an ultraviolet absorber and an anti-

The other polymer compound is not particularly limited, and examples thereof include curable resins such as epoxy resin and maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, Thermoplastic resins and the like.

The curing agent is a component for increasing deep curing and mechanical strength, and the type thereof is not particularly limited, and examples thereof include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

The epoxy compound is not particularly limited and includes, for example, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, Epoxy resins, glycidyl ester resins, glycidyl amine resins, or brominated derivatives of such epoxy resins; Aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof; Butadiene (co) polymeric epoxide; Isoprene (co) polymeric epoxide; Glycidyl (meth) acrylate (co) polymers; Triglycidyl isocyanurate and the like.

The oxetane compound is not particularly limited and includes, for example, carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane and the like .

The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound.

The curing auxiliary compound is not particularly limited, and examples thereof include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators. Commercially available polyvalent carboxylic acid anhydrides can be used as an epoxy resin curing agent.

The commercially available epoxy resin curing agent that can be used in the present invention is not particularly limited and includes, for example, a trade name (Adeka Hadona EH-700) (manufactured by Adeka Kogyo Co., Ltd.), a trade name (Rikashido HH) Ltd.) and a trade name (MH-700) (manufactured by Shin-Etsu Chemical Co., Ltd.).

The leveling agent is a component that improves the film formability of the photosensitive resin composition.

The leveling agent according to the present invention is not particularly limited and includes, for example, a fluorine-based surfactant, a silicon-based surfactant, or a mixture thereof.

The silicone surfactant is not particularly limited, and examples thereof include DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 of Dow Corning Toray Silicone Co., Ltd.; TS F-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 of GE Toshiba Silicones.

Examples of the fluorochemical surfactant include, but are not limited to, Megapis F-470, F-471, F-475, F-482 and F-489 commercially available from Dainippon Ink and Chemicals, Incorporated.

The leveling agent according to the present invention may include a first leveling agent and a second leveling agent having different polarities, if necessary.

In the present invention, the second leveling agent is a leveling agent having a polarity higher than that of the first leveling agent, and the second leveling agent moves to the surface of the coated composition together with the evaporation of the second solvent, And the first leveling agent is used for color layer formation. Preferably, the larger the difference in polarity between the second leveling agent and the first leveling agent, the better. In such a case, the polar material cured layer generation promoting effect can be maximized.

Examples of the adhesion promoter include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyl (meth) acrylate, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. These may be used alone or in combination of two or more.

The content of the adhesion promoter is not particularly limited and may be, for example, 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on the total weight of the colored photosensitive resin composition based on the solid content.

The kind of the antioxidant is not particularly limited and includes, for example, 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6- .

The type of ultraviolet absorber is not particularly limited, and examples thereof include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone.

The anti-aggregation agent is not particularly limited and may be, for example, sodium polyacrylate.

&Lt; Method for producing colored photosensitive resin composition >

As a method for preparing the colored photosensitive resin composition of the present invention, for example, a colorant and a dispersant are added to and dispersed in a solvent to prepare a colorant dispersion having a uniform particle diameter, and then a binder resin, a photopolymerizable compound, An initiator and other additives as required, and mixing the resultant with a colorant dispersion, and adding the solvent again if necessary.

<Color filter>

The present invention also provides a color filter made of the colored photosensitive resin composition.

The color filter includes a substrate, a color layer formed on the substrate, and a polar material cured layer formed on the color layer.

The substrate may be a substrate of the color filter itself, or may be a portion where the color filter is placed on a display device or the like, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiO _x ), or a polymer substrate. The polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The color layer may be a layer containing the colored photosensitive resin composition of the present invention, and may be a layer formed by applying the colored photosensitive resin composition and exposing, developing, and thermosetting the colored photosensitive resin composition in a predetermined pattern.

The polar material cured layer is formed after the drying process as described above, and improves the transmittance by lowering the refractive index difference between the media.

The color filter including the substrate and the color layer as described above may further include a partition wall formed between each color pattern, and may further include a black matrix. Further, it may further comprise a protective film formed on the color layer of the color filter.

<Liquid Crystal Display Device>

The present invention also relates to a liquid crystal display device provided with the color filter.

The liquid crystal display device of the present invention may include a configuration known to those skilled in the art without the color filter, and is not particularly limited in the present invention.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Example  And Comparative Example

A colored photosensitive resin composition having the composition and the content (parts by weight) of the following Table 1 was prepared.

division coloring agent
(A) Dispersant
(B) Binder resin
(C) Photopolymerizable compound
(D) Photopolymerization initiator
(E) solvent
(F) additive
(G) ingredient content ingredient content ingredient content Example 1 6 1.7 C-1 /
C-2 3.18 /
2.31 D-2 5.61 1.12 F-1 /
F-2 60 /
20 0.08 Example 2 6 1.7 C-1 /
C-2 3.18
/
2.31 D-1 5.61 1.12 F-1 /
F-2 60 /
20 0.08 Example 3 6 1.7 C-1 /
C-2 3.18 /
2.31 D-1 /
D-2 2.81 /
2.8 1.12 F-1 /
F-2 60 /
20 0.08 Comparative Example 1 6 1.7 C-1 5.49 D-2 5.61 1.12 F-1 /
F-2 60 /
20 0.08 Comparative Example 2 6 1.7 C-1 /
C-2 3.18 /
2.31 D-2 5.61 1.12 F-1 80 0.08 Comparative Example 3 6 1.7 C-1 /
C-2 3.18 /
2.31 D-2 5.61 1.12 F-1 /
F-3 60 /
20 0.08 A: CI Pigment Red 254,
B: BYK-2000 (BYKKEMASA),
C-1 (first resin): copolymer of styrene / acrylic acid (17:83 mol%, styrene-equivalent weight average molecular weight 15,000)
C-2 (second resin): Copolymer of 1,5-hexadien-3-ol / acrylic acid (17:83 mol%, weight average molecular weight in terms of styrene: 14,200)
D-1 (first photopolymerizable compound): A9550 (Shin Nakamura Chemical Co., Ltd.),
D-2 (second photopolymerizable compound): A9570W (Shin Nakamura Chemical Co., Ltd.),
E: Igacure OXE-01 (from BASF),
F-1 (first solvent): Propylene glycol monomethyl ether acetate (boiling point: 146 占 폚)
F-2 (second solvent): Propylene glycol monomethyl ether (boiling point: 119 占 폚)
F-3 (second solvent): diacetone alcohol (boiling point: 166 DEG C)
G (leveling agent): SH-8400 (Toray Silicone Co.)

The polarities of the binder resin, the photopolymerizable compound and the solvent were compared in Table 1, and evaluation methods and results are as follows.

Polarity can be compared by bond dipole moment, permittivity, solubility parameter, or solubility in water. Generally, a material with a high polarity has a large bond-dipole moment and a high dielectric constant, and is highly soluble in water.

The polarity between the binder resins was compared by the difference in solubility of each monomer in water. The solubilities of 1,5-hexadien-3-ol in water of C-1 and C-2, which show differences in structure between the two types of binders, were 160 mg / L and 12,298 mg / L, respectively , The higher the polarity of 5-hexadien-3-ol.

Since the photopolymerizable compounds D-1 and D-2 have the same structure except for the difference in the number of hydroxy groups, the polarity between the photopolymerizable compounds is compared with the hydroxyl value (OH value, OH content of the polar group). The hydroxyl value of D-1 is 60 mg (KOH) / g, D-2 is 85 to 100 mg (KOH) / g and the polarity of D-2 is higher.

The polarities of the solvents were compared by dielectric constant difference. The permittivity of F-1 was 8.3, the F-2 was 12.3 and the F-3 was 18.2. The polarities were F-1, F-2 and F- The polarity is the lowest, and the polarity of F-3 is the highest.

Experimental Example

The colored photosensitive resin compositions prepared in Examples and Comparative Examples were applied on a 2 inch glass substrate ("EAGLE XG", manufactured by Corning Incorporated) by a spin coating method in a clean room at 23 ° C and a humidity of 50% The solvent was removed for 17 seconds under a pressure of 65 Pa with the equipment. Thereafter, it was left in a convection oven at 100 캜 for 3 minutes, and then exposed at 40 mJ / cm ² . Then, it was developed with a 1% developer of JCD (JSR Corp.) at 26 ° C for 70 seconds, washed with deionized water for 10 seconds, and then cured in a convection oven at 230 ° C for 20 minutes to prepare a color filter.

(1) Measurement of thickness of color filter

The thickness of the color filter except for the substrate was measured, and the measurement results are shown in Table 2 below.

(2) Measurement of luminance

The luminance at the same color coordinates (x: 0.650, y: 0.343) of the manufactured color filter was measured with a BH3-MJL luminance meter (OLYMPUS). The measurement results are shown in Table 2 below.

division Layer thickness (탆) Luminance Example 1 2.95 (color layer + polarized layer) 23.79 Example 2 2.96 (color layer + polarized layer) 23.64 Example 3 2.94 (color layer + polarized layer) 23.70 Comparative Example 1 2.89 (color layer) 23.33 Comparative Example 2 2.99 (color layer) 23.45 Comparative Example 3 2.95 (color layer) 23.39

Referring to Table 1, the color filters prepared from the compositions of Examples 1 to 3 have a higher luminance than the color filter formed of the composition of the comparative example because a polar material cured layer is produced and the difference in refractive index with air is reduced to improve the transmittance Can be confirmed.

A cross-sectional photograph of the color filter of Example 1 is shown in Fig. Referring to FIG. 3, it can be confirmed that a polar material cured layer is formed on the color layer.

However, the color filters prepared with the compositions of Comparative Examples 1 to 3 did not have a polar material cured layer and thus had lower brightness than the color filters made of the composition of Example.

Claims (7)

A colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent;
Wherein the solvent comprises a first solvent and a second solvent having a lower boiling point and a higher polarity than the first solvent,
Wherein the binder resin comprises a first resin and a second resin having a higher polarity than the first resin so that the first resin and the second solvent can move to the surface together with the second solvent upon evaporation.
The colored photosensitive resin composition according to claim 1, wherein the photopolymerizable compound comprises a first photopolymerizable compound having a different polarity and a second photopolymerizable compound.
The colored photosensitive resin composition according to claim 1, wherein the first solvent has a higher content in the composition than the second solvent.
The colored photosensitive resin composition according to claim 1, further comprising a leveling agent.
A color filter made of the colored photosensitive resin composition according to any one of claims 1 to 4.
The color filter of claim 5, wherein the color filter comprises a substrate, a color layer formed on the substrate, and a polar material cured layer formed on the color layer.
A liquid crystal display device comprising the color filter of claim 5.

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