KR20190093915A - Colored photo sensitive resin composition, a color filter comprising the same, and a display devide comprising the color filter - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition, a color filter manufactured using the same, and a display device including the color filter. An objective of the present invention is to provide a colored photosensitive resin composition which is capable of forming a surface defect-free coating film with excellent flatness by preventing line stain or the like from being generated in a coating thin film applied to a substrate and suppressing surface roughness of the coating film in a thin film forming process, e.g., high speed slit coating, etc. According to the present invention, the colored photosensitive resin composition comprises a coloring agent (A), an alkali soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), wherein the coloring agent (A) includes a phthalocyanine pigment having Zn or Al as a central metal, the solvent (E) includes a first solvent and a second solvent, the first solvent has a boiling point of not less than 110°C to not more than 170°C and a viscosity of not less than 1.0 Pa·s to not more than 1.3 Pa·s at 25°C, the second solvent has a boiling point of not less than 170°C to not more than 190°C and a viscosity of not less than 1.1 Pa·s to not more than 2.0 Pa·s at 25°C, and a value calculated from mathematical expression 1, {(A*X_A+B*X_B)*(A*Y_A+B*Y_B)}/2, is within a range of not less than 1.6 to not more than 2.0. In mathematical expression 1, A, B, X and Y are each as follows: A: wt% of the first solvent with respect to the total weight of the colored photosensitive resin composition, B: wt% of the second solvent with respect to the total weight of the colored photosensitive resin composition, X: viscosity of the first solvent (A) or the second solvent (B), and Y: vapor pressure of the first solvent (A) or the second solvent (B) at 20°C.

Description

A colored photosensitive resin composition, a color filter manufactured using the same, and a display device including the color filter {COLORED PHOTO SENSITIVE RESIN COMPOSITION, A COLOR FILTER COMPRISING THE SAME, AND A DISPLAY DEVIDE COMPRISING THE COLOR FILTER}

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

The color filter is widely used in various display devices such as an image pickup device and a liquid crystal display (LCD), and its application range is rapidly expanding. The color filter used in the image pickup device, the liquid crystal display, or the like may be formed of a coloring pattern of three colors of red, green, and blue, or may include yellow, magenta, and cyan ( It consists of a coloring pattern of three colors of cyan).

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

Colored photosensitive resin is an essential material, such as a color filter, a liquid crystal display material, an organic light emitting element, a display. For example, in the color filter of a color liquid crystal display, a light shielding layer using a black photosensitive composition is formed at the boundary between the colored layers in order to increase the contrast and color development effects of red, green, and blue. In addition, recently, as well as the role of the black matrix is located on the array substrate to form a cell gap retention spacer is required to be able to play a variety of roles at once. Accordingly, not only an optical effect for basic light shielding but also a good elastic modulus and reliable characteristics are required.

Korean Patent Laid-Open Publication No. 10-2015-0037400 discloses a photosensitive resin composition comprising a binder resin, a photoactive compound, and a solvent, wherein the boiling point and / or viscosity of the solvent are included in a specific range, but the productivity in a thick film When the high-speed slit coating according to the increase, streaks occur, there is a problem that the pin marks stains in the drying process by using a high boiling point solvent of more than 190 ℃.

Republic of Korea Patent Publication No. 10-2015-0037400

The present invention does not generate streaks, etc. in the coating thin film applied to the substrate during the thin film forming process (for example, high-speed slit coating, etc.) and the roughness of the surface of the coating film is suppressed, thereby forming a coating film having excellent flatness without surface defects. It is an object to provide this possible colored photosensitive resin composition.

In addition, an object of the present invention is to provide a color filter manufactured using the colored photosensitive resin composition and a display device including the color filter.

In order to achieve the above object, the present invention includes (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photoinitiator and (E) a solvent, wherein the (A) coloring agent A phthalocyanine pigment having Zn or Al as the central metal, the (E) solvent comprises a first solvent and a second solvent, the first solvent has a boiling point of 110 ℃ to less than 170 ℃, the viscosity is 25 ℃ At 1.0 Pa · s or more and less than 1.3 Pa · s, the second solvent has a boiling point of 170 ° C. or more and less than 190 ° C., and has a viscosity of 1.1 Pa · s or more and 2.0 Pa · s at 25 ° C., The calculated value is contained in the range of 1.6 or more and less than 2.0, It provides the coloring photosensitive resin composition characterized by the above-mentioned.

[Equation 1]

{(A * X _A + B * X _B ) * (A * Y _A + B * Y _B )} / 2

(In Equation 1, A, B, X and Y are as follows:

A: weight% of the first solvent relative to the total weight of the colored photosensitive resin composition

B: weight% of the second solvent relative to the total weight of the colored photosensitive resin composition

X: viscosity of the first solvent (A) or the second solvent (B)

Y: vapor pressure of the first solvent (A) or the second solvent (B), 20 ° C.)

Moreover, this invention provides the color filter containing the coloring pattern manufactured from the said coloring photosensitive resin composition.

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

The coloring photosensitive resin composition of this invention provides the effect of forming the coating film excellent in the flatness without surface defect by using the solvent which has a specific boiling point and a viscosity.

In addition, the colored photosensitive resin composition does not generate streaks or the like on the coating thin film applied to the substrate during high-speed slit coating provides an effect that can suppress the roughness of the coating film surface.

In addition, a color filter manufactured using the colored photosensitive resin composition and a display device including the color filter provide excellent sensitivity.

1 is a view showing an image determined to be good when the VCD staining evaluation in the present invention.
2 is a view showing an image that is determined to be defective when evaluating VCD staining in the present invention.
Figure 3 is a view showing an image which is judged good when evaluating the line stain after coating in the present invention.
Figure 4 is a view showing an image which is determined to be defective when evaluating the line stain after coating in the present invention.

The present invention includes (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photoinitiator, and (E) a solvent, wherein the (A) colorant has Zn or Al as a center metal. It contains a phthalocyanine pigment, The said (E) solvent contains a 1st solvent and a 2nd solvent, The said 1st solvent has a boiling point of 110 degreeC or more and less than 170 degreeC, and the viscosity is 1.0 Pa.s or more and 1.3 Pa at 25 degreeC. Less than s, the second solvent has a boiling point of 170 ° C. or more and less than 190 ° C., and a viscosity of 1.1 Pa · s or more and less than 2.0 Pa · s at 25 ° C., and a value calculated from Equation 1 below 1.6 or less than 2.0 Provided is a colored photosensitive resin composition, a color filter manufactured using the same, and a display device including the color filter.

[Equation 1]

{(A * X _A + B * X _B ) * (A * Y _A + B * Y _B )} / 2

(In Equation 1, A, B, X and Y are as follows:

A: weight% of the first solvent relative to the total weight of the colored photosensitive resin composition

B: weight% of the second solvent relative to the total weight of the colored photosensitive resin composition

X: viscosity of the first solvent (A) or the second solvent (B)

Y: vapor pressure of the first solvent (A) or the second solvent (B), 20 ° C.)

The coloring photosensitive resin composition which concerns on this invention can form the coating film excellent in the flatness without surface defects by including the said solvent specified as mentioned above.

Since the coloring photosensitive resin composition which concerns on this invention contains the said solvent specified as mentioned above, a streak etc. do not generate | occur | produce in the coating thin film apply | coated to the board | substrate at the time of high speed slit coating, and can suppress the roughness of a coating film surface. Can be.

A color filter manufactured using the colored photosensitive resin composition according to the present invention and a display device including the color filter may have excellent sensitivity.

Hereinafter, each component which comprises the coloring photosensitive resin composition of this invention is demonstrated in detail. However, the present invention is not limited by these components.

(A) colorant

The colorant is characterized by containing at least one pigment (a1), and preferably comprises a phthalocyanine pigment having Zn or Al as the center metal.

When the colorant includes a phthalocyanine pigment having Zn or Al as the center metal, even if the colorant is included in a small amount, high color reproducibility can be realized and the transmittance is preferable.

(a1) Pigment

The pigment may include an organic pigment or an inorganic pigment generally used in the art as needed, but preferably includes a phthalocyanine pigment having Zn or Al as the central metal.

In addition, the pigment is a resin treatment, surface treatment using a pigment derivative introduced with an acidic group or a basic group, graft treatment of the surface of the pigment with a polymer compound, atomization treatment by a sulfate atomization method, and the like to remove impurities, if necessary A washing treatment with an organic solvent or water or the like or a removal treatment of ionic impurities by an ion exchange method or the like can also be performed.

The organic pigment may be used a variety of pigments used in printing inks, inkjet inks, and the like, specifically, phthalocyanine pigments, water-soluble azo pigments, insoluble azo pigments, quinacridone pigments, isoindolinone pigments, isoindolin pigments, Perylene Pigment, Perinone Pigment, Dioxazine Pigment, Anthraquinone Pigment, Dianthraquinoneyl Pigment, Anthrapyrimidine Pigment, Antanthrone Pigment, Indanthrone Pigment, Pravantron Pigment, Pyrantrone Pigment, Diketopyrrolopyrrole Pigment Etc. can be mentioned.

In addition, as the inorganic pigment, metal compounds such as metal oxides and metal complex salts may be used. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black, organic Oxides of metals such as black pigments, titanium black and red, green and blue, and pigments having a black color, or complex metal oxides;

In particular, the organic pigments and inorganic pigments include compounds that are specifically classified as pigments in the color index (Published by The society of Dyers and Colourists), and more specifically, the color index (CI) number of Although a pigment is mentioned, It is not necessarily limited to these.

C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 Yellow pigments such as, 147, 148, 150, 153, 154, 166, 173, 194, and 214;

C.I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and the like orange pigments;

Green pigments such as C.I pigment green 7, 36, 58, 59, 62, 63 having a halogenated phthalocyanine structure; Etc

The said pigment can be used individually or in mixture of 2 or more types.

For example, to form green pixels, C.I. Pigment green 7, 58, 59, 62, 63 and C.I. Pigment yellow 150 and 138, preferably containing at least one selected from the group consisting of C.I. Pigment green 58, 59, 62, 63 and C.I. More preferably, it contains at least one selected from the group consisting of Pigment Yellow 138.

The pigment may be included in 20 to 45% by weight, preferably 15 to 40% by weight based on the total weight of solids of the colorant. When the pigment is included in the above range, even if a thin film is formed, the color density of the pixel is sufficient, and since the omission of the non-pixel portion during development does not decrease, it is preferable because no residue occurs.

It is preferable that the said pigment uses the pigment dispersion liquid in which the particle diameter of a pigment was disperse | distributed uniformly. Examples of the method for uniformly dispersing the particle size of the pigment include (a2) a method of dispersing by containing a pigment dispersant. According to the above method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained. have.

(a2) pigment dispersant

The pigment dispersant is added to maintain the deagglomeration and stability of the pigment can be used without limitation generally used in the art, specific examples of the pigment dispersant are 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, respectively.

Specific examples of the cationic surfactant include amine salts and quaternary ammonium salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride.

Specific examples of the anionic surfactants 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, sodium dodecylbenzene sulfonate, 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 copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, etc. are mentioned.

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

In addition, the pigment dispersant preferably includes an acrylate dispersant (hereinafter, acrylate dispersant) containing 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 like. Each of the acrylate-based dispersants may be used alone or in combination of two or more thereof. Can be.

In addition to the acrylate dispersant, the pigment dispersant may use a pigment dispersant of another resin type. The other resin type pigment dispersant is a (partial) of known resin type pigment dispersants, in particular polycarboxylic acid esters, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids represented by polyurethanes, polyacrylates. Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-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 a poly (lower alkyleneimine); Water-soluble resins or water-soluble polymer compounds such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide; And phosphate esters.

As a commercial item of the said other resin type pigment dispersant, As a cationic resin dispersant, For example, brand names of BYK (BIC) Chemi Corporation: 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 brand name: 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: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; Kawaken Fine Chemical's trade names: HINOACT T-6000, Hinoact T-7000, Hinoact T-8000; Trade names of Ajinomoto Co., Ltd .: AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823; The brand names of Kyoeisha Chemical Co., Ltd .: FLORENE DOPA-17HF, Floren DOPA-15BHF, Floren DOPA-33, Floren DOPA-44, etc. are mentioned.

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

The pigment dispersant may be included in 5 to 60% by weight, preferably 15 to 50% by weight based on 100% by weight of the solids of the pigment. When the pigment dispersant is included in the above range, it is possible to maintain an appropriate viscosity level that is easy for the preparation of the colored photosensitive resin composition, and the gelation process after the atomization and dispersion of the pigment is preferred is preferred.

The content of the colorant may be included in 5 to 50% by weight, preferably 5 to 30% by weight based on the total weight of solids in the coloring photosensitive resin composition. When the colorant is included in the above range, the color density of the pixel at the time of thin film formation is sufficient, the omission of the non-pixel portion at the time of development is not reduced, it is preferable that the residue hardly occurs.

In the present invention, the total weight of solid content in the colored photosensitive resin composition means the total weight of the remaining components except for the solvent of the colored photosensitive resin composition.

(B) alkali soluble resin

In order to have solubility with respect to the alkaline developing solution used at the image development process at the time of forming a pattern, it is preferable to copolymerize and manufacture the ethylenically unsaturated monomer which has a (b1) carboxyl group.

The content of the alkali-soluble resin may be included in 10 to 80% by weight, preferably 10 to 70% by weight based on the total weight of solids in the colored photosensitive resin composition. When the alkali-soluble resin is contained within the above range, the solubility in a developing solution is sufficient, so that pattern formation is easy, and the film reduction of the pixel portion of the exposed portion is prevented at the time of development, so that the missing property of the non-pixel portion is good. Do.

It is preferable that the acid value of the said alkali-soluble resin is 30 mgKOH / g-150 mgKOH / g. When the acid value of the alkali-soluble resin is less than 30 mg · KOH / g, it is difficult to secure a sufficient developing speed of the colored photosensitive resin composition, and when it exceeds 150 mg · KOH / g, the adhesion with the substrate is reduced to short the pattern. This can happen.

(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; mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate, and the like, and acrylic acid and methacrylic acid are preferred.

The said alkali-soluble resin can be manufactured from the ethylenically unsaturated monomer which has the said carboxyl group, and the unsaturated monomer which can be copolymerized (b2).

(b2) Copolymerizable unsaturated monomers

Specific examples of the copolymerizable unsaturated monomers,

Glycidyl methacrylate, which is an unsaturated monomer having a glycidyl group;

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N Ethylenically unsaturated monomers having hydroxyl groups such as hydroxyethyl (meth) acrylates such as hydroxyethyl acrylamide;

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, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide compounds such as -methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-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] decane-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. Unsaturated oxetane compounds; Etc., but is not limited thereto.

The said copolymerizable unsaturated monomers can be used individually or in combination of 2 or more types.

(C) photopolymerizable compound

The photopolymerizable compound is a compound which can be polymerized by the action of the following (D) photopolymerization initiator, but may include monofunctional monomers, bifunctional monomers, other polyfunctional monomers, and the like, but is not limited thereto.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrroly Money, etc.

Specific examples of the bifunctional monomers include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyl oxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaeryte Lithol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

Of these, bifunctional or higher polyfunctional monomers are preferably used.

The content of the photopolymerizable compound may be included in an amount of 3 to 45% by weight, preferably 7 to 45% by weight, based on the total weight of solids in the colored photosensitive resin composition. When the said photopolymerizable compound is contained in the said range, since the intensity | strength and smoothness of a pixel part become favorable, it is preferable.

(D) photoinitiator

It is preferable that the said photoinitiator contains the (d1) oxime ester system photoinitiator.

(d1) Oxime ester type photoinitiator

Specific examples of the oxime ester photopolymerization initiator include 1,2-Octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime). Commercially available oxime ester photopolymerization initiators include Irgacure OXE-01, Irgacure OXE-02 and Irgacure OXE-03 from BASF. Since absorbance and the radical species which generate | occur | produce differ, it is preferable to use 2 or more types in mixture.

Moreover, photopolymerization initiators other than the said oxime ester system photoinitiator can also be used together. Typically, at least one compound selected from the group consisting of acetophenone compounds, benzophenone compounds, triazine compounds, biimidazole compounds, thioxanthone compounds, and carbazole compounds is preferably used.

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

As said benzophenone type compound, a benzophenone, methyl 0- benzoyl benzoate, 4- [0107] phenyl benzophenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3, 3 ', 4, 4' -Tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6 -(4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichloro Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4, The imidazole compound etc. which the phenyl group of a 4 ', 5,5'- tetraphenyl- 1,2'-biimidazole or a 4,4', 5,5 'position are substituted by the carboalkoxy group are mentioned. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4' , 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole are preferred Used.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. There is this.

Examples of the carbazole compound include 3- (2-methyl-2-dimethylamino propionyl) carbazole, 3- (2-methyl-2-morpholino propionyl) -9-methylcarbazole, 3- (2-methyl-hydroxy propionyl) -9-methyl carbazole, 3- (1-hydroxy cyclohexanoyl) -9-butylcarbazole and the like.

The oxime ester photopolymerization initiator may be included in 10 to 100% by weight, preferably 20 to 100% by weight based on the total weight of the photopolymerization initiator. When the content of the oxime ester photopolymerization initiator in the photopolymerization initiator is less than 10% by weight, a decrease in sensitivity due to the dye is not overcome, and a short circuit of the pattern is likely to occur during the development process.

In addition, the photopolymerization initiator may further include a (d2) photopolymerization initiation aid to improve the sensitivity and productivity of the colored photosensitive resin composition of the present invention.

(d2) photopolymerization start adjuvant

As a specific example of the photopolymerization start adjuvant, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and polyfunctional thiol compounds may be preferably used.

It is preferable to use an aromatic amine compound as the amine compound, and specifically, aliphatic amine compounds such as triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone ), 4,4'-bis (diethylamino) benzophenone and the like can be used.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

The polyfunctional thiol compounds include Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, Trimethylolpropane tris-3-mercaptopropionate), Pentaerythritol tetrakis-3-mercaptopropionate), Dipentaerythritol hexa-3-mercaptopropionate), and the like.

The photopolymerization initiation aid may be included in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total weight of the solid content of the alkali-soluble resin and the photopolymerizable compound. When the photopolymerization initiation aid is included in the above range, the sensitivity of the colored photosensitive resin composition may be higher, and the productivity of the color filter formed using the colored photosensitive resin composition may be improved.

The content of the photopolymerization initiator may be included in 0.5 to 40% by weight, preferably 10 to 30% by weight based on the total weight of solids in the colored photosensitive resin composition. When the said photoinitiator is contained in the said range, since the coloring photosensitive resin composition becomes high sensitivity and an exposure time is shortened, since productivity is improved and high resolution can be maintained, it is preferable. In addition, the intensity of the pixel portion formed using the colored photosensitive resin composition and smoothness on the surface of the pixel portion may be improved.

 (E) solvent

The solvent may be used without particular limitation as long as it is effective to dissolve other components included in the colored photosensitive resin composition.

In view of the roughness of the surface of the coating film generated at the time of high-speed coating on the coating film and drying under reduced pressure after coating, the solvent has a boiling point of 110 ° C. or higher and less than 170 ° C. and a viscosity of 1.0 Pa · s or higher and 1.3 Pa at 25 ° C. A first solvent having a s less than s and a boiling point of 170 ° C. or more and less than 190 ° C., and a viscosity of at least 1.1 Pa · s or more and less than 2.0 Pa · s at 25 ° C., and a value calculated from Equation 1 below 1.6 It is preferable to be included in the range of less than 2.0.

[Equation 1]

{(A * X _A + B * X _B ) * (A * Y _A + B * Y _B )} / 2

(In Equation 1, A, B, X and Y are as follows:

A: weight% of the first solvent relative to the total weight of the colored photosensitive resin composition

B: weight% of the second solvent relative to the total weight of the colored photosensitive resin composition

X: viscosity of the first solvent (A) or the second solvent (B)

Y: vapor pressure of the first solvent (A) or the second solvent (B), 20 ° C.)

In the case of using the solvent to meet such conditions, it was experimentally confirmed that the coating film having excellent flatness without surface defects during high-speed slit coating can be formed.

The first solvent is, for example, propylene glycol monomethyl ether acetate (boiling point 119 ° C., viscosity 1.1 mPa · s, vapor pressure 3.8 mmHg, 25 ° C.), methyl-3-methoxy propionate (boiling point 145 ° C., viscosity 1.1) mPas, vapor pressure 12 mmHg, 25 ° C.), propylene glycol methyl ether propionate (boiling point 161 ° C., viscosity 1.2 mPa · s, vapor pressure 0.9 mm Hg, 20 ° C.), pentyl propionate (boiling point 165 ° C., viscosity 1.0 mPa · s) , Vapor pressure 1.5mmHg, 20 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C, viscosity 1.2mPa · s vapor pressure 0.45mmHg, 20 ° C), etc.

The second solvent is, for example, dipropylene glycol dimethyl ether (boiling point of 175 ° C., viscosity 1.1 mPa · s, vapor pressure 0.38 mmHg, 20 ° C.), diethylene glycol ethylmethyl ether (boiling point of 176 ° C., viscosity 1.2 mPa · s, Vapor pressure 0.68 mmHg, 20 ° C), diethylene glycol diethyl ether (boiling point 188 ° C, viscosity 1.2 mPa · s, vapor pressure 0.38mmHg, 20 ° C), dipropylene glycol dimethyl ether (boiling point 171 ° C, viscosity 1.3mPa · s) , Vapor pressure 0.6 mmHg, 25 ° C., diethylene glycol methylethyl ether (boiling point 176, viscosity 1.3 mPa · s, vapor pressure 0.7 mmHg, 25 ° C.).

The solvents exemplified above may be used alone or in combination of two or more thereof.

The total weight of the colored photosensitive resin composition may include 15 wt% to 80 wt%, the second solvent 5 wt% to 30 wt%, and preferably 10 wt% to 15 wt%, and the solvent may include 30 wt%. To 90% by weight, preferably 70 to 85% by weight. When the solvent is included in the content range, the coating property is improved when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, etc. It is desirable to provide.

(F) additive

The coloring photosensitive resin composition of this invention uses additives, such as antioxidant, a filler, another high molecular compound, a hardening | curing agent, an adhesion promoter, a ultraviolet absorber, and an anti-agglomerate, as needed by those skilled in the art in the range which does not impair the objective of this invention other than the said component. It is also possible.

The antioxidant is specifically ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-80, ADK STAB 1178, ADK STAB TPP, ADK STAB 1500, ADK STAB 135A, ADK STAB 3010 may be used, but is not limited thereto.

The antioxidant may be included in 1 to 100% by weight, preferably 2 to 50% by weight based on the total weight of the photopolymerization initiator. When the said antioxidant is contained in the said range, since the coloring photosensitive resin composition can expect the transmittance | permeability improvement without degrading a sensitivity, it is preferable. When it is included in less than 1% by weight, it is difficult to expect the improvement in transmittance, and when it exceeds 100% by weight, the sensitivity is lowered, so that a pattern short circuit occurs easily during the developing process.

Specifically, the filler may be glass, silica, alumina, or the like, but is not limited thereto.

Specific examples of the other polymer compound include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. It may be, but is not limited thereto.

The curing agent is used to increase the core hardening and mechanical strength, and specifically, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, etc. may be used, but is not limited thereto. Specific examples of the epoxy compound include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, noblock type epoxy resins, other aromatic epoxy resins, cycloaliphatic epoxy resins, and glyce Aliphatic, cycloaliphatic or aromatic epoxy compounds other than cydyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, epoxy resins and brominated derivatives thereof, butadiene (co) polymer epoxides, isoprene (co) Polymer epoxides, glycidyl (meth) acrylate (co) polymers, triglycidyl isocyanurates and the like can be used, but are not limited thereto. Specifically, the oxetane compound may include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, cyclohexane dicarboxylic acid bis oxetane, and the like. It is not.

The said hardening | curing agent can use together the hardening auxiliary compound which can make ring-opening-polymerize the epoxy group of an epoxy compound, and the oxetane skeleton of an oxetane compound. Specifically, the curing auxiliary compound may be a polyhydric carboxylic acid, a polyhydric carboxylic anhydride, an acid generator, or the like. As said carboxylic anhydride, what is marketed can be used as an epoxy resin hardening | curing agent. As said commercially available epoxy resin hardening | curing agent, a brand name (Adekahadona EH-700) (made by Adeka Industrial Co., Ltd.), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), a brand name (MH-700) are mentioned, for example. (Manufactured by Nippon Ewha Co., Ltd.).

The hardening | curing agent and hardening auxiliary compound which were illustrated above can be used individually or in mixture of 2 or more types, respectively.

Specific examples of the adhesion promoter include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercapto propyl tree It is possible to use alone or mixtures thereof selected from the group consisting of methoxysilane, 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane.

The adhesion promoter may be included in an amount of 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the total weight of solids in the colored photosensitive resin composition.

Specifically, the ultraviolet absorber may use 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone, and the like, but is not limited thereto.

The aggregation inhibitor may specifically use sodium polyacrylate, but is not limited thereto.

Color filter and liquid crystal display

Moreover, this invention provides the color filter manufactured from the coloring photosensitive resin composition which concerns on this invention, and the display apparatus containing the said color filter.

The display device that may include such a color filter may include a liquid crystal display, an OLED, a flexible display, and the like, but is not limited thereto. Examples of all display devices known in the art may be applicable.

A color filter can be manufactured by apply | coating the coloring photosensitive resin composition of this invention mentioned above on a base material, photocuring and developing, and forming a pattern.

First, after apply | coating a coloring photosensitive resin composition to a base material, heat-drying removes volatile components, such as a solvent, and obtains a smooth coating film.

As a coating method, it can carry out by a spin coat, cast coating method, the roll coating method, the slit and spin coat, the slit coat method, etc., for example. After coating, heating and drying (prebaking) or drying under reduced pressure are carried out to volatilize volatile components such as a solvent. Here, heating temperature is 70 degreeC-200 degreeC normally, Preferably it is 80 degreeC-130 degreeC. The coating film thickness after heat drying is about 1-8 micrometers normally. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that the parallel light beam may be irradiated uniformly to the whole exposure part, and the exact alignment of a mask and a board | substrate is performed. When ultraviolet light is irradiated, the site to which ultraviolet light is irradiated is hardened.

G-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm) and the like can be used as the ultraviolet rays. The irradiation amount of ultraviolet rays may be appropriately selected as necessary, and the present invention is not limited thereto. When the coating film after hardening is contacted with a developing solution and the non-exposed part is melted and developed, the target pattern shape can be formed.

The developing method may be any of a liquid addition method, a dipping method, a spray method and the like. In addition, during development, the substrate may be tilted at an arbitrary angle. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate And sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine and the like.

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% by mass, more preferably 0.03 to 5% by mass.

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

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

Specific examples of the anionic surfactants include higher alcohol sulfate ester salts such as lauryl alcohol sulfate and sodium sodium or oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and dodecylbenzene sulfonic acid. Alkyl aryl 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 surfactant 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% by mass, preferably 0.05 to 8% by mass, more preferably 0.1 to 5% by mass. After image development, it washes with water and can also carry out post-baking for 10 to 60 minutes at 150 degreeC-230 degreeC as needed.

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail based on an Example, embodiment of this invention disclosed below is an illustration to the last, and the scope of the present invention is not limited to these embodiment. The scope of the invention is indicated in the appended claims, and moreover contains all modifications within the meaning and range equivalent to the claims. In addition, "%" and "part" which show content in a following example and a comparative example are a mass reference | standard unless there is particular notice.

Synthesis Example: Preparation of Alkali Soluble Resin

120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 13.0 parts of acrylic acid, 10 parts of benzyl methacrylate, into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube. 57.0 parts of 4-methylstyrene and 20 parts of methyl methacrylate and 3 parts of n-dodecyl mercapto were added and nitrogen-substituted. After stirring, the temperature of the reaction solution was raised to 110 and reacted for 6 hours. The solid acid value of the alkali-soluble resin thus synthesized was 100.2 mgKOH / g and the weight average molecular weight Mw measured by GPC was about 15110.

Preparation Example: Preparation of Pigment Dispersions (M1 to M5)

Pigment Dispersion (M1):

As a pigment, C.I. Pigment Green 58 10.0 parts by weight, 5 parts by weight of LPN-6919 (manufactured by BYK) as a pigment dispersant, 85.0 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed with a bead mill for 12 hours to obtain a pigment dispersion (M1). Prepared.

Pigment Dispersion (M2):

As a pigment, C.I. Pigment Green 59 10.0 parts by weight, 5 parts by weight of LPN-6919 (manufactured by BYK) as a pigment dispersant, and 85.0 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed with a bead mill for 12 hours to obtain a pigment dispersion (M2). Prepared.

Pigment Dispersion (M3):

As a pigment, C.I. Pigment Green 63 10.0 parts by weight, 5 parts by weight of LPN-6919 (manufactured by BYK) as a pigment dispersant, and 85.0 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed with a bead mill for 12 hours to obtain a pigment dispersion (M3). Prepared.

Pigment Dispersion (M4):

As a pigment, C.I. Pigment Green 36 10.0 parts by weight, 5 parts by weight of LPN-6919 (manufactured by BYK) as a pigment dispersant, and 85.0 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed with a bead mill for 12 hours to obtain a pigment dispersion (M4). Prepared.

Pigment Dispersion (M5):

As a pigment, C.I. Pigment Yellow 138 10.0 parts by weight, 5 parts by weight of LPN-6919 (manufactured by BYK) as a pigment dispersant, and 85.0 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed with a bead mill for 12 hours to obtain a pigment dispersion (M5). Prepared.

Preparation of the colored photosensitive resin composition which concerns on Examples 1-18 and Comparative Examples 1-11.

Example 1:

26.10 parts by weight of the pigment dispersion composition M2, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Preparation) A colored photosensitive resin composition was prepared by mixing 0.59 parts by weight, 0.16 parts by weight of additive F554 (manufactured by DIC Japan), 27.21 parts by weight of propylene glycol monomethyl ether acetate, and 8.55 parts by weight of diethylene glycol ethylmethyl ether.

Example 2:

26.10 parts by weight of the pigment dispersion composition M2, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 22.94 parts by weight of diethylene glycol ethyl methyl ether 12.83 parts by weight to prepare a colored photosensitive resin composition.

Example 3:

26.10 parts by weight of the pigment dispersion composition M2, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 18.66 parts by weight of diethylene glycol ethyl methyl ether 17.10 parts by weight to prepare a colored photosensitive resin composition.

Example 4:

26.10 parts by weight of the pigment dispersion composition M1, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 27.21 parts by weight diethylene glycol ethyl methyl ether 8.55 parts by weight was mixed to prepare a colored photosensitive resin composition.

Example 5:

26.10 parts by weight of the pigment dispersion composition M1, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 22.94 parts by weight of diethylene glycol ethyl methyl ether 12.83 parts by weight to prepare a colored photosensitive resin composition.

Example 6:

26.10 parts by weight of the pigment dispersion composition M1, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 18.66 parts by weight of diethylene glycol ethyl methyl ether 17.10 parts by weight to prepare a colored photosensitive resin composition.

Example 7:

26.10 parts by weight of the pigment dispersion composition M3, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 27.21 parts by weight diethylene glycol ethyl methyl ether 8.55 parts by weight was mixed to prepare a colored photosensitive resin composition.

Example 8:

26.10 parts by weight of the pigment dispersion composition M3, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 22.94 parts by weight of diethylene glycol ethyl methyl ether 12.83 parts by weight to prepare a colored photosensitive resin composition.

Example 9:

26.10 parts by weight of the pigment dispersion composition M3, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 18.66 parts by weight of diethylene glycol ethyl methyl ether 17.10 parts by weight to prepare a colored photosensitive resin composition.

Example 10:

26.10 parts by weight of the pigment dispersion composition M2, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Preparation) A colored photosensitive resin composition was prepared by mixing 0.59 parts by weight, 0.16 parts by weight of additive F554 (manufactured by DIC Japan), 27.21 parts by weight of propylene glycol monomethyl ether acetate, and 8.55 parts by weight of diethylene glycol diethyl ether.

Example 11:

26.10 parts by weight of the pigment dispersion composition M2, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 22.94 parts by weight diethylene glycol diethyl ether 12.83 parts by weight to prepare a colored photosensitive resin composition.

Example 12:

26.10 parts by weight of the pigment dispersion composition M2, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 18.66 parts by weight of diethylene glycol diethyl ether 17.10 parts by weight to prepare a colored photosensitive resin composition.

Example 13:

26.10 parts by weight of the pigment dispersion composition M1, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 27.21 parts by weight diethylene glycol diethyl ether 8.55 parts by weight to prepare a colored photosensitive resin composition.

Example 14:

26.10 parts by weight of the pigment dispersion composition M1, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 22.94 parts by weight diethylene glycol diethyl ether 12.83 parts by weight to prepare a colored photosensitive resin composition.

Example 15:

26.10 parts by weight of the pigment dispersion composition M1, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 18.66 parts by weight of diethylene glycol diethyl ether 17.10 parts by weight to prepare a colored photosensitive resin composition.

Example 16:

26.10 parts by weight of the pigment dispersion composition M3, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 27.21 parts by weight diethylene glycol diethyl ether 8.55 parts by weight to prepare a colored photosensitive resin composition.

Example 17:

26.10 parts by weight of the pigment dispersion composition M3, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 22.94 parts by weight diethylene glycol diethyl ether 12.83 parts by weight to prepare a colored photosensitive resin composition.

Example 18:

26.10 parts by weight of the pigment dispersion composition M3, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 18.66 parts by weight of diethylene glycol diethyl ether 17.10 parts by weight to prepare a colored photosensitive resin composition.

Comparative Example 1:

26.10 parts by weight of the pigment dispersion composition M2, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 31.49 parts by weight diethylene glycol ethyl methyl ether 4.28 parts by weight was mixed to prepare a colored photosensitive resin composition.

Comparative Example 2:

26.10 parts by weight of the pigment dispersion composition M2, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 10.11 parts by weight of diethylene glycol ethyl methyl ether 25.65 parts by weight to prepare a colored photosensitive resin composition.

Comparative Example 3:

26.10 parts by weight of the pigment dispersion composition M2, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 31.49 parts by weight propylene glycol diacetate 4.28 parts by weight was mixed to prepare a colored photosensitive resin composition.

Comparative Example 4:

26.10 parts by weight of the pigment dispersion composition M2, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 18.66 parts by weight propylene glycol diacetate 17.1 parts by weight was mixed to prepare a colored photosensitive resin composition.

Comparative Example 5:

26.10 parts by weight of the pigment dispersion composition M2, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 31.49 parts by weight 4.28 parts by weight of 3-methoxybutyl acrylate was mixed to prepare a colored photosensitive resin composition.

Comparative Example 6:

26.10 parts by weight of the pigment dispersion composition M2, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 18.66 parts by weight 17.1 parts by weight of 3-methoxybutyl acrylate was mixed to prepare a colored photosensitive resin composition.

Comparative Example 7:

26.10 parts by weight of the pigment dispersion composition M2, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 31.49 parts by weight diethylene glycol dimethyl ether 4.28 parts by weight was mixed to prepare a colored photosensitive resin composition.

Comparative Example 8:

26.10 parts by weight of the pigment dispersion composition M2, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 18.66 parts by weight of diethylene glycol dimethyl ether 17.1 parts by weight was mixed to prepare a colored photosensitive resin composition.

Comparative Example 9:

26.10 parts by weight of the pigment dispersion composition M2, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 31.49 parts by weight dipropylene glycol dimethyl ether 4.28 parts by weight was mixed to prepare a colored photosensitive resin composition.

Comparative Example 10:

26.10 parts by weight of the pigment dispersion composition M2, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Manufactured) 0.59 parts by weight, additive F554 (manufactured by Japan DIC Corporation) 0.16 parts by weight, propylene glycol monomethyl ether acetate 18.66 parts by weight dipropylene glycol dimethyl ether 17.1 parts by weight was mixed to prepare a colored photosensitive resin composition.

Comparative Example 11:

26.10 parts by weight of the pigment dispersion composition M4, 26.10 parts by weight of the pigment dispersion composition M5, 8.33 parts by weight of the resin of the above synthesis example, 2.96 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, PBG-327 (Tron Lysa) as a photopolymerization initiator. Preparation) A colored photosensitive resin composition was prepared by mixing 0.59 parts by weight, 0.16 parts by weight of additive F554 (manufactured by DIC Japan), 27.21 parts by weight of propylene glycol monomethyl ether acetate, and 8.55 parts by weight of diethylene glycol ethylmethyl ether.

The compositions of the colored photosensitive resin compositions according to Examples 1 to 18 and Comparative Examples 1 to 11 are shown in Tables 1 to 3 below.

TABLE 1

TABLE 2

TABLE 3

S1: Propylene Glycol Monomethyl Ether Acetate (PGMEA)

S2: diethylene glycol ethylmethyl ether (MEDG)

S3: diethylene glycol diethyl ether (DEDG)

S4: Propylene Glycol Diacetate (PGDA)

S5: 3-methoxybutyl acrylate (3-MBA)

S6: diethylene glycol dimethyl ether (DMDG)

S7: Dipropylene Glycol Dimethyl Ether (DPDM)

At this time, the types of colorants and the viscosity of the solvent, the vapor pressure and the values calculated from Equation 1 contained in the colored photosensitive resin compositions according to Examples 1 to 18 and Comparative Examples 1 to 11 are shown in Tables 4 and 5 below. It was.

TABLE 4

TABLE 5

Preparation Example: Preparation of Photosensitive Resin Film Using Colored Photosensitive Resin Composition

The colored photosensitive resin compositions according to Examples 1 to 18 and Comparative Examples 1 to 11 were respectively coated on a glass substrate of 1100 mm × 960 mm using a slit coater so that the film thickness after drying was 3.5 μm, and the coating speed was 200 mm / sec. It was set as. After coating, the substrate on which the coating film was formed was moved to a reduced pressure drying chamber (VCD), and dried under reduced pressure so that the time for reaching the pressure of 65 Pa was 20 sec. After drying under reduced pressure, the substrate was moved to a heating oven and prebaked at 100 ° C. for 3 minutes.

Test Example: Evaluation of Physical Properties of Photosensitive Resin Film Using Colored Photosensitive Resin Composition

VCD Stain Evaluation

For the photosensitive resin films prepared in Examples and Comparative Examples, stains generated in a reduced pressure drying process were confirmed at an X200 magnification through an optical microscope, and FIG. 1 was judged as good and FIG. 2 as defective, and is shown in Table 6 below. It was.

Line stain evaluation after coating

For the photosensitive resin films prepared in Examples and Comparative Examples, the appearance was visually checked under a sodium lamp to confirm the occurrence of streaks on the surface of the substrate. Judgment is shown in Table 6 below.

Coating streaks evaluation after nozzle stagnation

When coating the substrates of Examples and Comparative Examples, the nozzles were left in place for the first 10 minutes after the initial coating, and after the recoating, the appearance of the photosensitive resin film was visually checked under a sodium lamp to confirm the occurrence of streaks on the substrate surface. According to the presence or absence of streaks, it is determined in Figure 3 and Figure 4 as a bad, it is shown in Table 6 below.

TABLE 6

Therefore, the coloring photosensitive resin composition according to the present invention may provide an effect of suppressing unevenness of the coating thin film applied to the substrate during high-speed slit coating and suppressing roughness of the coating film surface.

Claims (10)

(A) a coloring agent, (B) alkali-soluble resin, (C) photopolymerizable compound, (D) photoinitiator and (E) solvent,
The (A) coloring agent includes a phthalocyanine pigment having Zn or Al as the center metal,
The solvent (E) comprises a first solvent and a second solvent,
The boiling point of the said 1st solvent is 110 degreeC or more and less than 170 degreeC, and a viscosity is 1.0 Pa * s or more and less than 1.3 Pa * s at 25 degreeC,
The second solvent has a boiling point of 170 ° C. or more and less than 190 ° C., and a viscosity of 1.1 Pa · s or more and less than 2.0 Pa · s at 25 ° C.,
The value computed from following formula (1) is contained in the range of 1.6 or more and less than 2.0, The coloring photosensitive resin composition characterized by the above-mentioned.
[Equation 1]
{(A * X _A + B * X _B ) * (A * Y _A + B * Y _B )} / 2
(In Equation 1, A, B, X and Y are as follows:
A: weight% of the first solvent relative to the total weight of the colored photosensitive resin composition
B: weight% of the second solvent relative to the total weight of the colored photosensitive resin composition
X: viscosity of the first solvent (A) or the second solvent (B)
Y: vapor pressure of the first solvent (A) or the second solvent (B), 20 ° C.)
The method according to claim 1,
With respect to the total weight of solids in the colored photosensitive resin composition,
The (A) coloring agent is included in 5 to 50% by weight,
The (B) alkali-soluble resin is contained in 10 to 80% by weight,
The (C) photopolymerizable compound is contained in 3 to 45% by weight,
The (D) photopolymerization initiator is contained in 0.5 to 40% by weight,
The solvent (E) is a colored photosensitive resin composition, characterized in that contained in 30 to 90% by weight based on the total weight of the colored photosensitive resin composition.
The method according to claim 2,
About the total weight of the said coloring photosensitive resin composition,
The first solvent is included in 15 to 80% by weight,
The second solvent is contained in 5 to 30% by weight colored photosensitive resin composition, characterized in that.
The method according to claim 1,
The coloring agent is a coloring photosensitive resin composition, characterized in that at least one selected from the group consisting of pigment green 58, pigment green 59, pigment green 62 and pigment green 63.
The method according to claim 1,
The alkali-soluble resin is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, fumaric acid, mesaconic acid, itaconic acid, fumaric anhydride, mesaconic anhydride, itaconic anhydride and ω-carboxypolycaprolactone mono (meth) acrylate. Coloring photosensitive resin composition, characterized in that at least one is produced by copolymerization.
The method according to claim 1,
The photopolymerizable compound is nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, 1 , 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyl oxy of bisphenol A Ethyl) ether, 3-methylpentanedioldi (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tree (meth) ) Acrylic acid, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa It is at least one selected from the group consisting of (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, and dipentaerythritol hexa (meth) acrylate, The coloring photosensitive resin composition characterized by the above-mentioned.
The method according to claim 1,
The photopolymerization initiator is 1,2-Octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3 -yl] ethanone 1- (O-acetyloxime), 1,2-Octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime) and Irgacure OXE-03 from BASF It contains at least one, The coloring photosensitive resin composition characterized by the above-mentioned.
The method according to claim 1,
The first solvent is at least one selected from the group consisting of propylene glycol monomethyl ether acetate, methyl-3-methoxy propionate, propylene glycol methyl ether propionate, pentyl propionate and diethylene glycol dimethyl ether ,
The second solvent is at least one selected from the group consisting of dipropylene glycol dimethyl ether, diethylene glycol ethylmethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether and diethylene glycol methylethyl ether The coloring photosensitive resin composition which makes it.
The color filter containing the coloring pattern manufactured from the coloring photosensitive resin composition of any one of Claims 1-8.
A display device comprising the color filter of claim 9.

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