KR20120019619A - A colored photosensitive resin composition, color filter and liquid crystal display device having the same - Google Patents

Abstract

PURPOSE: A colored photo-sensitive resin composition, a color filter, and a liquid crystal display device including the same are provided to prevent the reduction of transmission and the line-peeling phenomenon of patterns based on the low amount of exposure. CONSTITUTION: A colored photo-sensitive resin composition includes a coloring material, a binder resin, a photo-polymerizable compound, a photo-polymerization initiator, and a solvent. The photo-polymerization initiator includes a compound containing at least two photo-active oxime ester skeletons in one molecule. The compound is obtained by dimerizing a compound represented by chemical formula 18 based on the R1 or the R2. In chemical formula 18, the R1, the R2, and the R3 are respectively R11, OR11, COR11, SR11, CONR12R13, or CN; the R4 and the R5 are respectively R11, OR11, SR11, COR11, CONR12R13, NR12COR11, OCOR11, COOR11, SCOR11, OCSR11, COSR11, CSOR11, CN, halogen element, or hydroxyl group; the a and the b are respectively 0 to 3.

Description

A colored photosensitive resin composition, a color filter, and a liquid crystal display device having the same {A COLORED PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER AND LIQUID CRYSTAL DISPLAY DEVICE HAVING THE SAME}

The present invention provides a colored photosensitive resin composition, a color filter, and a liquid crystal display having the same, which are used to form a colored layer including pixels of a color liquid crystal display on a driving substrate of a thin film transistor (TFT) type color liquid crystal display. It is about.

Color filters are widely used in imaging devices, liquid crystal displays (LCDs), and the like, and their application ranges are rapidly expanding. The color filter used for a color liquid crystal display device, an image pick-up element, etc. spin-coats the coloring photosensitive resin composition containing the pigment corresponding to each color of red, green, and blue normally on the board | substrate with a black matrix patterned. After coating uniformly, the coating film formed by heat-drying (henceforth "preliminary baking" may be called) is exposed and developed, and further heat-hardening (henceforth "after-baking" may be called) as needed. The operation is manufactured by repeating the operation for each color to form pixels of each color.

As such a coloring photosensitive resin composition, the composition containing a photopolymerizable compound and a photoinitiator together with a pigment and binder resin is used abundantly, and the photosensitive resin composition containing a black pigment is used also for black matrix formation.

Recently, the colored photosensitive resin composition is required to have excellent sensitivity and excellent adhesion due to high transmittance even with a small exposure amount in order to improve the yield in the process.

In the prior art for this purpose, but to improve the sensitivity by increasing the content of the polyfunctional monomer in the coloring photosensitive resin composition to increase the degree of crosslinking, this method is left unsealed during development in the unexposed portion or the development type is peeled off because the development type is peeled off It caused the display defect by the phenomenon.

Recently, a photopolymerization initiator including a photoactive oxime ester group having excellent sensitivity in a colored photosensitive resin composition, that is, a compound including one photoactive oxime ester skeleton in one molecule, has been introduced to improve sensitivity. However, when the content of the photopolymerization initiator containing a photoactive oxime ester group exceeds an appropriate amount, there is a problem in that it causes a decrease in luminance and contaminates the exposure machine, and a solution for this is required.

Accordingly, an object of the present invention is to provide a colored photosensitive resin composition exhibiting excellent sensitivity because there is no line break of the pattern and no decrease in transmittance even when applied to a color filter at a low exposure amount.

Another object of the present invention is to provide a color filter manufactured using the colored photosensitive resin composition.

Another object of the present invention is to provide a liquid crystal display device having the color filter.

In order to achieve the said objective, this invention contains a coloring material (A), binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E), The said photoinitiator (D) Provides a colored photosensitive resin composition comprising a compound having at least two photoactive oxime ester skeletons in one molecule.

The present invention also provides a color filter comprising a color layer formed by forming the colored photosensitive resin composition according to the present invention in a predetermined pattern, followed by exposure and development.

This invention also provides the liquid crystal display device provided with the color filter which concerns on this invention.

The colored photosensitive resin composition according to the present invention can provide a high quality color filter and a liquid crystal display device having the same by showing excellent sensitivity due to not having a line break of the pattern even when applied to a color filter and having no decrease in transmittance even at low exposure doses. .

1A to 1H schematically show a step of forming a color filter using the colored photosensitive resin composition of the present invention.

Hereinafter, the present invention will be described in detail.

The coloring photosensitive resin composition which concerns on this invention is a coloring photosensitive resin composition containing a coloring material (A), binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E), The said photoinitiator (D) comprises a compound having at least two photoactive oxime esters skeleton in one molecule.

Coloring material (A)

It is preferable that the said coloring material (A) is an organic pigment or inorganic pigment generally used for a pigment dispersion resist as a pigment normally. Dye may be used for the said coloring material (A) as needed.

Examples of the inorganic pigments include metal compounds such as metal oxides and metal complex salts, and specific examples include metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, barium, calcium, and zinc. Oxides or composite metal oxides. It may also contain carbon black.

Specific examples of the organic and inorganic pigments include compounds classified as pigments in the Color Index (published by The society of Dyers and Colorists), and more specifically, the following color index (CI) numbers: Although a pigment is mentioned, It is not necessarily limited to these.

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

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, 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, etc.

These coloring materials (A) can be used individually or in combination of 2 or more types, respectively.

Content of the said coloring material (A) is 5-60 mass% in mass fraction with respect to solid content in colored photosensitive resin composition, Preferably it is 10-50 mass%. If the content of the coloring material (A) is in the range of 5 to 60% by mass based on the above criteria, even if a thin film is formed, the color density of the pixel is sufficient, and the omission of the non-pixel portion during development does not deteriorate, and thus residue is hardly generated. desirable.

Solid content in a coloring photosensitive composition in this invention means the sum total of the component remove | excluding the solvent.

When the coloring material is a pigment, the pigment dispersion liquid of the state in which the pigment was disperse | distributed uniformly in the solution can be obtained by containing a pigment dispersing agent and performing a dispersion process.

As said pigment dispersant, surfactant, such as silicone type, a fluorine type, polyester type, polyamine type, polyacrylic type, cationic type, anionic type, nonionic type, amphoteric, can be used, for example, These are independent or 2 types or more Can be used in combination.

When using a pigment dispersant, the usage-amount is per 1 mass part of coloring materials in a coloring photosensitive resin composition, Preferably it is 1 mass part or less, More preferably, it is 0.05 mass part-0.5 mass part. When the usage-amount of a pigment dispersant exists in the said range, since the pigment of a uniform dispersion state is obtained, it is preferable to use the said pigment dispersant in the said range.

Binder Resin (B)

The binder resin (B) usually has reactivity and alkali solubility due to the action of light or heat and acts as a dispersion medium of the coloring material. The binder resin (B) contained in the colored photosensitive resin composition of the present invention can be used as long as it is a binder resin that acts as a binder resin for the coloring material (A) and is soluble in the alkaline developer used in the developing step for producing the color filter. Can be.

Preferably, the binder resin (B) comprises a norbornene skeleton compound (B1), an aromatic vinyl compound or an N-substituted maleimide compound (B2) represented by the following formula (1), and a compound (B3) having an unsaturated bond with a carboxyl group It is preferable that it is a copolymer obtained by the copolymerization reaction of the compound to make it, More preferably, it is good that it is unsaturated group containing resin obtained by making the said obtained copolymer further react the compound (B4) which has an unsaturated bond and an epoxy group in 1 molecule.

<Formula 1>

Wherein n is 0 or 1, R 1 and R 2 are each independently hydrogen or an aliphatic or aromatic hydrocarbon containing or without a hetero atom having 1 to 12 carbon atoms, and R 3, R 4, R 5, and R 6 are Are each independently hydrogen, an aliphatic or aromatic hydrocarbon containing or without a hetero atom having 1 to 30 carbon atoms, and two of R 3, R 4, R 5, and R 6 are selected to be linked or unbranched.)

The coloring photosensitive resin composition containing the binder resin containing the norbornene frame | skeleton compound (B1) represented by the said Formula (1) shows the characteristic which is excellent in thermal and chemical resistance.

The norbornene skeleton compound (B1) represented by Formula 1 may be more specifically selected from at least one of compounds having the structural formulas of Formulas 2 to 17 below.

In addition, the (meth) acrylate recorded in this specification means an acrylate and / or a methacrylate.

Specific examples of the compound usable as the aromatic vinyl compound or the N-substituted maleimide compound (B2) are as follows. First, the aromatic vinyl compound includes styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, and m-vinylbenzylmethyl Ether, p-vinylbenzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, indene, and the like. Vinyl toluene has excellent developability and processability. It is preferable to. Examples of the N-substituted maleimide compound include N-cyclohexyl maleimide, N-benzyl maleimide, N-phenyl maleimide, N-phenyl maleimide, No-hydroxyphenyl maleimide, Nm-hydroxyphenyl maleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide and the like N-benzyl maleimide is preferable because it is excellent in developability and processability. These can be used individually or in combination of 2 types or more, respectively.

The compound (B3) having an unsaturated bond as the carboxyl group is not limited as long as it is a carboxylic acid compound having an unsaturated double bond that can be polymerized, and specific examples thereof include acrylic acid and methacrylic acid. Acrylic acid and methacrylic acid can be used individually or in combination of 2 types or more, respectively. In addition to these acrylic acid and methacrylic acid, one or more other acids may be used. As another acid, it is also possible to specifically use together the carboxylic acid chosen from 1 type or more of other unsaturated carboxylic acids, such as crotonic acid, itaconic acid, maleic acid, and fumaric acid. Moreover, you may use together the monomer containing a hydroxyl group and a carboxyl group in the same molecule, such as (alpha)-(hydroxymethyl) acrylic acid.

According to the present invention, in the copolymer obtained by copolymerizing the above (B1) to (B3) (which is included in the present invention even when monomers other than B1 to B3 are further included and copolymerized), each of (B1) to (B3) The proportion of the constituents derived from is preferably in the following ranges in mole fraction with respect to the total moles of the constituents constituting the copolymer.

Structural unit derived from (B1): 2 to 30 mol%,

Structural unit derived from (B2): 2 to 95 mol%,

Structural units derived from (B3): 2 to 70 mol%

In particular, the ratio of the constituents derived from each of the above (B1) to (B3) is more preferably in the following ranges in mole fraction with respect to the total moles of the constituents constituting the copolymer.

Structural unit derived from (B1): 5 to 30 mol%,

Structural unit derived from (B2): 5 to 80 mol%,

Structural units derived from (B3): 5-65 mol%

As described above, when the ratio of the constituents derived from each of (B1) to (B3) is in the above range, the balance of developability, solubility and heat resistance is good, so that a preferable copolymer can be obtained.

In one Embodiment of this invention, when the said copolymer is obtained by copolymerizing (B1)-(B3), it can manufacture by copolymerizing by the following methods.

To the flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot and a nitrogen introduction tube, 0.5 to 20 times the amount of solvent was introduced together on the basis of the total mass of (B1) to (B3) and the flask. I replace my atmosphere with nitrogen in the air. Then, after heating up a solvent at 40-140 degreeC, 0-20 times of a solvent by mass basis with respect to the predetermined amount of (B2) and (B3), and the total mass of (B2)-and (B3), and azo A solution in which a polymerization initiator, such as bisisobutyronitrile or t-butylperoxy 2-ethylhexyl carbonate, is added in an amount of 0.1 to 10 mol% by mole fraction with respect to the total number of moles of (B1) to (B3) (agitated and dissolved at room temperature or under heating). ) Is added dropwise to the flask from 0.1 dropping lot over 0.1 to 8 hours, and further stirred at 40 to 140 ° C for 1 to 10 hours.

In the above process, part or all of the polymerization initiator may be put in the flask, or part or all of (B1) to (B3) may be put in the flask. When (B4) is polymerized to the copolymer obtained by copolymerizing the said (B1)-(B3), you may add the remainder of (B1)-(B3) in the process.

As the solvent used in the above process, a solvent used in a normal radical polymerization reaction may be used, and specifically, tetrahydrofuran, dioxane, ethylene glycol dimethylethyl, diethylene glycol dimethylethyl, acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ethyl acetate, 3-methoxybutyl acetate, methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether , Toluene, xylene, ethylbenzene, chloroform, dimethyl sulfoxide and the like can be used. These solvents can be used alone or in combination of two or more thereof.

Moreover, as a polymerization initiator used for said process, the polymerization initiator normally used can be added, It does not restrict | limit in particular. Specifically, diisopropyl benzene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxy isopropyl carbonate, t-amyl peroxy-2-ethylhexanoate, t-butyl Organic peroxides such as peroxy-2-ethylhexyl carbonate; 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylbareronitoryl), dimethyl 2,2'-azobis (2-methylpropionate), etc. The nitrogen compound of can be used. These can be used individually or in combination of 2 or more types.

In addition, the copolymer obtained by copolymerizing the said (B1)-(B3) can also use (alpha) -methylstyrene dimer and a mercapto compound as a chain transfer agent in order to control molecular weight and molecular weight distribution in a superposition | polymerization process. The usage-amount of (alpha) -methylstyrene dimer and a mercapto compound is 0.005-5 mass% in mass fraction with respect to the total mass of (B1)-(B3). In addition, the said polymerization conditions can also adjust an input method and reaction temperature suitably in consideration of the amount of heat generation by a manufacturing facility, superposition | polymerization, etc ..

According to an embodiment of the present invention, the binder resin is a norbornene skeleton compound represented by Formula 1 (B1), an aromatic vinyl compound or an N-substituted maleimide compound (B2), and a compound having an unsaturated bond with a carboxyl group (B3) Light / thermosetting property can be provided to binder resin by adding the compound (B4) which has an unsaturated bond and an epoxy group in 1 molecule to the copolymer obtained by the copolymerization reaction of the compound containing these.

Specific examples of the compound (B4) having an unsaturated bond and an epoxy group in the above one molecule include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth). ) Acrylate, methylglycidyl (meth) acrylate, and the like. Among these, glycidyl (meth) acrylate is preferably used. These can be used individually or in combination of 2 types or more, respectively.

The compound (B4) having an unsaturated bond and an epoxy group in one molecule is preferably reacted at a molar fraction of 5 to 80 mol% with respect to the number of moles of the component derived from the compound (B3) having a carboxyl group and an unsaturated bond in the copolymer. In particular, 10 to 80 mol% is preferable. When compound (B4) which has an unsaturated bond and an epoxy group exists in the said range, since sufficient photocurability and thermosetting are obtained, a sensitivity and pencil hardness are compatible, and it is excellent in reliability, and it is preferable.

In one embodiment of the present invention, the binder resin (B) can be produced by reacting a copolymer obtained by copolymerizing the above (B1) to (B3) and (B4) by, for example, the following method. .

When the copolymer of (B1) to (B3) is obtained by the method described above, the atmosphere in the flask is replaced with nitrogen by air, and the constituents derived from the compound (B3) having an unsaturated bond with the carboxyl group in the copolymer As a reaction catalyst of 5-80 mol% (B4) and a carboxyl group and an epoxy group by molar fraction with respect to mole number, trisdimethylaminomethylphenol is 0.01-5, by mass fraction with respect to the total mass of (B1)-(B4), for example. As the mass% and the polymerization inhibitor, for example, by adding hydroquinone to the total mass of (B1) to (B4) in a mass fraction of 0.001 to 5% by mass into the flask and reacting at 60 to 130 ° C for 1 to 10 hours, The copolymer of and (B4) can be reacted. In addition, similarly to the polymerization conditions, the charging method and the reaction temperature may be appropriately adjusted in consideration of the amount of heat generated by the production equipment, the polymerization and the like.

In one embodiment of the present invention, the binder resin (B) preferably has a weight average molecular weight in terms of polystyrene in the range of 3,000 to 100,000, more preferably in the range of 5,000 to 50,000. If the weight average molecular weight of the binder resin (B) is in the range of 3,000 to 100,000, film reduction is unlikely to occur at the time of development, and it is preferable because the missing property of the non-pixel portion at the time of development is good.

The acid value of the binder resin (B) is preferably in the range of 30 to 150 mgKOH / g based on solid content. If the acid value is less than 30 mgKOH / g, there is a possibility that the developability to the alkaline water is lowered, leaving a residue on the substrate, and if the acid value exceeds 150 mgKOH / g, the possibility of desorption of the pattern is increased.

It is preferable that it is 1.5-6.0, and, as for the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of binder resin (B), it is more preferable that it is 1.8-4.0. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of 1.5 to 6.0 is preferable because it is excellent in developability.

Content of binder resin (B) is 5-90 mass% normally with respect to solid content in colored photosensitive resin composition, Preferably it is the range of 10-70 mass%. If the content of the binder resin (B) is 5 to 90% by mass based on the above criteria, the solubility in the developing solution is sufficient, and development residues are less likely to occur on the substrate of the non-pixel portion. Since it is hard to produce and the omission of a non-pixel part is favorable, it is preferable.

Photopolymerization  The compound (C)

The photopolymerizable compound (C) contained in the coloring photosensitive resin composition of this invention is a compound which can superpose | polymerize by the action | action of light and the photoinitiator mentioned later, A monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned. have.

The photopolymerizable compound (C) used in the present invention may be used by mixing two or more photopolymerizable compounds having different functional groups or functional groups in order to improve the developability, sensitivity, adhesion, and surface problems of the colored photosensitive resin composition. Can, and does not limit its scope

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

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyloxyethyl) 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, and pentaerythritol tree. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol Hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

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

The photopolymerizable compound (C) is usually used in a mass fraction of 1 to 60% by mass, preferably 5 to 50% by mass, with respect to the solid content in the colored photosensitive resin composition. If the photopolymerizable compound (C) is in the range of 1 to 60 mass% based on the above criteria, the intensity and smoothness of the pixel portion will be good, which is preferable.

Light curing Initiator (D)

The photoinitiator (D) contained in the coloring photosensitive resin composition of this invention contains the compound which has two or more photoactive oxime ester frame | skeleton in one molecule. The compound having two or more photoactive oxime ester skeletons in one molecule is preferably a compound dimerized through R ₁ or R ₂ represented by the following formula (18).

&Lt; Formula 18 >

Wherein R ₁ , R ₂ and R ₃ each independently represent R ₁₁ , OR ₁₁ , COR ₁₁ , SR ₁₁ , CONR ₁₂ R ₁₃ or CN, and R ₄ and R ₅ each independently represent R ₁₁ , OR ₁₁ , SR ₁₁ , COR ₁₁ , CONR ₁₂ R ₁₃ , NR ₁₂ COR ₁₁ , OCOR ₁₁ , COOR ₁₁ , SCOR ₁₁ , OCSR ₁₁ , COSR ₁₁ , CSOR ₁₁ , CN, a halogen atom or a hydroxyl group, a and b respectively Independently 0 to 3.

R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms Wherein the hydrogen atom of the alkyl group, aryl group, arylalkyl group and heterocyclic group is also R ₂₁ , OR ₂₁ , COR ₂₁ , SR ₂₁ , NR ₂₂ R ₂₃ , CONR ₂₂ R ₂₃ , -NR ₂₂ -OR ₂₃ ,- NCOR ₂₂ -OCOR ₂₃ , -C (= N-OR ₂₁ ) -R ₂₂ , -C (= N-OCOR ₂₁ ) -R ₂₂ , CN, halogen atom, -CR ₂₁ = CR ₂₂ R ₂₃ , -CO-CR _{21 = CR 22 R 23, OCO} -CR 21 = CR 22 R 23, OC 1 - 6 alkylene group -OCOR _21, COOR _21, optionally substituted with epoxy group, and optionally, R _21, R ₂₂ and R ₂₃ are each independently hydrogen, An atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, wherein R ₁₁ , R ₁₂ , R ₁₃ , R _21, R ₂₂ and the methylene of the alkylene part of the substituents represented by R ₂₃ groups bull 1 to 5 times may be interrupted by a fire bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond, and the alkyl portion of the substituent may have a branched side chain or a cyclic alkyl, The alkyl terminal of the said substituent may be an unsaturated bond, and R <_12> , R <_13> , R <_22> and R <_23> may each form the ring together, and R <_3> may form the ring with the adjacent benzene ring. R ₄ and R ₅ are each independently R ₁₁ , OR ₁₁ , SR ₁₁ , COR ₁₁ , CONR ₁₂ R ₁₃ , NR ₁₂ COR ₁₁ , OCOR ₁₁ , COOR ₁₁ , SCOR ₁₁ , OCSR ₁₁ , COSR ₁₁ , CSOR ₁₁ , CN , A halogen atom or a hydroxyl group, a and b are each independently 0 to 3).

Preferably, as the alkyl group represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ in Formula 18, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl , t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl , Hexadecyl, octadecyl, isocil, cyclopentyl, cyclohexyl, cyclohexylmethyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, pentyloxyethyl, octyl Oxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyoxyethyl, methoxypropyl, 2-methoxy--1-methylethyl and the like. As the aryl group represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ , for example, phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl, And phenyl, biphenylyl, naphthyl, anthryl and the like substituted with one or more of the above alkyl groups. Examples of the arylalkyl group represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ include benzyl, chlorobenzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and phenylethenyl Etc. can be mentioned. As the heterocyclic group represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ , for example, pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazole- 2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidil, pyrazolidyl, thiazolidyl, isothiazolidil, oxazolidyl, isoxazolidyl, piperidyl, piperazil, morpholinyl 5-7 membered heterocycles, such as these, are illustrated preferably. Moreover, as a ring which R <_12> and R <_13> may form together, the ring which R <_22> and R <_23> may form together, and a ring which R <_3> may form with an adjacent benzene ring, For example, a cyclopentane ring, 5-7 membered rings, such as a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, and a lactam ring, are mentioned. In addition, there may be mentioned _{R 11, R 12, R 13} , R 21, R 22 and R ₂₃ may be a halogen atom and R4, which is substituted halogen atom represented by R5 include fluorine, chlorine, bromine and iodine.

The methylene group of the alkylene moiety of the substituent may be interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond, and at this time, one or more bond groups are interrupted Two or more types of contribution may also be sufficient, and when it is the group which can be interrupted continuously, you may interrupt 2 or more consecutively. In addition, the alkyl part of the said substituent may have a branched side chain, cyclic alkyl may be sufficient, and the alkyl terminal of the said substituent may be an unsaturated bond.

Among the oxime ester compounds of the present invention, in the above formula (18), R ₁ is an alkyl group having 11 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, and a complex having 2 to 20 carbon atoms. Ventilation, OR ₁₁ , COR ₁₁ , SR ₁₁ , CONR ₁₂ R ₁₃ or CN, R ₃ is an alkyl group having 1 to 12 carbon atoms interrupted 1 to 5 times by ether or ester bond, 13 to 20 carbon atoms Alkyl group, OR ₁₁ , COR ₁₁ , SR ₁₁ , CONR ₁₂ R ₁₃ or CN, in particular R ₁ is an alkyl group having 11 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, or R ₃ is an alkylene of an alkyl group The methylene group of the part is a branched alkyl group having 8 or more carbon atoms which may be interrupted 1 to 5 times by an ether bond or an ester bond; The methylene group of the alkylene portion of the alkyl group is an alkyl group of 13 or more small atoms which may be interrupted 1 to 5 times by an ether bond or ester bond; R3 is an alkyl group which is interrupted 1 to 5 times by an ether bond; When R ₃ is an alkyl group which is interrupted 1 to 5 times by an ester bond, the synthesis is easy and high, and when used as a photopolymerization initiator, it is added to a solvent of propylene glycol-1-nomethylether-2-acetate or cyclohexanone. 1 mass% or more is melt | dissolved, and since it satisfy | fills the request as a photoinitiator, it is preferable.

In the oxime ester compound of the present invention, as shown in the following formulas (19) and (20), the compound represented by the formula (18) is preferably dimerized through R ₁ or R ₂ .

(19)

<Formula 20>

Wherein R ₁ to R ₅ are as defined in Formula 18.

Preferred specific examples of the oxime ester compound of the present invention represented by the formula (18) include the compounds represented by the following formulas (21) to (27). However, this invention is not restrict | limited at all by the following compounds.

<Formula 21>

<Formula 22>

<Formula 23>

<Formula 24>

<Formula 25>

<Formula 26>

<Formula 27>

As a preferable specific example of the oxime ester compound of this invention represented by said Formula (20), the compound of following formula (28) is mentioned. However, this invention is not restrict | limited at all by the following compounds.

<Formula 28>

As the compound having two or more photoactive oxime ester skeletons in one molecule, a commercially available compound can be used, and specifically, NCI-831 (ADEKA) can be mentioned as a commercial product having the structure of Formula 28.

The compound having two or more photoactive oxime ester skeletons in one molecule is 10% by mass or more, preferably 20 to 80% by mass, based on the solids content, with respect to the photopolymerization initiator in the colored photosensitive resin composition. When the photopolymerization initiator contains 10% by mass or more of a compound having two or more photoactive oxime ester skeletons in one molecule according to the present invention, the photopolymerization initiator exhibits high sensitivity to light, and thus has high crosslinking density even at a low exposure amount, and thus adhesion to a substrate. It is preferable because there is no tearing of the pattern during development and excellent thermal stability.

The photopolymerization initiator (D) contained in the colored photosensitive resin composition of the present invention is not limited to compounds having two or more photoactive oxime ester skeletons in one molecule, but is not limited to triazine compounds, acetophenone compounds, biimidazole compounds, and the like. One or more compounds selected from the group consisting of oxime compounds can be used together. The coloring photosensitive resin composition containing the said photoinitiator (D) is highly sensitive, and the film | membrane formed using this composition becomes favorable the intensity | strength and surface smoothness of the pixel part.

As said triazine type compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl)-, for example. 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-tri Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

Moreover, as said acetophenone type compound, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- ( 2-hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] And oligomers of propane-1-one.

Moreover, as an acetophenone type compound which can be used other than the acetophenone type compound enumerated above, the compound represented by following formula (29) is mentioned, for example.

<Formula 29>

In Formula 29, R1 to R4 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, a benzyl group or carbon number which may be substituted by an alkyl group having 1 to 12 carbon atoms. The naphthyl group which may be substituted by the alkyl group of 1-12 is shown.

Specific examples of the compound represented by Formula 29 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one and 2-ethyl-2-amino (4-morpholinophenyl) ethane- 1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl- 2-amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholin Nophenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propane-1- On, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. may be mentioned. have.

As said biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2,3-, for example) Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimi Dazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, or a phenyl group at the 4,4', 5,5 'position is carbo The imidazole compound substituted with the alkoxy group etc. are mentioned. Among them, 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole or 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole is preferably used.

Examples of the oxime compound include 0-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the compounds represented by the following formulas (30) to (32).

<Formula 30>

<Formula 31>

<Formula 32>

Moreover, as long as it does not impair the effect of this invention, the other photoinitiator etc. which are normally used in this field can also be used together. As another photoinitiator, a benzoin compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound etc. are mentioned, for example. These can be used individually or in combination of 2 or more types, respectively.

As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As said benzophenone type compound, for example, benzophenone, methyl 0- benzoyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3, 3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

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. Can be mentioned.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be mentioned.

Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl, a titanocene compound, etc. are mentioned as another photoinitiator.

In addition, you may use combining a photoinitiator (D-1) with a photoinitiator (D). When using a photoinitiator adjuvant (D-1) together with a photoinitiator (D), since the coloring photosensitive resin composition containing these becomes more sensitive and the productivity at the time of forming a color filter using this composition is preferable, it is preferable.

As the photopolymerization initiation assistant (D-1), an amine compound and a carboxylic acid compound are preferably used.

Specific examples of the amine compound in the photopolymerization initiation assistant (D-1) include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 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 Aromatic amine compounds, such as 4'-bis (diethylamino) benzophenone, are mentioned. As an amine compound, an aromatic amine compound is used preferably.

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

The amount of the photopolymerization initiator (D) is usually 0.1 to 40% by mass, preferably 1 to 30% by mass, in terms of mass fraction, based on the total amount of the binder resin (B) and the photopolymerizable compound (C) based on the solid content. The usage-amount of an adjuvant (D-1) is 0.1-50 mass% normally on the said reference | standard, Preferably it is 1-40 mass%.

When the usage-amount of a photoinitiator (D) exists in the said range, since the coloring photosensitive resin composition becomes high sensitivity, since the intensity | strength of the pixel part formed using this composition and the smoothness in the surface of this pixel part become favorable, it is preferable. Moreover, since the sensitivity of a coloring photosensitive resin composition becomes high and the productivity of the color filter formed using this composition improves, when the usage-amount of a photoinitiator auxiliary (D-1) exists in said range, it is preferable.

Solvent (E)

The solvent (E) contained in the colored photosensitive resin composition of this invention is not specifically limited, Various organic solvents used in the field of colored photosensitive resin composition can be used. Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene. Diethylene glycol dialkyl ethers such as glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol Alkylene glycol alkyl ether acetates such as monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate and methoxy pentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl ketone, ace Ketones such as methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, 3-methoxy Ester, such as methyl propionate, Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.

Among the solvents described above, organic solvents having a boiling point of 100 ° C. to 200 ° C. in the coating properties and drying properties are preferable, and alkylene glycol alkyl ether acetates, ketones, and 3-ethoxy are more preferable. Ester, such as ethyl propionate and the methyl 3-methoxy propionate, is mentioned, More preferably, propylene glycol monomethyl ether acetate, a propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy propionate, 3- Methyl methoxy propionate etc. are mentioned. These solvents (E) can be used individually or in mixture of 2 or more types, respectively.

Content of the solvent (E) in the coloring photosensitive resin composition of this invention is 60-90 mass% normally with a mass fraction with respect to the coloring photosensitive resin composition whole quantity containing it, Preferably it is 70-85 mass%. When the content of the solvent (E) is in the range of 60 to 90% by mass based on the above criteria, it is 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, or the like. Since applicability | paintability becomes favorable at the time, it is preferable.

Additive (F)

The coloring photosensitive resin composition of this invention is a filler, another high molecular compound, a hardening | curing agent, and a pigment dispersant as needed. It is also possible to use additives (F) such as adhesion promoters, antioxidants, ultraviolet absorbers and anti-agglomerates in parallel.

Specific examples of the filler include glass, silica, alumina and the like.

Specific examples of other high molecular compounds 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. have.

A hardening | curing agent is used in order to raise a deep part hardening and mechanical strength, As a hardening | curing agent, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, etc. are mentioned.

Examples of the epoxy compound in the curing agent include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, noblock type epoxy resins and other aromatic epoxy resins and alicyclic compounds. Epoxy resins, glycidyl ester resins, glycidylamine resins, or brominated derivatives of such epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co) polymer epoxides, Isoprene (co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate and the like.

As said oxetane compound in the said hardening | curing agent, carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, a terephthalate bis oxetane, a cyclohexane dicarboxylic acid bis oxetane, etc. are mentioned, for example. .

The curing agent may include a curing aid compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound with the curing agent. As a hardening auxiliary compound, polyhydric carboxylic acid, polyhydric carboxylic anhydride, an acid generator, etc. are mentioned, for example.

As carboxylic anhydrides, those commercially available as epoxy resin curing agents can be used. As this 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) ( New Nippon Ewha Co., Ltd.) etc. are mentioned. The said hardening | curing agent can be used individually or in mixture of 2 or more types.

Commercially available surfactants can be used as the pigment dispersant, and examples thereof include surfactants such as silicone, fluorine, polyester, polyamine, polyacrylic, cationic, anionic, nonionic and amphoteric. . These can be used individually or in combination of 2 types or more, respectively. As said surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane, Polyethyleneimines and the like, and other trade names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), Mega MEGAFAC (made by Dainippon Ink & Chemicals Co., Ltd.), Florad (made by Sumitomo 3M Co., Ltd.), Asahi guard, Suflon (above, manufactured by Asahi Glass Co., Ltd.), Sol SLSPERSE (made by Genka Corporation), EFKA (made by EFKA Chemicals), PB 821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.

As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, etc. are mentioned.

These adhesion promoters can be used individually or in combination of 2 or more types, respectively. It is 0.01-10 mass% normally with respect to solid content of a coloring photosensitive resin composition, Preferably it contains 0.05-2 mass%.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like.

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

Specifically as said aggregation inhibitor, sodium polyacrylate etc. are mentioned.

The coloring photosensitive resin composition of this invention can be manufactured by the following methods, for example. The coloring material (A) is previously mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the coloring material is about 0.2 µm or less. Under the present circumstances, a pigment dispersant is used as needed and one part or all part of binder resin (B) may be mix | blended. The remainder of binder resin (B), the photopolymerizable compound (C) and the photoinitiator (D), the other components used as needed, and the additional solvent as needed in the obtained dispersion liquid (henceforth a mill base). Is further added to a predetermined concentration to obtain a desired colored photosensitive resin composition.

The present invention provides a color filter comprising a color layer formed by forming the colored photosensitive resin composition according to the present invention in a predetermined pattern, followed by exposure and development, and a liquid crystal display device having the same.

The process of forming a color filter using the coloring photosensitive resin composition of this invention is demonstrated below using FIG.

When manufacturing the color filter by COA (Color Filter on Array) method using the coloring photosensitive resin composition which concerns on this invention, each pixel of red, green, blue color is directly on the TFT layer substrate in which the SiNx (protective layer) coating film was formed. Form a pattern. The pixel pattern is formed on the SiNx coating film (FIG. 1A).

In the process for forming an electrically conductive path between the TFT layer and the electrode (IZO layer), the positive photosensitive resin film is patterned using the mask to remove the SiNx (protective layer) coating film (FIG. 1B).

An electrically conductive path is formed by dry etching (dry etching) the SiNx (protective layer) located on the lower surface of the positive photosensitive resin film (electrically conductive path) (FIG. 1C).

In order to remove the positive photosensitive resin film remaining on the pixel pattern of Fig. 1C, the positive photosensitive resin film layer is removed using a stripper developer (Fig. 1D).

An IZO layer to be used as a common electrode (IZO layer) with a TFT layer is deposited (FIG. 1E).

In order to form the common electrode (IZO layer) layer, a positive photosensitive resin film is formed on the common electrode (IZO layer) layer (FIG. 1F).

The exposed portion of the formed positive photosensitive resin film (the portion where the Izo layer is exposed) is removed by wet etching (wet etching). (FIG. 1G)

In order to remove the remaining positive photosensitive resin film on the common electrode (IZO layer) of FIG. 1G, the positive photosensitive resin film is removed using a stripper developer (FIG. 1H).

The color filter manufactured as described above provides a liquid crystal display device of high quality because there is no line break of the pattern even at a low exposure amount.

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 changes within the meaning and range equivalent to the scope of the claims. In addition, "%" and "part" which show content in a following example and a comparative example mean the mass% or mass part with respect to a coloring photosensitive resin composition unless there is particular notice.

Binder Resin Synthesis Example : Resin (B)

90 g of propylene glycol monomethyl ether acetate, 90 g of propylene glycol monomethyl ether and 11.0 g of 2-norbornene (0.10 mol) were mixed into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube. The atmosphere in the flask was introduced into nitrogen from air, and after heating up to 80 ° C., 70.5 g (0.4 mol) of benzyl methacrylate, 45.0 g (0.5 mol) of methacrylic acid, and 136 g of propylene glycol monomethyl ether acetate were included. A solution obtained by adding 3.2 g of t-butylperoxy 2-ethylhexyl carbonate to the mixture was added dropwise to the flask over 2 hours from the dropping lot, followed by further stirring at 100 ° C for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 30 g of glycidyl methacrylate [0.2 mol (40 mol% based on the carboxyl group of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and 0.145 of hydroquinone g was thrown into the flask, and reaction was continued at 110 degreeC for 6 hours, and resin B with a solid acid value of 100 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 31,000, and molecular weight distribution (Mw / Mn) was 2.3.

At this time, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin was measured using a HLC-8120GPC (manufactured by Tosoh Corporation) apparatus, and the column was used by serially connecting TSK-GELG4000HXL and TSK-GELG2000HXL. The column temperature was 40 ° C, the mobile phase solvent was tetrahydrofuran, the flow rate was 1.0 ml / min, the injection amount was 50 µl, and the detector RI was used, and the measurement sample concentration was 0.6 mass% (solvent = tetrahydrofuran), for calibration. TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation) was used as a standard material.

<Examples 1-4 and Comparative Examples 1-5>

Among the components shown in Table 1 below, the total amount of the pigment (A) coloring material and the pigment dispersant (F) other additive is 20 in a mass fraction relative to the total amount of the mixture of the pigment, the pigment dispersant and the propylene glycol monomethyl ether acetate. The mixture was mixed up to the mass%, the pigment was sufficiently dispersed using the bead mill, and the bead mill was separated, and the remaining components including the remaining amount of propylene glycol monomethyl ether acetate were further added and mixed to obtain a colored photosensitive resin composition.

　 Example Comparative example One 2 3 4 One 2 3 4 5 Coloring material (A) Coloring materials (A1) 2.98 Coloring materials (A2) 0.50 Binder Resin (B) 6.52 6.52 6.52 6.52 6.52 6.52 6.52 6.52 6.52 Photopolymerizable Compound (C) 6.16 6.16 6.16 6.16 6.16 5.46 5.83 5.83 6.16 Photopolymerization Initiator (D) Initiator (D1) 1.46 1.06 1.06 1.79 - - - - - Initiator (D2) 0.33 - - - 1.79 2.49 1.79 0.33 1.06 Initiator (D3) - 0.58 0.73 - - - 0.33 1.79 0.58 Initiator (D4) - 0.15 - - - - - - 0.15 Solvent (E) 80.46 Additive (F) Additive (F1) 1.49 Additive (F2) 0.10

Each component used in Table 1 is as follows.

Coloring material (A1): blue pigment dispersion (C.I. Pigment Green 58)

Coloring material (A2): Yellow pigment dispersion (C.I. Pigment Yellow 150)

Photopolymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Initiator (D1): Formula 28 [NCI-831 <manufacturer: ADEKA>]

Initiator (D2): ethanone-1- [9-ethyl-6- (2-methyl-4tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) ( Irgacure OXE02; manufactured by Ciba Specialty Chemical

Initiator (D3): 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (Irgacure 369; manufactured by Ciba Specialty Chemical)

Initiator (D4): 4,4'-bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Kagaku Co., Ltd.)

Solvent (E): Propylene glycol monomethyl ether acetate

Additive (F1): acrylic pigment dispersant (Disperbyk-2009; manufactured by BYK)

Additive (F2): 3-methacryloxypropyltrimethoxysilane

<Measurement specimen preparation>

A glass substrate of 2 square inches (# 1737, manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. The coated photosensitive resin composition (Table 1) was exposed on the glass substrate at an exposure amount (365 nm) of 100 mJ / cm 2 and spin-coated so that the film thickness after post-firing when the development step was omitted was 3.2 占 퐉. Preliminary drying was carried out at 100 ° C for 3 minutes in a clean oven. After cooling, the gap between the substrate coated with the colored photosensitive resin composition and a quartz glass photomask (having a pattern for changing the transmittance stepwise in the range of 1 to 100% and a line / space pattern from 1 µm to 50 µm) Was made into 100 micrometers, and it irradiated with the exposure amount (365 nm) of 100 mJ / cm <2> in air | atmosphere using the ultrahigh pressure mercury lamp (brand name USH-250D) by Ushio Denki Corporation. Thereafter, the coating film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide at 26 ° C. for a predetermined time, and then dried at 230 ° C. for 60 minutes after washing with water. No surface roughness was found in the obtained pixel portion. In addition, the development residue did not generate | occur | produce on a non-pixel part on a board | substrate.

　 Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Line tear * 1 ○ ○ ○ ○ X ○ X X X Transmittance * 2
(Same x, y to Y) ○ ○ ○ ○ ○ X X X ○

* 1: After development, it is set as X when the minimum required exposure amount required to prevent line tearing in L / S is 20 mJ or less, and when it exceeds 20 mJ.

* 2: When the composition of the Example and the comparative example is 100% of the transmittance (Y) of the composition of Example 1 on the same (x, y) color coordinates, the transmittance falls below 5%. Set to X.

As shown in Table 2, Comparative Examples 1 to 5, which include D1, which is a compound containing two or more photoactive oxime ester skeletons in one molecule as a photopolymerization initiator according to the present invention, do not include the same. Compared with the low exposure dose, it can be seen that there is no line break of the pattern and no decrease in transmittance.

(Name of the reference number of the drawing)
Ⓐ: pixel pattern of R / G / B ⓑ: SiNx (protective layer)
Ⓒ: TFT layer ⓓ: glass substrate,
Ⓔ: Positive PR ⓕ: IZO layer (common electrode)

Claims (7)

It comprises a coloring material (A), binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E), and said photoinitiator (D) has at least 2 photoactive oxime ester frame | skeleton in one molecule. The coloring photosensitive resin composition characterized by including the compound which has.
The colored photosensitive resin composition according to claim 1, wherein the compound having at least two photoactive oxime ester skeletons in one molecule is dimerized through R ₁ or R ₂ .
<Formula 18>

(Wherein R ₁ , R ₂ and R ₃ each independently represent R ₁₁ , OR ₁₁ , COR ₁₁ , SR ₁₁ , CONR ₁₂ R ₁₃ or CN,
R ₄ and R ₅ are each independently R ₁₁ , OR ₁₁ , SR ₁₁ , COR ₁₁ , CONR ₁₂ R ₁₃ , NR ₁₂ COR ₁₁ , OCOR ₁₁ , COOR ₁₁ , SCOR ₁₁ , OCSR ₁₁ , COSR ₁₁ , CSOR ₁₁ , CN Represents a halogen atom or a hydroxyl group,
a and b are 0-3 each independently.
R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms Wherein the hydrogen atom of the alkyl group, aryl group, arylalkyl group and heterocyclic group is also R ₂₁ , OR ₂₁ , COR ₂₁ , SR ₂₁ , NR ₂₂ R ₂₃ , CONR ₂₂ R ₂₃ , -NR ₂₂ -OR ₂₃ ,- NCOR ₂₂ -OCOR ₂₃ , -C (= N-OR ₂₁ ) -R ₂₂ , -C (= N-OCOR ₂₁ ) -R ₂₂ , CN, halogen atom, -CR ₂₁ = CR ₂₂ R ₂₃ , -CO-CR _{21 = CR 22 R 23, OCO} -CR 21 = CR 22 R 23, OC 1 - ₆ and optionally substituted by an alkylene group -OCOR _21, COOR _21, an epoxy group,
R ₂₁ , R ₂₂ and R ₂₃ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms Indicates,
The methylene group of the alkylene moiety of the substituent represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ is an unsaturated bond, ether bond, thioether bond, ester bond, thioester bond, amide bond or urethane May be interrupted 1 to 5 times by a bond, the alkyl moiety of the substituent may have a branched chain, a cyclic alkyl may be used, or the alkyl terminal of the substituent may be an unsaturated bond,
In addition, R ₁₂ and R ₁₃ and R ₂₂ and R ₂₃ may each form a ring together, and R ₃ may form a ring together with an adjacent benzene ring.)
The colored photosensitive resin composition according to claim 2, wherein the compound having at least two photoactive oxime ester skeletons in one molecule is a compound represented by the following general formula (19) or (20).
<Formula 19>

<Formula 20>

(Wherein R ₁ to R ₅ are as defined in claim 2).
The colored photosensitive resin composition according to claim 2, wherein the compound having at least two photoactive oxime ester skeletons in one molecule is a compound represented by the following Chemical Formula 28:
<Formula 28>

The method of claim 1,
Content of the said photoinitiator (D) is 0.1-40 mass% in mass fraction with respect to the total amount of binder resin (B) and a photopolymerizable compound (C) based on solid content,
The compound which has 2 or more photoactive oxime ester frame | skeleton in the said one molecule is contained 10 mass% or more by mass fraction with respect to the photoinitiator in a coloring photosensitive resin composition based on solid content.
The color filter formed by exposing and developing after forming the coloring photosensitive resin composition of any one of Claims 1-5 in a predetermined pattern on a board | substrate, The color filter characterized by the above-mentioned.
The color filter of Claim 6 is provided, The liquid crystal display device characterized by the above-mentioned.

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