TWI418933B - Colored photosensitive resin composition, color filter and liquid crystal display device prepared by using the same - Google Patents

Description

Colored photosensitive resin composition, color filter manufactured by the same, and liquid crystal display device

The present invention relates to a colored photosensitive resin composition, a color filter produced thereby, and a liquid crystal display device.

A color filter is built in a color photographic device such as a complementary metal oxide semiconductor (CMOS) or a charge coupled device (CCD) having image sensing elements. , you can get real color images. In addition, it is widely used in image sensors, plasma display devices (PDPs), liquid crystal display devices (LCDs), electric field emission display devices (FELs), light-emitting diode displays (LEDs), etc., and The scope of application is still rapidly expanding. In particular, the application of LCDs has been expanded in recent years, and therefore, color filters have been recognized as one of the most important parts.

Such a color filter is produced by a method of forming a desired coloring pattern using a coloring photosensitive resin composition containing a coloring agent. More specifically, after forming a coating layer made of a colored photosensitive resin composition on a substrate, a pattern is formed on the formed coating layer, and exposure and development are performed. Thereafter, heat hardening treatment is performed. The above process is repeated to produce a color filter.

Recently, in order to improve the productivity and yield of LCD manufacturing engineering, when manufacturing color filters, A pixel is formed under a low exposure amount to manufacture a color filter. Therefore, a colored photosensitive resin composition capable of exhibiting high sensitivity characteristics even under low exposure conditions was used. However, although it is known that the conventional color-sensitive photosensitive resin composition has a high sensitivity characteristic, when a pixel is formed under a low exposure amount, a disadvantage of a surface defect such as a development spot may occur.

Therefore, there is an urgent need in the art to develop an engineering-improving color-sensitive photosensitive resin composition capable of preventing surface defects and improving LCD even when forming a pixel under a low exposure amount, which is suitable for color filter manufacturing. Productivity and productivity of manufacturing engineering.

A main object of the present invention is to provide a colored photosensitive resin composition which does not cause a problem such as spots on the surface of the film even when a pixel (pixel) forming condition of a low exposure amount is formed.

Another object of the present invention is to provide a color filter which does not cause a problem of developing speckles in a pixel portion.

Still another object of the present invention is to provide a liquid crystal display having the above color filter.

In order to achieve the above object, the present invention provides a colored photosensitive resin composition characterized by comprising (A) a colorant, (B) an alkali soluble resin, (C) a photopolymerizable compound, and (D) photopolymerization initiation. A solvent, (E) a solvent, and (F) a fluorine-based reactive additive as described in Chemical Formula 1 below.

(In Chemical Formula 1, R ₁ is independently ethylene, (iso)propylene, butene, (poly)ethylene glycol or (poly)propylene glycol, R ₂ is hydrogen or methyl, and Rf is a fluorine-based polyol, and the following Chemical formula 2 indicates.)

(In Chemical Formula 2, R ₃ is a mutually symmetric structure of methylene or (poly)ethylene glycol; and in the case where R ₄ is a carbon atom, R ₅ is independently nitrogen, methyl, propyl, butyl or CH ₂ -O-CH ₂ -CPF _2P+1 ; wherein, in the case where R ₄ is CF ₂ O-(CF ₂ CF ₂ O) _a -(CF ₂ O) _b , R ₅ is absent, wherein a and b is each an integer of 0 or more, and a+b is an integer of 1 to 20; wherein P is an integer of 1 to 10, and n is an integer of 1 to 20.)

The (F) fluorine-based reactive additive is preferably a compound obtained by reacting a (meth)acrylic acid isocyanate with a fluorine-based polyol.

In this case, the (meth)acrylic acid isocyanate is preferably produced by reacting a (meth)acrylamide with a phosgene reaction or by reacting a (meth) acrylate containing a hydroxyl functional group with an excess of a diisocyanate. . Further, the fluorine-based polyol preferably has a fluorine content in the molecule of 10 to 90% by weight and contains at least one ether.

The content of the (F) fluorine-based reactive additive may be a solid portion content in the colored photosensitive resin composition, and is added in an amount of 0.001 to 14% by mass based on the mass ratio.

In order to achieve another object of the present invention, the present invention provides a color filter characterized in that the color filter includes exposure and development in a predetermined pattern after the colored photosensitive resin composition is applied onto the upper portion of the substrate. The colored layer formed.

In order to achieve still another object of the present invention, the present invention provides a liquid crystal display characterized by having the color filter.

As described above, the colored photosensitive resin composition of the present invention is in a low-exposure pixel condition It can also exhibit high sensitivity characteristics. Therefore, when the colored photosensitive resin composition of the present invention is applied to a color filter manufacturing process, since it has excellent engineering properties, it is possible to produce a color filter in which a pixel portion does not cause surface defects such as development spots. Since only a small amount of exposure is used, the effect of improving productivity and productivity can be achieved in engineering. According to the above characteristics, the colored photosensitive resin composition of the present invention can be effectively applied to the production of a high-quality color filter.

10‧‧‧Substrate

11‧‧‧Colored layer

11R‧‧‧ coloring pattern

20‧‧‧Photomask

30‧‧‧Light

1a-1c is a schematic view showing a process of manufacturing a color filter using a colored photosensitive resin composition according to an embodiment of the present invention.

In order to achieve the above object, the present invention provides a colored photosensitive resin composition comprising (A) a colorant, (B) an alkali soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization A starting agent, (E) a solvent, and (F) a fluorine-based reactive additive. The colored photosensitive resin composition may optionally contain a photopolymerization initiation aid, a pigment dispersant, or other additives.

Hereinafter, the various components contained in the colored photosensitive resin composition of the present invention will be described in detail below, but the following are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention.

(A) colorant

(A) The coloring agent does not limit the color tone, and the color tone can be selected in accordance with the use of the color filter. More specifically, the (A) colorant may be used singly or in combination of two or more kinds of pigments, dyes or natural pigments. The (A) coloring agent is one selected from the group consisting of pigments, dyes, and natural colors, and one type or a mixture of two or more types is used at the same time. The pigment may be an inorganic pigment classified as a pigment of a pigment in a color index (published by The Society of Dyers and Colourists) or an inorganic pigment such as a metal salt, a metal salt or a barium sulfate, but preferably heat resistance is used. Excellent color development Organic pigments.

Specific examples of compounds classified as Pigment in the Color Index (published by The Society of Dyers and Colourists) are as follows: CI Pigment Yellow 1,3,12,13,14,15,16,17,20, Yellow pigments of 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 185, 214, 214, etc.; CI pigment (Pigment) orange 13,31,38,40,42,43,51,55,59,61,64,65,71 , orange pigment of 73, etc.; red pigment of CI pigment (Pigment) red 9,97,105,122,123,144,149,166,168,176,177,180,192,209,215,216,224,242,254,255,264,265, etc.; CI pigment (Pigment) blue 15,15:3,15:4,15:6,21,28,64,60 , blue pigment of 76; etc.; purple pigment of CI pigment (Pigment) purple 14,19,23,29,32,33,36,37,38; CI pigment (Pigment) green 7,10,15,25, Green pigments such as 36, 47, and 58; brown pigments such as CI pigments 23, 25, and 28; or black pigments such as CI pigment black 1, Pig pigment black 7.

In the (A) colorant, it is preferred to select CI pigment yellow 138, CI pigment yellow 139, CI pigment yellow 150, Pig pigment yellow 185, CI pigment. (Pigment) Red 177, Pig Pigment Red 242, Pig Pigment Red 254, Pig Pigment Purple 23, Pig Pigment Blue 15:6, Pig Pigment Green 7, CI At least one of the group consisting of Pigment Green 36 and Pig Pigment Blue 58 Choose more than one.

The organic pigment and the inorganic pigment may be used singly or in combination of two or more. More specifically, when a red pixel is to be formed, a CI Pigment Red 254 and a Pig Pigment Red 177 may be combined; when a green pixel is to be formed, a CI Pigment Green 58 and a CI Pigment (Pigment) may be used. Yellow 150 or CI Pigment Yellow 138 are combined; when blue pixels are to be formed, CI Pigment Blue 15:6 and CI Pigment Purple 23 can be combined.

The (A) colorant is added in an amount of 5 to 60% by mass based on the mass fraction of the solid content of the colored photosensitive resin composition of the present invention. It is preferably 10 to 50% by mass. (A) When the colorant is 5 to 60% by mass in this standard, a sufficient pixel concentration can be exhibited after the film is formed, and the pixel leakage rate of the non-pixel portion is not lowered during development. Therefore, it is not easy to cause a residual phenomenon.

At this time, the total content of the total solid portion in the colored photosensitive resin composition is the total content of the remaining components after the solvent is removed from the colored photosensitive resin composition.

When the (A) coloring agent is used as a pigment, it is preferred to use a uniform particle size. A method of making the particle size uniform is, for example, a dispersion treatment by adding a pigment dispersant. Using this method, a pigment dispersion liquid which is uniformly dispersed in a solution can be obtained.

As the pigment dispersant, a surfactant such as a surfactant such as a positive ion system, an anion system or a nonionic surfactant can be used as it is. These surfactants may be used alone or in combination of two or more. The product name of the surfactant is, for example, Mega Pack (manufactured by Dainippon Ink and Chemicals, Inc.), BYK, Disperbyk (manufactured by Big Chemi Japan Co., Ltd.), and Solspas (manufactured by Zenake Co., Ltd.).

The pigment dispersant is added in an amount of less than 1 part by mass to 1 part by mass of the (A) colorant. Among them, preferably The amount added is 0.05 to 0.5 parts by mass. When the content of the pigment dispersant is in the above range, a dispersed pigment of uniform particles can be obtained, which is preferable.

(B) Alkaline soluble resin

The (B) alkali-soluble resin is a solvent which is soluble in the solvent of the present invention, and is a resin which has an adhesive function to the (A) coloring agent and is soluble in an alkaline developing solution, and the type is not particularly limited. .

Preferably, the (B) alkali-soluble resin uses a carboxyl group-containing monomer and a polymerizable monomer (b1) having an unsaturated bond, and may have an unsaturated bond polymerizable monomer (b2) copolymerized with the (b1). a copolymer (B-1), or a photopolymerizable unsaturatedly bonded polymer obtained by reacting the epoxy group (b3) which is additionally unsaturatedly bonded to the copolymer (B-1) ( B-2).

Among them, a specific example of the polymerizable monomer (b1) which is unsaturatedly bonded to the carboxylic acid group is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid or crotonic acid (CA). Monocarboxylic acid). In addition, maleic acid, fumaric acid, citraconic acid, mesaconic acid, methylene butyrate can also be used. An unsaturated monocarboxylic acid such as itaconic acid (ITA) and the unsaturated monocarboxylic anhydride. Further, the polymerizable monomer exemplified in (b1) may be used alone or in combination of two or more. Further, a monomer having a carboxyl group and a carboxyl group in the same molecule such as α-(hydroxymethyl)acrylic acid can also be used.

Specific examples of the unsaturated bonded comonomer (b2) copolymerizable with the (b1) are styrene, vinyl toluene, α-methyl styrene, and P-chlorostyrene, methoxystyrene, m-methoxystyrene, p-methoxystyrene, vinyl benzyl methyl ether, methylene Aroma of benzyl dimethyl ether, p-vinyl benzyl dimethyl ether, vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether Group of vinyl compounds; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (n-propyl) Meth)acrylate), isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (methyl) Alkyl (meth) acrylates such as acrylate, t-butyl (meth) acrylate, etc.; cyclopentyl (meth) acrylate (cyclopentyl (meth)) Acrylate), cyclohexyl (meth)acrylate, 2-methyl cyclohexyl (meth)acrylate, tricyclic [5.2.1.0 ^{2, 6} ] decane-8-fluorene (meth) acrylate, 2-cyclopentenyl oxyethyl acrylate, isobornyl (meth) acrylate, etc. Alicyclic (meth) acrylates; aryl (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate; 2-hydroxyethyl ( Hydroxyethyl) hydroxyalkyl (meth) acrylates such as (meth) acrylate, 2-hydroxypropyl (meth) acrylate; N-cyclohexyl marlinimine (N -cyclohexyl maleimide), N-benzyl maleimide, N-phenyl maleimide, N-phenyl maleimide, N- O-hydroxyphenyl maleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide (methylphenylmaleimide), N-m-methylphenyl mala Amine, N-p-methylphenylmaleimide, N-o-methoxyphenyl methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-p-methoxybenzene An N-substituted maleimide compound such as carbamazepine or an unsaturated amine compound such as (meth)acrylamide or N,N-dimethyl(meth)acrylamide (unsaturated) Mamide compound); 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyl propylene oxide (ethyl oxetane) , 3-(methacrylomethoxymethyl)-2-trifluoromethyl oxetane, 3-(methacrylomethoxymethyl)-2-phenyl propylene oxide, 2-( An unsaturated propylene oxide compound such as methacryloyloxymethyl) propylene oxide or 2-(methacrylomethoxymethyl)-4-trifluoromethyl propylene oxide. Further, the polymerizable monomer exemplified in (b2) may be used alone or in combination of two or more.

Specific examples of the compound (b3) having the unsaturated bond and the epoxy group are epoxypropyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 2,3-epoxy Epoxycyclopentyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, methyl [5.2.1.0 ^2,6 ]decane-9-fluorene (meth) acrylate of methyl glycidyl (meth) acrylate, 3,4-epoxytricyclo (epoxytricyclo) Wait. Further, the compounds exemplified in (b3) may be used singly or in combination of two or more.

The (B) alkali-soluble resin according to the present invention is a copolymer (B-1) obtained after the copolymerization of (b1) and (b2) described above, or obtained by copolymerization of the (b1) and (b2) The copolymer (B-1), or the copolymer (B-1) obtained after the copolymerization of (b1) and (b2), and the photopolymerizable unsaturated bond obtained after the reaction process is carried out as (b3) The copolymer (B-2) of the knot, the ratio of the component derived from the copolymer (b1) obtained by copolymerization of the (b1) and (b2) is a molar ratio with respect to the total moles of the constituents constituting the copolymer. The fractional rate is preferably within the following range. At this time, in addition to the (b1) and (b2), the copolymer may be added with another monomer for copolymerization treatment.

The ratio of the components derived from the (b1) and (b2) to the total moles of the constituents constituting the copolymer is as follows: the unit of the composition derived from (b1): 2 to 95 mol% The constituent unit derived from (b2): 2 to 70 mol%; the ratio of the components derived from the respective (b1) and (b2), and the molar fraction relative to the total number of moles constituting the composition of the copolymer as follows: The unit of composition derived from (b1): 2 to 70 mol%; the unit of derivation derived from (b2): 2 to 50 mol%; as shown above, if the component derived from (b1) and (b2) When the ratio is in the above range, a copolymer which is excellent in developability, solubility, and adhesion to a substrate can be obtained.

The (b3) is preferably carried out in an amount of from 2 to 80 mol% based on the total number of moles of the components derived from the (b1). Among them, the best results are obtained when the reaction is carried out at 2 to 50 mol%. When the ratio of the (b3) compound is in the above range, crosslink density and superior sensitivity and developability can be improved.

The (B) alkali-soluble resin is a copolymer obtained by copolymerization of (b1) and (b2), or a copolymer obtained by copolymerization of (b1) and (b2), and then reacted with (b3). The copolymer obtained after the production method is as follows.

In a flask having a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, after introducing a solvent which is 0.5 to 20 times the total amount of the (b1) and (b2), The ambient air in the flask was replaced with nitrogen. Next, after raising the temperature of the solvent to 40 to 140 ° C, the predetermined amount of (b1) and (b2), the total amount of the (b1) and (b2), and 0.5 to 20 times of the solvent and the couple a polymerization initiator such as nitrogen diisobutyl phthalate or benzoyl peroxide is added to a solution in which 0.1 to 10 mole percent of the total number of moles of the above (b1) and (b2) is added (mixing and stirring at room temperature or under heating) After that, the solution was dropped into the flask over a period of 0.1 to 8 hours using a dropping funnel, and stirred at a temperature of 40 to 140 ° C for 1 hour to 10 hours.

In the above procedure, in order to control the molecular weight, an α-methylstyrene dimer or a thiol compound may be added as a chain transfer agent. In this case, the amount of the α-methylstyrene dimer or the thiol group compound to be added is 0.005 to 5% by mass based on the total mass of the above (b1) and (b2). Further, the copolymerization conditions can be adjusted according to the calorific value of the production equipment or copolymerization, and the appropriate addition manner or reaction temperature can be adjusted.

As described above, after the (b1) and (b2) compounds are copolymerized, a copolymer can be produced.

Next, the ambient air in the flask is replaced with air, and the constituent unit derived from (b1) in the copolymer obtained by the copolymerization of (b1) and (b2) is added to a molar fraction of 2 to 80 mol% (b3), for example, a reaction catalyst such as a tris(dimethylaminophenol)carboxyl group and an epoxy group, or a copolymerization inhibitor such as hydroquinone. In this case, the reaction catalyst is based on the total amount of (b1) and (b3). After adding 0.01 to 5 mass%, the reaction is carried out at a temperature of 60 to 130 ° C for 1 to 10 hours.

In this case, in the same manner as the above-described copolymer, the amount of addition or the reaction temperature can be appropriately adjusted depending on the amount of heat generated in the production equipment and the copolymerization operation.

(B) an alkali-soluble resin which completes the polymer (B-2) containing a photopolymerizable unsaturated bond can be manufactured. Next, the copolymer obtained by the (b1) and (b2) copolymerization treatment, or (b1) after the (b2) copolymerization treatment, can be produced to obtain the photopolymerizable unsaturated binding copolymer (B2) (B). Alkali-soluble resin.

According to the present invention, the polystyrene-equivalent weight average molecular weight of the (B) alkali-soluble resin is preferably in the range of 3,000 to 100,000, and the most preferable range is 5,000 to 50,000. When the weight average molecular weight of the (B) alkali-soluble resin is in the range of 3,000 to 100,000, the film thickness can be prevented from being reduced during the development process, and the problem of leakage of the pattern portion can be improved, which is extremely advantageous.

The acid value of the (B) alkali-soluble resin is 50 to 150 (KOH mg/g), and it is preferred that the (B) alkali-soluble resin has an acid value of 60 to 140. A better range is 80 to 135, and the best range is 80 to 130. When the acid value of the (B) alkali-soluble resin is in the range of 50 to 150, the solubility of the developing solution can be improved, and the residual film ratio can be improved. In this case, the acid value refers to a value obtained by measuring the amount (mg) of potassium hydroxide required to dissolve 1 g of the acrylic polymer, and an appropriate acid value is usually obtained using an aqueous potassium hydroxide solution.

The solid content of the (B) alkali-soluble resin relative to the colored photosensitive resin composition of the present invention According to the mass fraction, 5 to 85 mass% is added, preferably 10 to 70 mass%. When the content of the (B) alkali-soluble resin is 5 to 85 mass%, the developing solution has sufficient solubility and is relatively easy to form a pattern. In addition to this, when development is performed, the phenomenon that the film layer of the pixel portion of the exposed portion is lowered can be prevented, and the problem of leakage of non-pixels is improved.

(C) Photopolymerizable compound

The (C) photopolymerizable compound is a compound which can be subjected to a copolymerization procedure by an active radical or an acid generated by (D) a photopolymerization initiator from a light irradiation method, and is not particularly limited. range. For example, a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound, a trifunctional or higher polyfunctional photopolymerizable compound, or the like can be used.

Specific examples of the monofunctional photopolymerizable compound are: mercaptophenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyl Ethyl acrylate, N-vinyl pravone, etc., currently available on the market are ARONIX M-101 (East Asian Synthetic), KAYARAD TC-110S (Nippon Chemical), Viscount 158 (OSAKA YUKI Chemical).

Specific examples of the difunctional photopolymerizable compound are: 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, butanediol di(meth)acrylic acid Ester, hexanediol di(meth) acrylate, diethylene glycol di(meth) acrylate, triethylene glycol di(meth) acrylate, tetraethylene glycol di(meth) acrylate, poly Ethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxylate neopentyl glycol diacrylate, propoxylated neopentyl Alcohol diacrylates, etc., currently sold on the market are ARONIX M-210, M-1100, 1200 (East Asia Synthetic), KAYARAD HDDA (Nippon Chemical), Viscount260 (OSAKA YUKI Chemical), AH-600, AT-600, UA-306H (KOEISHA Chemicals), etc.

Specific examples of the trifunctional or higher polyfunctional photopolymerizable compound are trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol propoxylate. Tris(meth)acrylate, propyl isocyanate tri(methyl) aryl ester, dimethyl alcohol propane tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(methyl) Acrylate, ethoxylate dipentaerythritol hexa(meth) acrylate, ethoxylate trimethylolpropane tri(meth) acrylate, propoxylated dipentaerythritol hexa(meth) acrylate, C Oxylated trimethylolpropane tri(meth)acrylate, etc., currently available on the market are KAYARAD TMPTA, KAYARAD DPHA (Nippon Chemical).

(C) Photopolymerizable compound It is recommended to use a difunctional or higher photopolymerizable compound among the above compounds, and in particular, the most preferable photopolymerizable compound is a trifunctional or higher polyfunctional photopolymerizable compound.

(C) The photopolymerizable compound is preferably added in an amount of 5 to 50% by mass based on the solid content of the colored photosensitive resin composition, and particularly preferably 7 to 45. Percentage of mass. When the (C) photopolymerizable compound is added in an amount of 5 to 50% by mass based on the above ratio, the strength and smoothness of the optimum pixel portion can be obtained.

(D) Photopolymerization initiator

The (D) photopolymerization initiator is such that the (B) alkali-soluble resin and the (C) photopolymerizable compound can be copolymerized, and the content thereof is not particularly limited, particularly in terms of copolymerization characteristics. From the viewpoints of absorption wavelength, availability, and price, one or more compounds may be selected from the group consisting of a triazine-based compound, an acetophenone-based compound, a diimidazole-based compound, and an anthracene compound.

Wherein, a specific example of the triazine compound is 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4 - bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three Pyridazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxy Styrene)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-i1)vinyl]-1,3, 5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-i1)vinyl]-1,3,5-triazine, 2,4-dual ( Trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl) 6-[2-(3,4-Dimethoxyphenyl)vinyl]-1,3,5-triazine and the like.

Specific examples of the acetophenone-based compound are diethoxyethyl benzene, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, and 2- Hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methyl sulphide Phenyl)-2-morpholinpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinyl)butan-1-one, 2-hydroxy-2 -methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4) - morpholine phenyl) butan-1-one and the like.

Specific examples of the non-imidazole compound are 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl nonimidazole, 2,2'-bis(2,3-di Chlorophenyl)-4,4',5,5'-tetraphenyl nonimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy) Phenyl) non-imidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl) nonimidazole, 2,2-bis (2, After 6-dichlorophenyl)-4,4'5,5'-tetraphenyl-1,2'-nonimidazole or 4,4',5,5' position of phenyl group is replaced by alkoxycarbonyl group Imidazole compounds and the like. Among them, it is recommended to use 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl nonimidazole, 2,2'-bis(2,3-dichlorophenyl) -4,4',5,5'-tetraphenyl nonimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4'5,5'-tetraphenyl-1,2 '- Non-imidazole.

Specific examples of the ruthenium compound are o-ethoxycarbonyl-α-oxyimino-1-phenylprop-1-ane and a compound represented by the following Chemical Formulas 3-5.

[Chemical Formula 3]

In addition to the above photopolymerization initiator, other photopolymerization initiators which do not have any influence on the effects of the present invention may be used in combination. Specific examples of the other photopolymerization initiators include a benzophenone compound, an benzophenone compound, an isopropyl compound, an anthraquinone compound, and the like, and these components may be used singly or in combination of two or more.

Specific examples of the benzophenone ketone compound are: benzophenone, benzophenone methyl ether, benzophenone ethyl ether, benzophenone isopropyl ether, and benzophenone ketone isobutyl ether. Wait.

Specific examples of the benzophenone-based compound are: benzophenone, 0-benzoquinone benzoic acid methyl, 4-phenylbenzophenone, 4-phenylhydrazine-4'-methyldiphenyl sulfide, 3, 3',4,4'-tetrakis(n-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the isopropyl compound are: 2-isopropylisopropyl, 2,4-diethylisopropyl, 2,4-dichloroisopropyl, 1-chloro-4-propoxy Isopropyl and the like.

Specific examples of the lanthanide compound are: 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9, 10-diethoxy oxime and the like.

Specific examples of other photopolymerization initiators are: 2,4,6-trimethylphenylphosphonium diphenyloxide, 10-butyl-2-chloroazetidone, 2-ethylhydrazine, benzyl 9,10-phenanthrenequinone, camphorone, phenylglyoxylic acid, methyl, titanocene compound, and the like.

The photopolymerization initiator (D-1) may be added to the (D) photopolymerization initiator. When the photopolymerization initiator (D-1) is added to the photopolymerization initiator, the sensitivity of the coloring photosensitive resin composition can be improved, so that the production efficiency can be improved.

Specific examples of the photopolymerization initiator (D-1) include one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group.

Specific examples of the amine compound are: an aliphatic amine compound such as triethanolamine, methyldiethanolamine and triisopropanamine, 4-dimethylammonium benzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4 - dimethylammonium benzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N,N-dimethyl-p-toluidine, 4, 4'-bis(dimethylamino)benzophenone (commonly known as: Michler's ketone), 4,4'-bis(diethylamino)benzophenone aromatic amine compound. Among them, the amine compound recommended for comparison is an aromatic amine compound.

Specific examples of the carboxylic acid compound are: phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, Methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid An aromatic isophthalic acid such as N-naphthylglycine or naphthyloxyacetic acid.

Specific examples of the thiol group-containing organic sulfur compound are: 2-sulfanylbenzothiazole, 1,4-bis(3-sulfanylbutoxy)butane, 1,3,5-para ( 3-thiol butyl ethoxy)-1,3,5-trioxazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane ginseng (3-sulfhydryl propyl Acid), pentaerythritol tetrakis(3-thiohydropropionic acid), pentaerythritol tetrakis(3-thiohydropropionic acid), dipentaerythritol hexa(3-sulfhydrylpropionic acid), tetraglycol glycol bis (3- Thiohydropropionic acid) and the like.

The amount of the (D) photopolymerization initiator to be used is 0.1 to 40 parts by mass based on 100 parts by mass of the total of (B) the alkali-soluble resin and (C) the photopolymerizable compound, based on the solid portion. . Among them, it is preferably 1 to 30 parts by mass. When the amount of the photopolymerization initiator (D) to be used is in the above range, since the sensitivity of the colored photosensitive resin composition can be improved, the exposure time can be shortened and the effect of improving the production efficiency can be obtained. In addition, it can maintain a high resolution. Therefore, the pixel portion formed by using the composition has better strength, and the smoothness of the surface of the pixel portion can be improved.

The photopolymerization initiator (D-1) is used in an amount of 0.1 to 50 based on 100 parts by mass of the total amount of the (B) alkali-soluble resin and (C) photopolymerizable compound, which is based on the solid portion. Parts by mass. Among them, it is preferably from 1 to 40 parts by mass. When the amount of the photopolymerization initiator (D-1) to be used is in the above range, the sensitivity of the colored photosensitive resin composition can be improved. Therefore, a color filter formed using the composition can achieve higher production efficiency.

(E) solvent

The solvent is not particularly limited in its kind as long as it can effectively disperse or dissolve other components in the colored photosensitive resin composition. In particular, it is recommended to use ethers, aromatic hydrocarbons, ketones, alcohols, esters, guanamines, and the like.

Specific examples of the (E) solvent are ethylene glycol monoalkyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and the like. Diethylene glycol dioxane such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether Glycol alkyl ether acetates such as glycol ethers, glycolic acid glycol, ethyl acetate, etc., propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether An alkyl glycol alkyl ether acetate such as acetate, methoxybutyl acetate or methoxypentyl acetate; or an aromatic hydrocarbon such as benzene, toluene, xylene or trimethylbenzene. Methyl ketone such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone or cyclohexanone, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, An alcohol such as glycerin, an ester such as 3-ethoxypropionic acid ethyl or 3-methoxypropionic acid methyl, or a cyclic ester such as γ-butyrolactone.

From the viewpoint of coatability and drying property, an organic solvent having a boiling point of 100 ° C to 200 ° C is recommended for the solvent (E). More preferably, alkyl glycol alkyl ether acetates, ketones, and esters such as 3-ethylethoxypropionate or 3-methylmethoxypropionate are used. Most preferred are propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethylethoxy propionate, 3-methylmethoxypropionate, and the like.

In this case, the (E) solvent may be used singly or in combination of two or more solvents.

In the colored photosensitive resin composition of the present invention, the content of the solvent (E) is the total amount of the colored photosensitive resin composition, and is added in an amount of 60 to 90% by mass, preferably 70% by mass. ~85 mass%. When the content of the (E) solvent is 60 to 90% by mass, a spin coating method, a slit and a spin coating method, and a slit coating method are also known (also referred to as a slit coating method). When a coating operation is performed by a method such as a die coating method, a roll coating method, a spray coating method, or an inkjet coating method, a relatively preferable coating effect can be obtained.

(F) Fluorine reactive additive

The (F) fluorine-based reactive additive is a compound which can be copolymerized with a reactive group or an acid which is generated from the (D) photopolymerization initiator by light irradiation, and the (F) fluorine-based reactive additive and (B) An alkaline soluble resin or (C) photopolymerizable compound performs a very excellent reaction operation, so after the image forming operation Since a high contact angle and a low surface energy can be maintained, it is possible to produce a color-sensitive photosensitive resin composition having high sensitivity and high engineering performance without spots.

The chemical formula 1 of the (F) fluorine-based reactive additive according to the present invention is as follows.

(In Chemical Formula 1, R ₁ is an independent vinyl group, an (iso)propenyl group, a butenyl group, a (poly)ethylene glycol group or a (poly)propylene glycol group, R ₂ is hydrogen or a methyl group, and Rf is a fluorine-based plural. The alcohol group is represented by the following chemical formula 2.)

(In Chemical Formula 2, R ₃ is a mutually symmetric structure of a methylene group or a (poly)ethylene glycol group; and in the case where R ₄ is a carbon atom, R ₅ is independently nitrogen, methyl, ethyl, and C. Base, butyl or CH ₂ -O-CH ₂ -CPF _2P+1 ; wherein, in the case where R ₄ is CF ₂ O-(CF ₂ CF ₂ O) _a -(CF ₂ O) _b , R _{5 is} not There is an integer in which a and b are each 0 or more, and a+b is an integer of 1 to 20; wherein P is an integer of 1 to 10, and n is an integer of 1 to 20.

The fluorine-based reactive additive of the chemical formula 1 can be obtained by reacting a fluorine-based polyol and (meth)acrylic acid isocyanate.

The fluorine-based polyol is bonded to at least one fluorine in its molecular structure, and the fluorine may be contained in a main chain or a secondary chain of the polyol. Further, the fluorine-based polyol contains 10 to 90% by weight of fluorine in its molecular structure, and preferably has a content of 40 to 70% by weight. If the fluorine content in the molecular structure is small When the weight is 10% by weight, it is difficult to increase the surface energy, and when it is more than 90% by weight, the phenomenon of the squirting phenomenon, the pinhole blocking phenomenon, and the reduction of the surface floating force are liable to occur on the surface.

The (meth)acrylic acid isocyanate is a product which can be directly used as a commercially available product or can be reacted using a (meth)acrylic monomer having a hydroxyl group and a diisocyanate. At this time, if the molar ratio of the diisocyanate is raised a little and the isocyanate is left to the end, (meth)acrylic acid isocyanate can be obtained. The (meth) propylene monomer containing the hydroxyl group may be 2-hydroxyethyl (meth) acrylate, 2-hydroxy propyl (meth) acrylate, or 4-hydroxy butyl Base (meth) acrylate, caprolactone denatured hydroxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate with diol oxide added, hydroxyl group with propylene oxide added (Meth) acrylate, etc. The diisocyanate can be directly used in the market, for example, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 2,4-toluene diisocyanate, 4 a diisocyanate such as 4-methylene diisocyanate. Further, a catalyst can also be used in the reaction. The catalyst can be a catalyst which can carry out urethane reaction, for example, a tertiary amine system, a tin system or the like.

The content of the (F) fluorine-based reactive additive is the content of the solid portion in the colored photosensitive resin composition of the present invention, and may be added in an amount of 0.001 to 14% by mass based on the mass fraction. Among them, it is more recommended to add 0.05 to 10% by mass. When the content of the (F) fluorine-based reactive additive is 0.001 to 14% by mass, a coloring photosensitive resin composition capable of preventing a problem such as development of spots or the like can be produced even under a low exposure amount of pixel formation conditions.

(G) additive

Additives such as a filler, another polymer compound, a curing agent, an surfactant, an adhesion promoter, an oxidation inhibitor, an ultraviolet absorber, and a coagulation inhibitor may be added to the colored photosensitive resin composition of the present invention as required. . The above additives can be added separately or two The above ingredients are added at the same time. The amount of the additive to be added is not particularly limited insofar as it does not affect the physical properties of the colored photosensitive resin composition of the present invention and can achieve the purpose of the additive, and is not particularly limited. More preferably, the content of the solid portion in the colored photosensitive resin composition is 0.01 to 10% by mass, and the optimum amount is 0.05 to 5% by mass based on the mass fraction.

Specific examples of the use of the filler are: glass, cerium oxide, aluminum oxide, and the like.

Specific examples of the other polymer compound are a curable resin such as an epoxy resin or a maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, or polyfluorinated alkyl acrylate. A thermoplastic resin such as polyester or polyurethane.

The curing agent is mainly used for improving deep curing and mechanical strength. Specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and a propylene oxide compound. Specific examples of the epoxy compound include a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol fluorine epoxy resin, a hydrogenated bisphenol fluorine epoxy resin, and a novolak epoxy resin. Other aromatic epoxy resin, alicyclic epoxy resin, glycidyl ester resin, or epoxypropylamine resin, or a brominated derivative of these epoxy resins, an epoxy resin, and the bromination Aliphatic, alicyclic or aromatic epoxy compounds other than the derived body, butadiene (co)polymer epoxide, isoprene (co)polymer epoxide, epoxypropyl (methyl) Acrylate (co)polymer, triepoxypropyl isocyanate monomer. Specific examples of the propylene oxide compound are: carbonate dipropylene oxide, xylene dipropylene oxide, adipic acid dipropylene oxide, terephthalate dipropylene oxide, cyclohexane dicarboxylic acid double ring Oxypropane and the like.

The hardener is used together with a hardening auxiliary compound which copolymerizes the hardener and the epoxy group of the epoxy compound and the propylene oxide compound. Specific examples of the curing auxiliary compound are polyvalent carboxylic acids, polyvalent carboxylic anhydrides, acid generators, and the like. Among them, the carboxylic acid anhydride can be a commercially available epoxy resin hardener. Specific examples of the epoxy resin hardener are: Product name (ADEKAHADONA EH-700) (made by Asahi Kasei Co., Ltd.), trade name (LIKASITDO HH) (manufactured by Nippon Chemical and Chemical Co., Ltd.), trade name (MH-700) (manufactured by Nippon Chemical and Chemical Co., Ltd.) Wait. The above-mentioned hardeners may be used singly or in combination of two or more kinds of components.

The surfactant is a film forming property capable of improving the composition of the photosensitive resin, and a fluorine-based surfactant, a siloxane-based surfactant, and a siloxane-based surfactant containing a fluorine-based atom are usually used.

The commercial products of the siloxane surfactant are DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc. of DOWCONING DOREY SILICONE, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF of GE TOSIBA SILICONE. -4460, TSF-4452, etc., and the commercial products of the fluorine-based surfactant are MEGAPIS F-470, F-471, F-475, F-482, F-489, etc. of Nippon Ink Chemicals. The commercial product of the fluorine atom-containing oxoxane surfactant is a siloxane coupling and a fluorinated chain surfactant. Specifically, MEGAPACR08, MEGAPACBL20, MEGAPACF275, MEGAPACF475, MEGAPACF477, MEGAPACF443, etc. of INK Chemicals Co., Ltd. of Japan.

The above surfactants may be used singly or in combination of two or more kinds.

Specific examples of the adhesion promoter are ethylene trimethoxy decane, ethylene triethoxy decane, vinyl fluorene (2-methoxyethoxy) decane, and N-(2-aminoethyl)-3-aminopropyl group. Dimethoxyoxane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycineoxypropyltrimethoxydecane, 3Glycidyloxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloro Propyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3-hydrothiopropyltrimethoxydecane, 3-isocyanatepropyltrimethoxydecane, 3-isocyanatepropyltriethoxy Decane and so on. Adhesion above The enhancer may be used singly or in combination of two or more components.

Specific examples of the oxidation preventing agent are: 2,2'-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like.

Specific examples of the ultraviolet absorber are 2-(3-n-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone and the like.

Specific examples of the coagulation preventing agent are sodium polyacrylate and the like.

The colored photosensitive resin composition of the present invention can be produced by the following method. However, the method for producing the colored photosensitive resin composition of the present invention is not limited to the following examples.

(A) First, a mixing operation of the colorant and the solvent is carried out (A) The coloring agent is dispersed by a grinder until the average particle diameter of the coloring agent is less than 0.2 μm. At this time, a pigment dispersant may be used as needed, or a small amount or a large amount of (B) an alkali soluble resin may be added. The remaining (B) basic soluble resin, (C) photopolymerizable compound, (D) photopolymerization initiator and (F) are added to the dispersion obtained by this process (hereinafter referred to as "mill base"). In the case of a component such as a fluorine-based reactive additive, in order to adjust the concentration of the solvent, other components may be added. In this way, the colored photosensitive resin composition of the present invention can be obtained.

The colored photosensitive resin composition of the present invention can be used for color filter production, and the color filter of the present invention and the method for producing the color filter will be described below.

The color filter of the present invention comprises a substrate and a colored layer formed on the substrate using the colored photosensitive resin composition of the present invention.

The color filter can be directly used as a substrate, and can be applied to various display devices. There are no particular restrictions on its use.

The substrate is a glass plate, a germanium wafer, and a polyethersulfone (PES). A plastic substrate such as polycarbonate (PC) or the like. That is, the substrate is a substrate made of yttrium (Si), a siloxane oxide (SiOx), a glass plate, or a polymer substrate made of a plastic material.

The colored layer is a layer formed of the colored photosensitive resin composition of the present invention, wherein the colored photosensitive resin composition contains (A) a colorant, (B) an alkali soluble resin, and (C) photopolymerizable property. A component such as a compound, (D) a photopolymerization initiator, (E) a solvent, and (F) a fluorine-based reactive additive. After the colored photosensitive resin composition is applied onto the substrate, exposure and development work are performed in a predetermined pattern to form the colored layer.

In addition to the substrate and the coloring layer, the color filter formed by the method described above may further form a separator and a black matrix between the respective coloring patterns. Further, a protective film may be formed on the upper portion of the color filter layer of the color filter.

Hereinafter, the manufacturing process of the color filter will be described in more detail with reference to the attached drawings.

Fig. 1a and Fig. 1c show a comparatively preferred embodiment of the process for producing a color filter using the colored photosensitive resin composition of the present invention.

In the present invention, first, after the colored photosensitive resin composition of the present invention is applied onto a substrate, as shown in FIG. 1a, a colored layer composed of a colored photosensitive resin composition is formed on the substrate (10). ). In order to carry out this process, a spin coating method, a slit and spin coating method, a slit coating method, a roll coating method, and a spray coating method are used ( In a method such as a spray coating method or an inkjet coating method, a colored photosensitive resin composition diluted with a solvent is applied to the upper portion of the substrate, and then volatile components such as a solvent are volatilized. By this method, the coloring layer (11) composed of the colored photosensitive resin composition can be formed, and in this case, the colored layer is formed by combining the solid components of the colored photosensitive resin composition, and it is not completely contained therein. Contains volatile substances. In addition, the colored layer The thickness depends on the coating conditions of the viscosity of the colored photosensitive resin composition, the concentration of the solid portion, the coating speed, and the like. When the colored photosensitive resin composition of the present invention is used, a coloring layer (11) having a thickness of 0.5 to 5 μm can be formed.

Next, as shown in Fig. 1b, the formed coloring layer (11) is exposed. At this time, the exposure method is a method of irradiating the predetermined pattern of light (30) onto the colored layer (11) through the reticle (20). The light (30) generally used in the exposure process is a g-line (wavelength: 436 nm) of ultraviolet rays, an h-line, an i-line (wavelength: 365 nm), or the like. The reticle (20) may include a light shielding layer and a light transmissive layer, wherein the light shielding layer covers the light (30) irradiated on the glass plate in a predetermined pattern, and the light transmissive layer is fixed on the glass plate. The pattern illuminates the light (30). Thereby, the corresponding colored layer (11) is exposed in accordance with the pattern of the light transmitting portion. The amount of irradiation of the light (30) is appropriately selected in accordance with the colored photosensitive resin composition to be used. Since the light-curing phenomenon of the rapidly colored photosensitive resin composition occurs at the place where the light (30) is irradiated, it exhibits a very low solubility compared to the portion where the light (30) is not irradiated. As a result, the difference in solubility between the two methyl groups is maximized.

After the exposure work is completed, next, a development operation is performed to form a color pattern (11R) as shown in Fig. 1c. For example, in order to perform a developing operation, the colored photosensitive resin composition layer after the completion of the exposure operation is immersed in the developing liquid. In this case, the developing solution may be an aqueous solution using a basic compound such as sodium carbonate, sodium hydroxide, potassium hydroxide, potassium carbonate or tetramethylammonium hydroxide. When a developing operation is performed, in the layer formed by coloring the photosensitive resin composition, a colored pattern does not appear in the unexposed portion, and conversely, a colored pattern (11R) appears on the exposed portion.

After the development work is completed, the layer after the development work is finished with water, and the predetermined color pattern is obtained through the drying operation. In addition, after the drying operation, heating work can also be performed. At this time, the colored pattern (11R) formed by the heat treatment generates a thermosetting reaction, and thus Improve mechanical strength. As a result, the mechanical strength of the colored pattern (11R) can be improved by heat treatment, so it is recommended to use a colored photosensitive composition containing a hardener. At this time, the heating temperature is usually 180 ° C or more, and it is recommended to use a temperature between 200 and 250 ° C.

The liquid crystal display device of the present invention comprises a color filter, and the color filter comprises a substrate and a coloring layer.

As described above, the color filter includes a substrate and a colored layer formed on an upper portion of the substrate. In the method of forming the colored layer, the colored photosensitive resin composition is applied to the upper portion of the substrate, and then exposed and developed in a predetermined pattern. In this case, the colored photosensitive resin composition contains (A) a colorant, (B) an alkali soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a solvent, and (F) Fluorine-based reactive additives and the like.

Other technical features of the liquid crystal display device of the present invention are the same as those of the general technical field in the related art of the present invention, in addition to the features of the color filter.

The above description is intended to be illustrative, and not restrictive, and many modifications, variations, and equivalents may be made without departing from the spirit and scope of the invention. All of them will fall within the scope of the scope of the patent application of the present invention.

Unless otherwise specified, the content symbols "percent" and "parts" used in the following examples and comparative examples are based on the mass, and the amount used is an overall coloring photosensitive resin composition. Quasi-rate ratio.

Synthesis Example 1 <Synthesis of Fluorine Reactive Additive>

The fluorine-based polyol PolyFox ^TM PF-656 (OMNOVA Inc.) 83.8 parts by mass, acrylic isocyanate AOI (Showa Denko Co.) 15 parts by mass of the catalyst is dibutyltin laurate 0.8 parts by mass of the stabilizer is methoxy benzene 0.4 parts by mass of diphenol and 100 parts by mass of propylene glycol monomethyl ether acetate are placed in a 3-port 500 mL reactor, and equipped with a condenser, a mechanical stirrer, a thermometer, a heating plate, and the like. The stirring operation is performed on the reaction device. Before the initial 60 ° C, slowly after the self-heating reaction, when the temperature gradually decreased, maintain the temperature of 70 ° C, and then react for 5 hours. Next, after the measurement of FT-IR, the reaction operation was stopped when the peak of the characteristic of the isocyanate 2260 cm ^-1 completely disappeared. The overall reaction chemical formula is shown in Reaction Scheme 1.

Synthesis Example 2 <Synthesis of Fluorine Reactive Additive>

83.8 parts by mass of fluorine-based polyol Fluorolink E10-H (SOLBAY), 15 parts by mass of acrylic acid isocyanate AOI (Showa Denko), and the catalyst was 0.8 parts by mass of dibutyl laurate, and the stabilizer was methoxy-p-phenylene. 0.4 parts by mass of phenol and 100 parts by mass of propylene glycol monomethyl ether acetate are placed in a three-port 500 mL reactor, and equipped with a condenser, a mechanical stirrer, a thermometer, a heating plate, and the like. The stirring operation was performed on the reaction apparatus. Before the initial 60 ° C, slowly after the self-heating reaction, when the temperature gradually decreased, maintain the temperature of 70 ° C, and then react for 5 hours. Next, after the measurement of FT-IR, the reaction operation was stopped when the peak of the characteristic of the isocyanate 2260 cm ^-1 completely disappeared. The overall reaction chemical formula is shown in Reaction Scheme 2.

<Reaction formula 2>

Synthesis Example 3 <Synthesis of Fluorine Reactive Additive>

10.6 parts by mass of 2-hydroxyethyl acrylate, 20.6 parts by mass of isophorone diisocyanate, 0.1 parts by mass of dibutyl laurate, 0.1 parts by mass of methoxyhydroquinone, and the like. After a 500 mL reactor, the stirring operation was carried out on a reaction apparatus equipped with a condenser, a mechanical stirrer, a thermometer, a heating plate, and the like. After self-heating at normal temperature, the temperature was raised to about 80 ° C, and then, after cooling operation, the temperature was maintained at 70 ° C, and the reaction was further carried out for 3 hours. At this time, the NCO% transmitted through the wet analysis was 12.4%.

After cooling the temperature of the reactor to room temperature, 68.9 parts by mass of a fluorine-based polyol Fluorolink E10-H (SOLBAY Co., Ltd.), 0.1 part by mass of dibutyl laurate, and a stabilizer of methoxymethoxy hydroquinone After 0.1 parts by mass of the diluent and a component such as 100 parts by mass of propylene glycol monomethyl ether acetate were placed, the temperature was maintained at 70 ° C and the reaction was further carried out for 5 hours. Next, after the measurement of FT-IR, the reaction operation was stopped when the peak of the characteristic of the isocyanate 2260 cm ^-1 completely disappeared. The overall reaction chemical formula is shown in Reaction Scheme 3.

Example 1 <Production of Colored Photosensitive Resin Composition>

The coloring agent (A) is 5.25 parts of CI pigment (Pigment) red 254, and (B) the basic soluble resin is a copolymer of (meth)acrylic acid and benzyl group of methacrylic acid and benzyl methacrylate. The molar ratio of the methacrylate unit is 27:73, the acid value is 83, the weight average molecular weight is 18,000), 2.938 parts, and the photopolymerizable compound is 2.938 parts of dipentaerythritol hexaacrylate. (D) Photopolymerization initiation The agent is 0.353 parts of 2-methyl-2-morpholin-1-(4-methylthiophenyl)propan-1-one, and the photopolymerization initiator is 4,4'-bis(diethylamino)benzene. 0.176 parts of ketone, (F) a fluorine-based reactive additive is 0.012 parts of the fluorine-based reactive additive synthesized in Synthesis Example 1, and (E) a solvent is 85 parts of propylene glycol monomethyl ether acetate, (G) The additive is 2.625 parts of pigment dispersant Disperbyk-2001 (BYK company), the thermal bridging agent is 0.588 parts of epoxy resin (SUMI-EPOXY ESCN-195XL), and the adhesion promoter is 0.12 parts of allyl trimethoxy decane methacrylic acid. After the components are mixed and dispersed, the colored photosensitive resin composition of the present invention is produced.

Example 2 <Production of Colored Photosensitive Resin Composition>

The (F) fluorine-based reactive additive in Example 1 was replaced by 0.012 parts of the fluorine-based reactive additive synthesized in <Synthesis Example 2>, and the other contents were the same as in Example 1.

Example 3 <Production of Colored Photosensitive Resin Composition>

The content of the (F) fluorine-based reactive additive in Example 1 was replaced by 0.012 parts of the fluorine-based reactive additive synthesized in <Synthesis Example 3>, and the other contents were the same as in Example 1.

Comparative Example 1 <Production of Colored Photosensitive Resin Composition>

The upper Example 1 (F.) Fluorine-substituted non-reactive additives one reactive fluorine-based additive PolyFox ^TM PF-656 (OMNOVA Inc.) 0.012 parts, in addition, other content same as Example 1.

Comparative Example 2 <Production of Colored Photosensitive Resin Composition>

The (F) fluorine-based reactive additive in the first embodiment is substituted with one of the non-reactive fluorine-based additives. The same applies to Example 1 except that Fluorolink E10-H (SOLBAY Co., Ltd.) was 0.012 parts.

Comparative Example 3 <Production of Colored Photosensitive Resin Composition>

The other contents were the same as in Example 1 except that the (F) fluorine-based reactive additive of Example 1 was not added.

<Formation of Colored Layer and Evaluation of Development Spots>

The colored photosensitive resin compositions produced in Examples 1 to 3 and Comparative Examples 1 to 3 were applied onto the upper portion of the glass substrate by a spin coating method, and then placed on a hot plate at 100 ° C for 3 minutes to form. Colored layer film. Next, a photomask is placed on the colored layer film. At this time, the mask is a pattern having a stepwise change in transmittance in the range of 1 to 100%. Next, the test reticle was irradiated with ultraviolet rays at intervals of 100 μm. At this time, the ultraviolet light source was a 1 kW high pressure mercury lamp including g, h, and i lines, and the irradiation amount thereof was an exposure amount of 100 mJ/cm ² . In addition, no special optical filters were used during this process. Next, the coloring layer film which had been irradiated with ultraviolet rays was placed in a KOH aqueous solution developing solution having a pH of 10.5 and immersed for 2 minutes, and then developed.

Next, after the glass substrate on which the colored layer film had been formed was rinsed with distilled water, the drying operation was carried out under nitrogen. Finally, the development spots were confirmed in such a manner that the contact angle was measured for ultrapure dialysis water. The measurement results are shown in Table 1.

At this time, the measurement and measurement operation of the development spot was performed under the conditions of exposure amounts of 100, 60, and 40 mJ/cm ² . And the evaluation criteria are as follows.

- For ultrapure dialysis water contact angle greater than 60°, and when visually confirmed, when no spots on the substrate are seen: ○

- for ultrapure dialysis water contact angle less than 50 ° and greater than 40 °, and confirmed by the naked eye, on the substrate When a tiny imaging spot appears: △

- For ultrapure dialysis water contact angle less than 40°, and when visually confirmed, when serious imaging spots appear on the substrate: ×

As shown in Table 1, the color filter produced by the colored photosensitive resin compositions of Examples 1 to 3 containing the (F) fluorine-based reactive additive contained therein was low in exposure amount of 40 mJ/cm ² . The development work is carried out under the development conditions, and no development spots are produced.

On the other hand, the color filter produced by the color-sensitive photosensitive resin compositions of Comparative Examples 1 to 3 does not cause development spots under the development conditions in which the exposure amount is high, but the exposure amount is lowered. The more imaging spots appear.

Therefore, when the coloring photosensitive resin composition containing the (F) fluorine-based reactive additive of the present invention is used for development, it is possible to solve the problem of surface defects such as development spots or water stains, and also improve engineering. Productivity and harvest rate. In addition to this, a high-quality color filter pattern in which no development spots and defects on the pattern occur can be formed.

Above, more specific contents will be described through the embodiments of the present invention. The above is intended to be illustrative only and not limiting. Any equivalent modifications or alterations to the spirit and scope of the invention are intended to be included in the scope of the appended claims.

10‧‧‧Substrate

11‧‧‧Colored layer

Claims (7)

A colored photosensitive resin composition comprising (A) a colorant, (B) an alkali soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a solvent, and a chemical formula 1 (F) fluorine-based reactive additive, In Chemical Formula 1, R ₁ is an independent vinyl group, an (iso)propenyl group, a butenyl group, a (poly)ethylene glycol group or a (poly)propylene glycol group; R ₂ is hydrogen or a methyl group; and Rf is a fluorine-based polyol. Base, expressed by the following chemical formula 2: In Chemical Formula 2, R ₃ is a mutually symmetric structure of a methylene group or a (poly)ethylene glycol group; and in the case where R ₄ is a carbon atom, R ₅ groups are each independently selected from hydrogen, methyl, ethyl, Propyl, butyl or CH ₂ -O-CH ₂ -CPF _2P+1 ; in the case where R ₄ is CF ₂ O-(CF ₂ CF ₂ O) _a -(CF ₂ O) _b , R ₅ does not exist Wherein a and b are each an integer of 0 or more, and a+b is an integer of 1 to 20, wherein P is an integer of 1 to 10, and n is an integer of 1 to 20. The colored photosensitive resin composition according to claim 1, wherein the (F) fluorine-based reactive additive is a compound obtained by reacting (meth)acrylic acid isocyanate with the fluorine-based polyol. The colored photosensitive resin composition according to claim 2, wherein the (meth)isocyanate is produced by phosgenating (meth)acrylamide or may contain The (meth) acrylate of the hydroxyl functional group is reacted with an excess of diisocyanate. The colored photosensitive resin composition according to claim 2, wherein the fluorine-based polyol has a fluorine content in the molecule of 10 to 90% by weight and contains at least one ether. The colored photosensitive resin composition according to claim 1, wherein the content of the (F) fluorine-based reactive additive is a mass fraction of the solid portion in the colored photosensitive resin composition. Quasi, add 0.001 to 14% by mass. A color filter comprising a colored photosensitive resin composition coated on an upper portion of a substrate according to any one of claims 1 to 5, and exposing and developing the image in a predetermined pattern Forming the color layer. A liquid crystal display device having the color filter as described in claim 6 of the patent application.