KR20100088529A - Negative photosensitive resin composition and color filter, black matrix and spacer using the same, and liquid crystal display device and solid state imaging device - Google Patents

Abstract

PURPOSE: A negative photosensitive resin composition, a color filter using the same, a black matrix, a spacer, a liquid crystal display, and a solid imaging device are provided to obtain excellent resolution, sensitivity, and adhesive force with a substrate and to have high performance. CONSTITUTION: A negative photosensitive resin includes dipentaerythritol acrylates which is marked by chemical formula 1 and has a hydroxyl number of 70mgKOH/g-130mgKOH/g. In chemical formula 1, a and b are positive integers and satisfy conditions including a+b=6 and 1<=a<=6, 0<=b<=5. The negative photosensitive resin composition includes a binder polymer, a pigment, and a photopolymerization initiator additionally. A color filter, a black matrix, and a spacer are obtained by hardening the negative photosensitive resin composition.

Description

NEGATIVE PHOTOSENSITIVE RESIN COMPOSITION AND COLOR FILTER, BLACK MATRIX AND SPACER USING THE SAME, AND LIQUID CRYSTAL DISPLAY DEVICE AND SOLID STATE IMAGING DEVICE}

The present invention relates to a negative photosensitive resin composition, and more particularly, to a photosensitive resin composition used in the production of color filters, black matrices or spacers used in color liquid crystal displays, color video cameras, color digital cameras, electronic papers, and the like. The present invention relates to a color filter, a black matrix, and a spacer having a pattern formed thereon.

Color filters, black matrices and spacers are required for liquid crystal display devices such as liquid crystal displays (LCDs) such as laptops and liquid crystal televisions. The color filter is required for the colorization of the solid-state image sensor which represents the charge coupling element (CCD, CMOS) used as an input device, such as a digital camera and a color copier.

The photosensitive resin composition used for these liquid crystal display devices and a solid-state image sensor is refine | miniaturized and thinned with light and small size reduction of the apparatus itself. For this reason, omitting reduction of the resin component in a composition, and omission of an organic base film are examined.

In order to adapt to the flow of this miniaturization and thinning, several studies have been made. For example, Patent Literature 1 describes a method of reinforcing the decrease in adhesion to the glass of the black matrix accompanying the thinning. Moreover, in patent document 2, favorable resolution and thinning are achieved by studying binder resin of a color filter. However, neither method solves all the adhesiveness, resolution, and developability to a board | substrate.

Japanese Laid-Open Patent Publication 2004-0046551 Japanese Patent No. 3218256

An object of the present invention is to obtain a negative photosensitive resin composition having excellent adhesiveness, resolution, developability, and sensitivity to a substrate in applications such as color filters, black matrices, and spacers.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, the present inventors used the acrylate of the dipentaerythritol represented by following formula (1) to a board | substrate by using the hydroxyl value: It was found out that a resin composition excellent in all of adhesiveness, resolution, developability, and sensitivity was obtained, and thus, the present invention was completed.

(In Formula 1, a and b are positive integers, where a + b = 6, 1 ≦ a ≦ 6, and 0 ≦ b ≦ 5.)

That is, the present invention,

(1) A negative photosensitive resin composition comprising an acrylate of dipentaerythritol represented by the following formula (1), wherein the hydroxyl value is 70 mgKOH / g or more and 130 mgKOH / g or less;

<Formula 1>

(In Formula 1, a and b are positive integers, where a + b = 6, 1 ≦ a ≦ 6, and 0 ≦ b ≦ 5.)

(2) The negative photosensitive resin composition as described in (1) which further contains a binder polymer, a pigment, and a photoinitiator,

(3) a color filter, a black matrix, or a spacer obtained by curing the negative photosensitive resin composition according to (1) or (2);

(4) a liquid crystal display device comprising the color filter, the black matrix, or the spacer according to (3),

(5) It relates to the solid-state image sensor provided with the color filter, black matrix, or spacer as described in (3).

By using acrylates of dipentaerythritol having a hydroxyl value of 70 mgKOH / g or more and 130 mgKOH / g or less, the balance of adhesion, resolution, developability, and sensitivity to the substrate is excellent, and conventional acrylate monomers alone and in combination are obtained. A negative photosensitive resin composition for color filters, black matrices, and spacers with unparalleled high performance can be obtained.

(Form to carry out invention)

The negative photosensitive resin composition of the present invention contains not only a specific photopolymerizable monomer, but also a binder polymer, a photopolymerizable monomer other than the specific photopolymerizable monomer, a pigment, a photopolymerization initiator and an organic solvent, a surfactant, a thermosetting agent, a polymerization inhibitor, and the like. It is a negative photosensitive resin composition containing various additives as needed.

Although there is no special limitation in the photopolymerizable monomer used in this invention, At least as a acrylate of the dipentaerythritol represented by following formula (1), a hydroxyl value of 70 mgKOH / g or more and 130 mgKOH / g or less is used. In the composition of this invention, another photopolymerizable monomer can also be mixed and used.

<Formula 1>

(In Formula 1, a and b are positive integers, where a + b = 6, 1 ≦ a ≦ 6, and 0 ≦ b ≦ 5.)

When the hydroxyl value of the said photopolymerizable monomer is less than 70 mgKOH / g, compared with the conventional pentaerythritol hexaacrylate, a big difference cannot be acquired about adhesiveness, resolution, developability, and a sensitivity with respect to a board | substrate. Moreover, when it is larger than 130 mgKOH / g, roughness will appear on the pattern surface at the image development process, and it is not suitable as a photopolymerizable monomer for photosensitive resin compositions for color filters, a black matrix, and a spacer.

An acrylate of dipentaerythritol having a hydroxyl value of 70 mg KOH / g or more and 130 mg KOH / g or less is obtained by acrylateating dipentaerythritol by a method generally used. In order to obtain a desired hydroxyl value, the amount of acrylic acid added to dipentaerythritol may be appropriate. Specifically, about 0.9 to 1.2 equivalents is preferable with respect to the number of moles of hydroxyl groups of dipentaerythritol.

Specific examples of other photopolymerizable monomers that can be used in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and ethylene glycol di (Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, an acrylate of dipentaerythritol having a hydroxyl value of less than 70 mgKOH / g, glycerol (meth) acrylate, bisphenol-A epoxy di ( Meta) acrylate, bisphenol-F type epoxy di (meth) acrylate, bisphenol-fluorene type epoxy di (meth) acrylate, etc. The can.

These may be used independently and may be used in combination of 2 or more type. A photopolymerizable monomer is used in the ratio which occupies 5-60 mass% normally, Preferably it is 10-50 mass% in the total solid of the composition of this invention.

The binder polymer which can be used as a component of a negative photosensitive resin composition will not be specifically limited if it raises the film-forming property of a composition. Preferably, it can be melt | dissolved in the developing solution used in the image development process process at the time of color filter manufacture. As a binder polymer which can be melt | dissolved in a developing solution, alkali-soluble resin or water-soluble resin is mentioned, for example.

As alkali-soluble resin, if it is resin which can melt | dissolve in alkaline solution or alkaline aqueous solution, it can use without a restriction | limiting in particular. As such alkali-soluble resin, the polymer which has a carboxyl group is mentioned, for example. As the polymer having a carboxyl group, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter simply referred to as an "unsaturated monomer having a carboxyl group") and another copolymerizable ethylenically unsaturated monomer (hereinafter simply referred to as "another unsaturated monomer") Preferred is a copolymer (hereinafter, simply referred to as "copolymer having a carboxyl group") of a monomer mixture. Specific examples of the unsaturated monomer having a carboxyl group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid and cinnamic acid; Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or acid anhydrides thereof; And trivalent or higher unsaturated polyvalent carboxylic acids or anhydrides thereof. The unsaturated monomer which has these carboxyl groups can be used individually or in mixture of 2 or more types.

Moreover, as a specific example of the said other unsaturated monomer, styrene, (alpha) -methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, o-chloro styrene, m-chloro styrene, p-chloro styrene, p-meth Aromatic vinyl compounds such as oxystyrene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, i-propyl acrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl acrylate, i-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, n-butyl methacrylate, i-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-hydroxy Unsaturated carboxylic acid esters such as ethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate and benzyl methacrylate; Unsaturated carboxylic acid amino such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 3-aminopropyl acrylate, and 3-aminopropyl methacrylate Alkyl esters; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carbonic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, and metalryl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; Unsaturated amides or unsaturated imides such as acrylamide, methacrylamide, α-chloroacrylamide, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide and maleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Having a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecular chain, such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly n-butyl acrylate, poly n-butyl methacrylate, polysilicon, etc. Macromonomers; and the like. These other unsaturated monomers can be used individually or in mixture of 2 or more types.

As a preferable combination of the unsaturated monomer which has these carboxyl groups, and another unsaturated monomer, acrylic acid and / or methacrylic acid, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate And at least one other unsaturated monomer selected from the group consisting of acrylates, styrenes, polystyrene macromonomers, and polymethylmethacrylate macromonomers. Preferable specific examples of the polymer having a carboxyl group include acrylic acid / benzyl acrylate copolymer, acrylic acid / benzyl acrylate / styrene copolymer, acrylic acid / methyl acrylate / styrene copolymer, acrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, acrylic acid / Benzyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / methyl acrylate / polystyrene macromonomer copolymer, acrylic acid / methyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / benzyl methacrylate copolymer Copolymer, acrylic acid / benzyl methacrylate / styrene copolymer, acrylic acid / methyl methacrylate / styrene copolymer, acrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / benzyl methacrylate / polymethyl methacrylate macro Monomer Polymer, acrylic acid / methyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macro Acrylic acid copolymers such as monomer copolymers and acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymers; Methacrylic acid / benzyl acrylate copolymer, methacrylic acid / benzyl acrylate / styrene copolymer, methacrylic acid / methyl acrylate / styrene copolymer, methacrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, methacrylic Acid / benzylacrylate / polymethylmethacrylate macromonomer copolymer, methacrylic acid / methylacrylate / polystyrene macromonomer copolymer, methacrylic acid / methylacrylate / polymethylmethacrylate macromonomer copolymer, methacryl Acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / methyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, Methacrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / methacrylate Methacrylate / polystyrene macromonomer copolymer, methacrylic acid / methylmethacrylate / polymethylmethacrylate macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer Methacrylic acid copolymers, such as a copolymer and methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethylmethacrylate macromonomer copolymer, etc. are mentioned.

Moreover, the polymer which introduce | transduced the unsaturated double bond further in the side chain of the said polymer which has the said carboxyl group is also useful for this invention. Examples of such polymers include alcoholic hydroxyl groups such as hydroxyethyl acrylate in the maleic anhydride portion of copolymers of maleic anhydride and styrene, vinylphenol, acrylic acid, acrylic ester, acrylamide and the like copolymerizable therewith. With a compound obtained by reacting an acrylate having an epoxy group such as acrylate or glycidyl methacrylate with a semi-esterified compound and an acrylate having an alcoholic hydroxyl group such as acrylic acid, acrylic acid ester and hydroxyethyl acrylate. The compound which made acrylic acid react further to the hydroxyl group of a copolymer is mentioned.

Next, as water-soluble resin, acrylic resin, methacryl resin, polyvinyl alcohol resin, polyvinylpyrrolidone resin, acryloyl morpholine resin etc. are mentioned. Examples of acrylic resins include polymers and copolymers such as acrylic acid, soda acrylic acid, acrylamide, and the like. Examples of methacrylic resins include polymers or copolymers such as methacrylic acid, methacrylic acid sodium and 2-hydroxymethacrylic acid. Each can be mentioned.

As an alkaline solution or alkaline aqueous solution which can dissolve the above-mentioned alkali-soluble resin or water-soluble resin, For example, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution, sodium hydrogen carbonate aqueous solution, potassium hydrogen carbonate aqueous solution, tetra Although the methyl ammonium hydroxide aqueous solution, the diethanolamine aqueous solution, the ethanolamine aqueous solution, etc. and these mixed suitably with surfactant are mentioned, It is not limited to these in this invention.

In this invention, the said binder polymer can be used individually or in mixture of 2 or more types. When the binder polymer in this invention is used in the total solid (other components except organic solvent, the same below) of the negative photosensitive resin composition of this invention, it is 5-80 mass% normally, Preferably it is 10- It uses in the ratio which occupies 60 mass%. When content of a binder polymer is less than 5 mass%, alkali developability may fall, for example, scuffing and film | membrane residue may generate | occur | produce in the area | regions other than the part in which a pixel is formed.

As a weight average molecular weight (Mw) of a binder polymer, it is 2,000-1,000,000 normally, Preferably it is 3,000-400,000. In the case where the weight average molecular weight is 2,000 or less, and the weight average molecular weight is 400,000 or more, there is a fear that the sensitivity and developability deteriorate.

A pigment etc. can be used for the negative photosensitive resin composition of this invention as needed. Moreover, as a pigment used for this invention, if it has a suitable spectral spectrum, an organic pigment and an inorganic pigment can be used without a restriction | limiting in particular.

As an example of the organic pigment which can be used for this invention, an anthraquinone type, a phthalocyanine type, a benzoimidazolone type, a quinacridone type, an azochelate type, an azo type, an isoindolin type, an isoindolinone type, pyran, for example Pigments and acid dyes, basic dyes, such as srone-based, indanthone-based, anthrapyrimidine-based, dibromo-anxanthone-based, flavane-based, perylene-based, perinone-based, quinophthalone-based, thioindigo-based, and dioxazine-based Lake pigment, dye Lake pigment, etc. which insolubilized direct dye etc. with each precipitant are mentioned. These organic pigments can be used individually or in combination of 2 or more types as needed.

Examples of the inorganic pigments that can be used in the present invention include composite metal oxide pigments, carbon black, black lower titanium oxynitride, titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, Bengala, ultramarine blue. Metal oxides, such as wires, chromium oxide, antimony white, iron black, podium, zinc sulfide, cadmium yellow, cadmium red, zinc, manganese violet, cobalt violet, barium sulfate, magnesium carbonate, metal sulfides, sulfates, metal hydroxides, metal carbonates Etc. can be mentioned. These inorganic pigments can be used individually or in combination of 2 or more types as needed.

When using a pigment in this invention, when used in the total solid of the negative photosensitive resin composition of this invention, when used, it is normally used in the ratio which occupies 5-70 mass%, Preferably it is 10-60 mass%. Content of a pigment is suitably determined according to the desired film thickness of a cured film, and a spectral characteristic. Moreover, as a color of the pigment | dye used by this invention, colors, such as red, blue, green, black, yellow, magenta, cyan, are mentioned.

In the composition of this invention, a photoinitiator can be used as needed. As a photoinitiator used for this invention, if it has sufficient sensitivity to the ultraviolet-ray radiated | emitted from the ultrahigh pressure mercury lamp etc. generally used as an exposure light source, it can be used without a restriction | limiting. Specific examples of the photopolymerization initiator include benzyl, benzoin ether, benzoin butyl ether, benzoin propyl ether, benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, benzoylbenzoic acid, and esters of benzoylbenzoic acid, 4- Benzoyl-4'-methyldiphenyl sulfide, benzyl dimethyl ketal, 2-butoxyethyl- 4-methylamino benzoate, chloro thioxanthone, methyl thioxanthone, ethyl thioxanthone, isopropyl thioxanthone, dimethyl thi Oxanthone, diethyl thioxanthone, diisopropyl thioxanthone, dimethylaminomethylbenzoate, dimethylaminobenzoic acid isoamyl ester, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1 -One, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl- 1-phenyl propane- 1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-one, methylbenzoylformate, 2-methyl-1- (4-methylthiopee ) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, 2.2'-bis (2-chlorophenyl)- 4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra- (4-methoxyphenyl) bisimime Dazole, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-s-triazine, 2,4,6-tris (trichloromethyl) -1,3 , 5-s-triazine, 2,4-bis (tribromomethyl) -6- (4'-methoxyphenyl) -1,3,5-s-triazine, 2,4,6-tris Tribromomethyl) -1,3,5-s-triazine, 2,4-bis (trichloromethyl) -6- (1,3-benzodioxolane-5-yl) -1,3,5- s-triazine, 1- (4-phenylsulfanylphenyl) butane-1,2-dione- 2-oxime-O-benzoate, 1- (4-methylsulfanylphenyl) butane- 1,2-dione 2-oxime-O-acetate, 1- (4-methylsulfanylphenyl) butane-1-one oxime-O-acetate, Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyl oxime), etc. are mentioned.

These photoinitiators can be used individually or in combination of 2 or more types. In this invention, a photoinitiator is used in the total solid of the composition of this invention, and when used, it is 0.5-30 mass% normally, It is used in the ratio which occupies 1-25 mass%.

In the composition of this invention, an organic solvent can be used as needed. As an organic solvent used for this invention, what melt | dissolves the binder polymer which is a structural component of the negative photosensitive resin composition of this invention, a photopolymerizable monomer, a photoinitiator, etc. is selected suitably. Specific examples of the organic solvent include cellosolves such as benzene, toluene and xylene, methyl cellosolve, ethyl cellosolve and butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate and butyl cell. Cellosolve acetic acid esters such as rosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoalkyl ether acetate esters such as propylene glycol monobutyl ether acetate, methyl methoxypropionate, methoxy propionic acid Propionic acid esters such as ethyl, methyl ethoxypropionate and ethyl ethoxypropionate, lactic acid esters such as methyl lactate, ethyl lactate, and butyl lactate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether and the like To methyl acetate, acetic acid Acetone esters, such as butyl and butyl acetate, ethers, such as dimethyl ether, diethyl ether, tetrahydrofuran, dioxane, ketones, such as acetone, methyl ethyl ketone, methyl butyl ketone, and cyclohexanone, etc. are mentioned.

These can be used individually or in combination of 2 or more types. In addition, in this invention, content of an organic solvent is 50-2,000 mass parts normally when it is used with respect to 100 mass parts of total solids of a negative photosensitive resin composition, Preferably it is 100-1,000 mass parts.

The negative photosensitive resin composition of this invention is manufactured by stirring, dissolving, or disperse | distributing said binder polymer, a photopolymerizable monomer, a photoinitiator, a pigment | dye, and an organic solvent with a dissolver, a homomixer, etc.

The negative photosensitive resin composition of this invention can contain various additives further, for example, a filler, surfactant, a thermal polymerization inhibitor, an adhesion promoter, antioxidant, a ultraviolet absorber, and an aggregation inhibitor as needed. In addition, the negative photosensitive resin composition of this invention can also be fine-filtered with a filter etc. in order to remove a foreign material etc. after preparation.

Next, the manufacturing method of the color filter, black matrix, and spacer of this invention is demonstrated. First, the negative photosensitive resin composition of the present invention is applied onto a substrate such as a glass substrate or a silicon substrate by a spin coating method, a roll coating method, a bar coating method, or the like so as to have a film thickness of approximately 0.1 to 7 µm. The film is formed by performing a prebaking treatment under the same conditions as the temperature of 60 to 120 ° C. for 1 to 50 minutes. Next, radiation (e.g., electron beams, ultraviolet rays, preferably ultraviolet rays) is irradiated through a predetermined mask pattern by a photolithography method, and an aqueous surfactant solution, an alkaline (aqueous) solution or a (surfactant + alkali agent) is applied. ) The solution is developed with an aqueous solution to remove the uncured portion, and rinsed with water to obtain a cured product pattern of the negative photosensitive resin composition of the present invention on a substrate.

In the above, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, etc. can be used as surfactant, When they are used, the aqueous solution of 0.05-1.0 mass% is normally used. Moreover, as alkali, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, diethanol amine, tetramethylammonium hydroxide, etc. are used, Usually, those aqueous solution of 0.05-1.0 mass% is used. In this invention, use of the aqueous solution containing an alkali and surfactant among the above is preferable. The development is usually carried out under the conditions of the temperature of 10 to 50 ° C, preferably 20 to 40 ° C, and the time of 30 to 180 seconds, preferably 30 to 120 seconds.

The hardened | cured material of the negative photosensitive resin composition of this invention is useful for the color filter, black matrix, and spacer for liquid crystal display devices, or as a color filter for solid-state image sensors for a digital camera.

The liquid crystal display of the present invention is produced in a structure in which a backlight, a polarizing film, a display electrode, a liquid crystal, an alignment film, a common electrode, a color filter of the present invention, a polarizing film and the like are laminated in this order, for example.

The solid-state imaging device of the present invention is produced by, for example, forming the color filter layer of the present invention on a silicon wafer on which a transfer electrode and a photodiode are formed, and then laminating microlenses.

(Example)

The present invention will be described in more detail with reference to the following Examples. In the examples,% means mass%.

Example 1

32 g of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) of methacrylic acid / benzyl methacrylate copolymer (20/80 mass ratio, weight average molecular weight 22,000) as a binder polymer, and a hydroxyl value of 70 mgKOH as a photopolymerizable monomer 7 g of acrylates of / g dipentaerythritol, 1 g of Irgacure 907 (manufactured by Chiba Specialty Chemicals) as a photopolymerization initiator, 0.5 g of Kayakure DETX-S (manufactured by Nippon Kayaku Co., Ltd.), and a pigment as a red pigment dispersion. (CI Pigment Red 177 / CI Pigment Yellow 83 / Dispersant / PGMEA = 16/4/5/75 weight ratio) 86 g and PGMEA 30g were mixed as a solvent and the red negative photosensitive resin composition 1 of this invention was obtained.

Comparative Example 1

32 g of PGMEA 22% solution of methacrylic acid / benzyl methacrylate copolymer (20/80 mass ratio, weight average molecular weight 22,000) as a binder polymer, 7 g of acrylate of dipentaerythritol having a hydroxyl value of 48 mg KOH / g as a photopolymerizable monomer, As a photoinitiator, it is a red pigment dispersion liquid (CI pigment red 177 / CI pigment yellow 83) as Irgacure 907 (made by Chiba Specialty Chemicals) 1 g, Kayacure DETX-S (made by Nippon Kayaku Co., Ltd.), and a pigment. / Dispersant / PGMEA = 16/4/5/75 weight ratio) 86g, PGMEA30g was mixed as a solvent, and the red negative photosensitive resin composition 2 was obtained.

Comparative Example 2

32 g PGMEA 22% solution of methacrylic acid / benzyl methacrylate copolymer (20/80 mass ratio, weight average molecular weight 22,000) as a binder polymer, pentaerythritol triacrylate (130 mgKOH / g hydroxyl value is 130 mgKOH / g) as a photopolymerizable monomer, photopolymerization As an initiator, 1 g of Irgacure 907 (made by Chiba Specialty Chemicals), Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.), 0.5 g, a pigment, a red pigment dispersion (CI pigment red 177 / CI pigment yellow 83 /) Dispersant / PGMEA = 16/4/5 / 75weight ratio) 86g and PGMEA30g were mixed as a solvent and the red negative photosensitive resin composition 3 was obtained.

Example 2

23 g of PGMEA 22% solution of methacrylic acid / benzyl methacrylate copolymer (20/80 mass ratio, weight average molecular weight 22,000) as a binder polymer, 5 g of acrylate of dipentaerythritol having a hydroxyl value of 130 mg KOH / g as a photopolymerizable monomer, Irgacure OXE02 (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), Chiba specialty chemical as a photoinitiator 1), 45 g of PGMEA 22% solution of carbon black dispersion liquid, and 34 g of PGMEA as a solvent were mixed as a pigment, and the black negative photosensitive resin composition 4 of this invention was obtained.

Comparative Example 3

23 g of PGMEA 22% solution of methacrylic acid / benzyl methacrylate copolymer (20/80 mass ratio, weight average molecular weight 22,000) as a binder polymer, 5 g of acrylate of dipentaerythritol having a hydroxyl value of 48 mg KOH / g as a photopolymerizable monomer, Irgacure OXE02 (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), Chiba specialty chemical as a photoinitiator 45g of PGMEA 22% solution of carbon black dispersion liquid and PGMEA 34g as a solvent were mixed as 1g and the pigments, and the black negative photosensitive resin composition 5 was obtained.

Comparative Example 4

23 g of PGMEA 22% solution of methacrylic acid / benzyl methacrylate copolymer (20/80 mass ratio, weight average molecular weight 22,000) as a binder polymer, pentaerythritol triacrylate (130 mg KOH / g of hydroxyl value) as photopolymerizable monomer, photopolymerization Irgacure OXE02 (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyl oxime), Chiba Specialty Chemicals Co., Ltd. 1g, 45 g of PGMEA 22% solutions of the carbon black dispersion liquid as a pigment, and 34 g of PGMEA as a solvent were mixed, and the black negative photosensitive resin composition 6 was obtained.

The red negative photosensitive resin composition 1, the black negative photosensitive resin composition 4, and the red negative photosensitive resin composition 2, 3, and the black negative photosensitive resin composition 5, 6 of this invention obtained above were spin-coated on a glass substrate. After application | coating at 1,000 rpm and prebaking on the conditions of 80 degreeC x 100 second, the mask (Toppan-Test-Chart) which the circuit pattern was drawn using the ultraviolet exposure apparatus (Oksei Corporation, model HMW-680GW). -200 mJ / cm <2> and 400mJ / cm <2> ultraviolet-rays were respectively irradiated through -No1-N). After exposure, 60 seconds of shower development with a 0.1% tetramethylammonium hydroxide (TMAH) aqueous solution containing a surfactant and rinsing with water were followed by heat treatment at 200 ° C to obtain a red pattern and a black pattern.

The adhesion and resolution to the glass substrate were determined by measuring the minimum line width (占 퐉) remaining after development. The smaller these widths, the better the adhesion and resolution. In addition, developability was confirmed by the time (second; break point) which started dissolution at the time of image development. The developability is excellent with shorter break point. The sensitivity was determined by shaking the exposure dose and patterning the result by checking the surface sclerosis with an optical microscope.

As is evident from the above results, by using an acrylate of dipentaerythritol having a hydroxyl value of 70 mgKOH / g or more and 130 mgKOH / g or less in the photosensitive resin composition, adhesiveness to an inorganic substrate, which cannot be obtained with a conventional acrylate monomer, A well-balanced photosensitive resin composition excellent in all of resolution, developability, and sensitivity can be obtained.

Claims (5)

A negative photosensitive resin composition comprising an acrylate of dipentaerythritol represented by the following formula (1), wherein the hydroxyl value is 70 mgKOH / g or more and 130 mgKOH / g or less.
<Formula 1>

(In Formula 1, a and b are positive integers, where a + b = 6, 1 ≦ a ≦ 6, and 0 ≦ b ≦ 5.) The method of claim 1,
Furthermore, the negative photosensitive resin composition containing a binder polymer, a pigment, and a photoinitiator. The color filter, black matrix, or spacer obtained by hardening | curing the negative photosensitive resin composition of Claim 1 or 2. A liquid crystal display device comprising the color filter, the black matrix, or the spacer according to claim 3. The solid-state imaging device provided with the color filter of Claim 3, a black matrix, or a spacer.