JPH11125902A - Resist composition for forming colored image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resist compsn. having satisfactory sensitivity and giving a transparent colored image having high light transmissivity even when a mask which does not sufficiently transmit light of <=310 nm wavelength is used. SOLUTION: The resist compsn. contains a pigment, a carboxyl group-contg. copolymer, a photopolymerizable monomer, a photopolymn. initiator and a solvent. A phosphine oxide compd. represented by the formula (where R<1> -R<0> are each H, a 1-4C alkyl or 1-4C alkoxy) is used as at least a part of the photopolymn. initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist composition for forming a colored image (also referred to as a pixel) used in a color liquid crystal display device or an image pickup device. More specifically, the present invention relates to a colored image forming resist composition having excellent transparency and capable of forming a cured film with a small amount of exposure.

[0002]

2. Description of the Related Art A color filter in a color liquid crystal display device or an image pickup device is usually manufactured by forming three primary color pixels of red, green and blue on a glass substrate or a silicon wafer. Further, it is usual to provide a black matrix for shielding light between these pixels.
Then, in order to form pixels of these colors, on a glass substrate or a silicon wafer on which a light-shielding layer is formed by patterning,
After uniformly applying a resist solution containing a pigment corresponding to each color with a spin coater, heating and drying (prebaking)
And the method of exposing and developing the coating film is adopted,
By repeating these operations for each color required for the color filter, an image of each color is obtained. As such a resist, together with a pigment and a binder resin,
Compositions containing a photopolymerizable monomer and a photopolymerization initiator are often used. In addition, a resist containing a black pigment may be used for forming a black matrix.

Exposure is performed through a mask on which a predetermined pattern is formed. The mask used is made of glass, but in many cases, when forming the red, green and blue pixels, a soda-lime glass whose production cost is relatively low is used. Soda-lime glass hardly transmits light having a wavelength of 310 nm or less because of its main components. Therefore, when a soda-lime glass mask is used, the resist to be used must have sufficient sensitivity at least in a wavelength region of 310 nm or more. Therefore, a compound having strong absorption in a wavelength region of 310 nm or more is used as the photopolymerization initiator component in the resist.

[0004]

However, on the assumption that a soda-lime glass mask is used, when a pixel is formed from a resist containing a photopolymerization initiator having a strong absorption in a wavelength region of 310 nm or more, photopolymerization is difficult. For example, the absorption area of the initiator overlaps the light transmission area of the blue pixel, which results in a decrease in the light transmission of the pixel. On the other hand, when a resist containing a photopolymerization initiator having a small absorption in a wavelength region of 310 nm or more is used to increase the transmittance of a pixel, particularly a blue pixel, the sensitivity is insufficient and the target thickness is hardened. There is a problem that a film cannot be obtained.

An object of the present invention is to form a colored image
Provide a resist composition that has sufficient sensitivity and has a high light transmittance to give a transparent colored image even when using a mask that does not easily transmit light having a wavelength of 310 nm or less, such as soda lime glass. Is to do.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems of the prior art, and as a result, they have contained a photopolymerization initiator having a specific structure together with pigments and binder resins. If a resist composition is used, 31
It has been found that excellent results can be obtained even when a mask having no sufficient light transmission region at 0 nm or less is used, and the present invention has been completed.

That is, the present invention provides (A) a pigment, (B) a carboxyl group-containing copolymer, (C) a photopolymerizable monomer,
(D) a photopolymerization initiator and (E) a solvent which provides a colored image-forming resist composition containing a phosphine oxide compound represented by the following formula (I): It is.

[0008]

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R
⁶ , R ⁷ , R ⁸ and R ⁹ independently represent hydrogen, alkyl having 1 to 4 carbons or alkoxy having 1 to 4 carbons.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The resist composition of the present invention is what is called a pigment dispersion type, in which a pigment is dispersed in a solvent, and further, a binder resin, a photopolymerizable monomer and a photopolymerization initiator, optionally other additives are dissolved or Distributed.

The pigment may be an organic pigment or an inorganic pigment usually used for a colored image forming resist. Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts.Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony Oxides or composite metal oxides are mentioned. As the organic pigment, specifically, a color index (Color Index) (The Societ
y of Dyers and Colorists published)
gment). These pigments can be used alone or in combination of two or more. More specifically, compounds having the following color index (CI) numbers can be mentioned, but are not limited thereto.

CI Pigment Yellow 20, 24, 31, 53,
83, 86, 93, 94, 109, 110, 117,125, 137, 138, 139,
147, 148, 153, 154, 166 and 173; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 6
1, 64 and 65; CI Pigment Red 9, 97, 105, 12
2, 123, 144, 149, 166, 168, 176,177, 180, 192, 21
5, 216 and 224; CI Pigment Violet 14, 1
9, 23, 29, 32, 33, 36, 37 and 38; CI Pigment Blue 15 (15: 3, 15: 4, 15: 6 etc.), 21, 22, 28, 60
And 64; CI Pigment Green 7, 10, 15, 25, 36
And 47; CI Pigment Brown 28; CI Pigment Black 1 and 7.

The pigment is used in an amount of preferably 5 to 60% by weight, more preferably 10 to 50% by weight, based on the total solid content in the colored image forming resist composition.

The binder resin imparts alkali developability to the unexposed coating film, and may also act as a pigment dispersion medium. In the present invention, a copolymer having a carboxyl group is used as the binder resin. The copolymer having a carboxyl group is a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable therewith.

The carboxyl group-containing monomer is, for example,
It can be an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid or unsaturated dicarboxylic acid, and specifically, acrylic acid,
Methacrylic acid, crotonic acid, itaconic acid, maleic acid,
Fumaric acid and the like. These can be used alone or in combination of two or more. Further, a monomer copolymerizable with these carboxyl group-containing monomers is a compound having a polymerizable unsaturated bond. Specifically, styrene, α-methylstyrene, aromatic vinyl compounds such as vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl Unsaturated carboxylic acid esters such as (meth) acrylate, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate, vinyl acetate and vinyl propionate Carboxylic acid vinyl ester, (meth)
And vinyl cyanide compounds such as acrylonitrile and α-chloroacrylonitrile. These monomers can also be used alone or in combination of two or more. In this copolymer, the carboxyl group-containing monomer is used in an amount of preferably 10 to 50% by weight, more preferably 15 to 40% by weight, based on the whole monomer.

Preferred specific examples of such a copolymer having a carboxyl group include benzyl methacrylate / methacrylic acid copolymer, benzyl methacrylate / methacrylic acid / styrene copolymer, methyl methacrylate / methacrylic acid copolymer, methyl Examples include methacrylate / methacrylic acid / styrene copolymer. These copolymers having a carboxyl group preferably have a weight-average molecular weight in terms of polystyrene of 10,000 to 400,000, more preferably 20,000 to 300,000. The carboxyl group-containing copolymer is generally contained in the range of 5 to 90% by weight, preferably 20 to 70% by weight, based on the total solid content in the resist composition.

The photopolymerizable monomer can be a bifunctional or other polyfunctional monomer in addition to a monofunctional monomer. Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. Also 2
Specific examples of the functional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate.
Acrylates, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like, and other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( Meta)
Examples include acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. Among them, a bifunctional or higher polyfunctional monomer is preferably used. The photopolymerizable monomer is generally contained in the range of 5 to 90% by weight, preferably 20 to 70% by weight, based on the total solid content in the resist composition.

Next, in the present invention, the phosphine oxide compound of the above formula (I) is used as a photopolymerization initiator.
In the formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R
⁶ , R ⁷ , R ⁸ and R ⁹ may be the same or different from each other, and may be hydrogen, alkyl having 1 to 4 carbons or 1 to 4 carbons.
Is an alkoxy. Here, examples of alkyl include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and the like, and examples of alkoxy include methoxy, ethoxy, propoxy, butoxy and the like. Among the phosphine oxide compounds of the formula (I), two or three of R ¹ , R ² and R ³ and two or three of R ⁴ , R ⁵ and R ⁶ are each alkyl, especially Those corresponding to the following formula (II) are advantageous.

[0019]

In the formula, R ¹¹ , R ¹² , R ¹⁴ and R ¹⁵ each independently represent alkyl having 1 to 4 carbon atoms, and R ¹³ , R ¹⁶ ,
R ¹⁷ and R ¹⁸ independently represent hydrogen or alkyl having 1 to 4 carbons.

The phosphine oxide compound represented by the above formula (I) or (II) can be prepared according to the method described in JP-A-6-298818 or JP-A-61-130296. It can be produced by reacting one or two kinds of substituted benzoyl chlorides with unsubstituted or substituted phenylphosphine to form a dibenzoylphosphine compound, and oxidizing the compound. Specifically, as such a phosphine oxide-based photopolymerization initiator,
The following formula (III)

[0022]

The screw (2, 2) sold by Ciba-Geigy under the trade name of "Irgacure 819"
4,6-trimethylbenzoyl) phenylphosphine oxide, which is preferably used in the present invention. Other specific examples include bis (2,6-
Dimethylbenzoyl) phenylphosphine oxide,
Bis (2,4,6-trimethylbenzoyl) (2,5-
(Dimethylphenyl) phosphine oxide and the like.

In the present invention, as the photopolymerization initiator,
It is essential to use the dibenzoylphenylphosphine oxide compound of the formula (I), but other photopolymerization initiators can be used in combination. The photopolymerization initiator to be used in combination can be one commonly used in this field, and examples thereof include acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based, triazine-based, and other initiators. More specifically,
The following compounds can be mentioned, and one or more of these can be used in combination with the phosphine oxide compound of the formula (I).

(A) acetophenone initiator diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) Phenyl] -2-methylpropane-1-
On, 1-hydroxycyclohexyl phenyl ketone,
2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-
1-one, 2-hydroxy-2-methyl-1- [4-
(1-methylvinyl) phenyl] oligomers of propan-1-one and the like.

(B) Benzoin initiators Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and the like.

(C) Benzophenone initiator Benzophenone, methyl o-benzoylbenzoate,
Phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like.

(D) Thioxanthone initiator 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone,
4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

(E) Triazine initiator 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- ( 4-methoxynaphthyl)-
1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine,
2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2- Yl) ethenyl] -1,3,5-triazine,
2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine,
2,4-bis (trichloromethyl) -6- [2- (4-
Diethylamino-2-methylphenyl) ethenyl]-
1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

(F) Other initiators 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl)
-4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone,
2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds and the like.

Further, a photopolymerization initiator may be used in combination with a photoinitiator. Specific examples of the photoinitiating aid include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate,
Isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine,
4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene,
9,10-diethoxyanthracene, 2-ethyl-9,
10-diethoxyanthracene and the like. These photoinitiating aids can be used alone or in combination of two or more.

The phosphine oxide compound of the formula (I) is preferably used in an amount of 0.01 to 35 parts by weight based on 100 parts by weight of the total of the carboxyl group-containing copolymer and the photopolymerizable monomer in the resist composition. And more preferably 5
Used in the range of ３０30 parts by weight. When other photopolymerization initiators are used in combination and, optionally, a photoinitiator is used, the total amount of these including the phosphine oxide compound of the formula (I) is defined as the carboxyl group-containing copolymer. And preferably 3 to 40 parts by weight, more preferably 5 to 3 parts by weight, based on 100 parts by weight of the photopolymerizable monomer.
Used in the range of 0 parts by weight.

The solvent can be any of those used in this field. Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol. Diethylene glycol dialkyl ethers such as dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl Propylene glycol alkyl ether acetates such as chromatography ether acetate; benzene, toluene, aromatic hydrocarbons such as xylene; methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone; ethanol, propanol,
Alcohols such as butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; 3
Esters such as ethyl ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone. These solvents can be used alone or in combination of two or more. The amount of the solvent to be used is preferably 60 to 90% by weight, more preferably 70 to 85% by weight, based on the total amount of the resist composition containing the solvent.

The resist composition for forming a colored image of the present invention may contain, if necessary, a filler, another polymer compound, a surfactant (a pigment dispersant), an adhesion promoter, an antioxidant, and an ultraviolet absorber. Further, additives such as an anti-agglomeration material can be mixed and used. Specific examples of the filler include glass, silica, and alumina, and specific examples of other polymer compounds include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. As the (pigment dispersant), various types such as nonionic, cationic, and anionic are used. Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (2-methoxyethoxy) silane. , N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane,
N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3
-Glycidoxypropylmethyldimethoxysilane, 2-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. are oxidized. Specific examples of the inhibitor include 2,2'-thiobis (4-methyl-
6-tert-butylphenol), 2,6-di-tert-butylphenol and the like, specifically, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro Benzotriazole, alkoxybenzophenone and the like, and specific examples of the coagulant include sodium polyacrylate.

The resist composition of the present invention can be prepared, for example, as follows. That is, the pigment is previously mixed with a partial amount of the final required amount of the solvent, and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, a dispersant is used if necessary,
A part or all of the carboxyl group-containing copolymer serving as a binder resin may be blended. The obtained pigment dispersion (mill base) is mixed with a solvent, a carboxyl group-containing copolymer, a residual amount, a photopolymerizable monomer, a photopolymerization initiator, and other components used as required at a predetermined concentration. To obtain the desired colored image forming resist composition.

The resist composition thus prepared can be applied to a substrate, for example, as described below, and cured by light and developed to form a colored image. First, a resist solution is spin-coated on a substrate (usually a glass substrate), and the solvent is heated and dried (prebaked) to obtain a smooth coating film. At this time, the thickness of the coating film is about 1-2 μm. The obtained coating film is irradiated with ultraviolet rays through a negative mask for forming a target image. At this time, it is preferable to use a device such as a mask aligner so that the entire exposed portion is uniformly irradiated with parallel rays and the mask and the substrate are accurately aligned. Thereafter, the cured coating film is brought into contact with a dilute aqueous alkaline solution to dissolve the unexposed portion and develop it, thereby obtaining an intended image. After the development, post-baking (post-baking) at 150 to 230 ° C. for about 10 to 60 minutes can be performed, if necessary.

The developer used for the development after the patterning exposure is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be any of inorganic and organic alkaline compounds. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide,
Disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate , Potassium borate, ammonia and the like. Further, specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine,
Triethylamine, monoisopropylamine, diisopropylamine, ethanolamine and the like. These inorganic and organic alkaline compounds can be used alone or in combination of two or more. The preferred concentration of the alkaline compound in the alkaline developer is
0.01 to 10% by weight, more preferably 0.0 to 10% by weight.
5 to 5% by weight.

The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant. Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, and polyoxyethylene alkyl ether. Oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like can be mentioned. Specific examples of anionic surfactants include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; sodium dodecylbenzene sulfonate; Alkyl aryl sulfonates such as sodium dodecylnaphthalene sulfonate, and the like. Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. These surfactants can be used alone or in combination of two or more. The concentration of the surfactant in the alkali developer is usually 0.0
1 to 10% by weight, preferably 0.05 to 8% by weight,
More preferably, the content is 0.1 to 5% by weight.

Through the above operations of coating and drying the resist solution, patterning exposure to the obtained dried coating film, and developing, pixels corresponding to the color of the pigment in the resist are obtained. Is repeated by the number of colors required for the color filter to obtain a color filter. That is, a color filter is usually one in which each pixel of red, green and blue is arranged on a substrate, but by performing the above operation using the resist composition of the present invention containing a pigment corresponding to a certain color. The same operation was performed using the resist composition of the present invention containing a pigment corresponding to the desired color for the other colors to obtain a pixel of that color,
Three color pixels can be arranged on the substrate. Of course, the resist composition of the present invention can be applied to only one or two of the three colors. Further, the resist composition of the present invention containing a black pigment can be used for forming a black matrix which is a light shielding layer.

[0040]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, percentages and parts representing the content or the used amount are based on weight unless otherwise specified. Also,
The carboxyl group-containing copolymer and the photopolymerizable monomer used in Examples and Comparative Examples are as follows.

(B) Carboxyl group-containing copolymer: weight ratio of benzyl methacrylate / methacrylic acid 80/2
0 (polystyrene-equivalent weight average molecular weight 35,00
0) (C) Photopolymerizable monomer: dipentaerythritol hexaacrylate (“Kayarad DPH” manufactured by Nippon Kayaku Co., Ltd.)
A ”)

Further, the photopolymerization initiators used are as follows, and are indicated below by the respective symbols, particularly in the tables.

(D) Photopolymerization initiator D1: bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (“Irgacure 819” manufactured by Ciba Geigy) DA: 2-methyl-1- [4- (methylthio) ) Phenyl) -2-morpholinopropanone-1 (“Irgacure 907” manufactured by Ciba-Geigy) DB: 2-benzyl-2-dimethylamino-1- (4-
Morpholinophenyl) -butanone-1 ("Irgacure 369" manufactured by Ciba Geigy) DC: 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine ("Triazine manufactured by Siebel-Hegner Japan") PP ") DD: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (" Lucillin TP manufactured by BASF)
O ”)

Example 1 and Comparative Examples 1 to 3 (blue resist) The total amount of each of the pigment and the pigment dispersant shown in Table 1 was previously mixed with a partial amount of propylene glycol monomethyl ether acetate as a solvent, and the mixture was mixed with a bead mill. Then, the pigment was sufficiently dispersed and subjected to micronizing treatment, and the remaining components including the remaining amount of propylene glycol monomethyl ether acetate were added thereto and mixed to obtain a resist solution having the composition shown in Table 1.

[0045]

Table 1 Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3顔料 Pigment: CI pigment blue 15: 6 4.8 parts 4.8 parts 4.8 parts 4.8 parts CI Pigment Violet 23 0.2 part 0.2 part 0.2 part 0.2 part Polymer 7.3 parts 7.3 parts 7.9 parts 8.6 parts ────────────────────────────────── Photopolymerizable monomer 3.1 parts 3.1 part 3.4 part 3.7 part ────────────────────────────────── Photopolymerization initiator: D1 3.1 part − − − DA − 3.1 part − − DB − − 2.2 part − DC − − − 1.2 part ──── ────────────────────────────── Nonionic pigment dispersant 1.5 parts 1.5 parts 1.5 parts 1.5 parts ────── ────────────────────────────Propylene glycol monomethyl ether acetate 80 parts 80 parts 80 parts 80 parts ━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━

A 2-inch square quartz glass substrate was washed sequentially with a neutral detergent, water and alcohol, and then dried.
Each of the resist solutions prepared above was spin-coated on the glass substrate so as to have a predetermined thickness, and then prebaked in a clean oven at 100 ° C. for 3 minutes. The resist film was covered with 1.3 mm thick soda-lime glass, and the entire coating was irradiated with light at an exposure of 200 mJ / cm ² from above the soda-lime glass using an ultra-high pressure mercury lamp manufactured by Ushio Inc. . Thereafter, post-baking was performed at 220 ° C. for 30 minutes to obtain a transmittance measurement sample. Using this sample, the transmittance of the coating film was measured at two wavelengths of 415 nm and 460 nm. The transmittance measurement was performed only on the blue coating film which is easily affected by the coloring of the coating film by the photopolymerization initiator. Table 2 shows the results.

On the other hand, in the same manner as in the transmittance measurement sample above, after pre-baking and light irradiation through a soda-lime glass mask, a development using a 0.2% aqueous solution of sodium carbonate containing a nonionic surfactant was carried out. The sample was immersed in the solution for 1 minute, washed with water, and post-baked at 220 ° C. for 30 minutes to obtain a sample for checking the sensitivity of the remaining film. The residual film sensitivity was evaluated by comparing the residual film thickness with the sample that had been post-baked without being immersed in a developer after pre-baking and light irradiation. The post-baked sample was immersed in the developer and the post-baked sample was immersed in the developer.
If the film thickness is almost the same, this irradiation exposure amount (200 mJ /
It is determined that there is a residual film sensitivity in cm ² ). The results are also shown in Table 2.

[0048]

[Table 2] Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Photopolymerization initiator D1 DA DB DC ──────透過 Film transmittance Film thickness 1.4μm 1.4μm 1.4μm 1.4μm 415nm transmittance 61.5% 61.9% 59.0% 51.0% 460nm transmittance 83.2% 83.2% 80.7% 73.7% ───────────────────────────────── ── 200 mJ / cm ² film thickness after post-baking in the remaining film sensitivity undeveloped 1.4 [mu] m 1.4 [mu] m 1.4 [mu] m 1.4 [mu] m development, thickness 1.4 [mu] m peel 1.4 [mu] m 1.4 [mu] m exposure after post-baking, there no film loss after development None None ──────────────────────────────── ─── Overall judgment ○ × × × ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

As can be seen from Table 2, the screw (2,4,6
The composition of Example 1 in which -trimethylbenzoyl) phenylphosphine oxide was used as a photopolymerization initiator had a high coating film transmittance and a sensitivity of 200 mJ / cm ² remaining film. In the composition of the comparative example using the agent, those having a high coating film transmittance could not attain a residual film sensitivity of 200 mJ / cm ² , while those having a 200 mJ / cm ² residual film sensitivity could be confirmed to have the coating film transmittance. Was low.

Example 2 and Comparative Examples 4 to 5 (Red Resist) A pigment consisting of 4.5 parts of CI Pigment Red 177 and 1.5 parts of CI Pigment Yellow 139, and a nonionic pigment dispersant 1. 8 parts were mixed with 24 parts of propylene glycol monomethyl ether acetate, the pigment was sufficiently dispersed using a bead mill and finely treated, and 56 parts of propylene glycol monomethyl ether acetate and a carboxyl group-containing copolymer 6.6 were added. Parts, 2.8 parts of a photopolymerizable monomer and 2.8 parts of a photopolymerization initiator shown in Table 3 were added and mixed to obtain a resist solution. Using this resist solution, the sensitivity of the residual film was evaluated in the same manner as in Example 1.
Table 3 also shows the results.

[0051]

Table 3 Example 2 Comparative Example 4 Comparative Example 5 ━━━━━━━━━━━━━━━━━━━━━━━ Photopolymerization initiator D1 DA DD ──────────────────── ────────── 200 mJ / cm ² Residual film sensitivity Undeveloped film thickness after post-baking 1.4 μm 1.4 μm 1.4 μm Film thickness after developing and post-baking 1.3 μm Peeling 0.8 μm After exposure and development Film reduction Almost none Yes Yes 総 合 Overall judgment ○ × × ○ ━━━━━━━━━━━━━━━━━━━━━

As can be seen from Table 3, the screws (2, 4, 6
The composition of Example 2 using (trimethylbenzoyl) phenylphosphine oxide as a photopolymerization initiator was 200 mJ
/ Cm ² remaining film sensitivity was confirmed, whereas the composition of the comparative example using another photopolymerization initiator could not achieve a remaining film sensitivity of 200 mJ / cm ² .

Example 3 and Comparative Examples 6 to 7 (Green Resist) A pigment consisting of 5.7 parts of CI Pigment Green 36 and 2.3 parts of CI Pigment Yellow 139, and a nonionic pigment dispersant 2. One part was mixed with 32 parts of propylene glycol monomethyl ether acetate, the pigment was sufficiently dispersed using a bead mill, and the mixture was subjected to micronization treatment. This was mixed with 48 parts of propylene glycol monomethyl ether acetate and a copolymer having a carboxyl group of 5.9. , 2.5 parts of a photopolymerizable monomer and 2.5 parts of a photopolymerization initiator shown in Table 4 were added and mixed to obtain a resist solution. Using this resist solution, the sensitivity of the residual film was evaluated in the same manner as in Example 1.
Table 4 also shows the results.

[0054]

Table 4 Example 3 Comparative Example 6 Comparative Example 7 ━━━━━━━━━━━━━━━━━━━━━━━ Photopolymerization initiator D1 DA DD ──────────────────── ────────── 200 mJ / cm ² Residual film sensitivity Undeveloped film thickness after post-baking 1.4 μm 1.4 μm 1.4 μm Film thickness after development and post-baking 1.4 μm Peeling 1.0 μm After exposure and development Film reduction No Yes Yes ────────────────────────────── Overall judgment ○ × × ━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━

As can be seen from Table 4, bis (2,4,6)
The composition of Example 3 using -trimethylbenzoyl) phenylphosphine oxide as a photopolymerization initiator was 200 mJ
/ Cm ² remaining film sensitivity was confirmed, whereas the composition of the comparative example using another photopolymerization initiator could not achieve a remaining film sensitivity of 200 mJ / cm ² .

[0056]

The resist composition for forming a colored image of the present invention has a good residual film sensitivity regardless of the composition of red, blue and green, and can form a cured film with a small amount of exposure. . In addition, even when a blue pixel is formed using a mask that does not sufficiently transmit light having a wavelength of 310 nm or less, a colored film having high transmittance can be formed by using this composition, and thus a colored image having excellent transparency can be formed. Can be formed.

Claims (4)

[Claims] A resist composition comprising (A) a pigment, (B) a carboxyl group-containing copolymer, (C) a photopolymerizable monomer, (D) a photopolymerization initiator, and (E) a solvent. Wherein the photopolymerization initiator has the formula (I) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ ,
R ⁸ and R ⁹ independently represent hydrogen, alkyl having 1 to 4 carbons or alkoxy having 1 to 4 carbons). Composition. 2. The phosphine oxide compound of the formula (I)
I) (Wherein, R ¹¹ , R ¹² , R ¹⁴ and R ¹⁵ independently represent alkyl having 1 to 4 carbons, and R ¹³ , R ¹⁶ , R ¹⁷ and R ^15
18 independently represent hydrogen or alkyl having 1 to 4 carbons). 3. The phosphine oxide compound according to claim 1, wherein
The composition according to claim 1, which is (2,4,6-trimethylbenzoyl) phenylphosphine oxide. 4. The method according to claim 1, wherein the phosphine oxide compound comprises a carboxyl group-containing copolymer and a photopolymerizable monomer.
The composition according to any one of claims 1 to 3, which is present in the range of 0.1 to 35 parts by weight based on 0 part by weight.