KR20110024394A - Colored photosensitive resin composition for color filter of solid state imaging device, color filter and solid state imaging device including the same - Google Patents

Abstract

PURPOSE: A colored photosensitive resin composition for the color filter of a solid state imaging device, the color filter fabricated using the same, and the solid state imaging device including the same are provided to include a colored pattern with the high resolution and the superior sensitivity. CONSTITUTION: A colored photosensitive resin composition contains pigment and dye. The dye is selected from color index solvent, and the pigment is selected from color index pigment. A photo-polymerization initiator includes an oxime ester-based photo-polymerization initiator and other photo-polymerization initiator. The colored photosensitive resin composition is coated on a substrate, and a pre-set pattern is exposed and developed to obtain a colored pattern using exposure equipment.

Description

Colored photosensitive resin composition for manufacturing a color filter of a solid-state imaging device using an ultra-short wavelength exposure device of 300 nm or less, a color filter prepared using the same, and a solid-state imaging device comprising the same filter and solid state imaging device including the same}

The present invention provides a color photosensitive resin composition for manufacturing a color filter of a solid-state imaging device, which comprises a colorant composed of a mixture of pigments and dyes, using an ultra-short wavelength exposure device of 300 nm or less, a color filter manufactured using the same, and a solid-state imaging device including the same. It is about.

As is well known, an image pickup device for implementing a color image is provided with a color filter on an upper portion of a light sensing portion that receives and receives light from the outside to generate and accumulate photocharges. The color filter is composed of a coloring pattern of three colors of red, green, and blue, or coloring of three colors of yellow, magenta, and cyan. It consists of a pattern.

The coloring pattern of each said color filter is formed using the coloring photosensitive resin composition containing a pigment or dye. Colored pattern processing using the colored photosensitive resin composition is usually carried out in a lithography process. As a wavelength of the light source for the lithography process used for the said coloring pattern manufacture, g-ray (wavelength 436nm) or i-ray (wavelength 365nm) wavelength is used normally.

On the other hand, in recent years, solid-state imaging devices such as digital cameras require that the pixel size is reduced to less than 2um from the existing 4-5um in order to improve the high pixel quality and image quality, and the coloring pattern is also required to have ultrafine and square.

Accordingly, the inventors of the present invention conducted an attempt to ultrafine the colored pattern size of the color filter for a solid-state image sensor by using an ultra short wavelength exposure machine of 300 nm or less. However, the conventional colored photosensitive resin composition is hardly curable at an ultra short wavelength of 300 nm or less. There is a problem that it does not work well. In addition, as the size of the pixel decreases, the thickness of the coating film must be maintained at 0.8um or less, so that curing is performed at an ultra-short wavelength of 300 nm or less.

Moreover, in order to obtain a coloring pattern effectively using a coloring photosensitive resin composition, it is preferable to use the coloring photosensitive composition containing a coloring agent in high concentration. However, in the case of the coloring photosensitive resin composition containing a high concentration of the colorant, the content of the binder polymer, the photopolymerizable compound, and the photopolymerization initiator may be relatively decreased, resulting in inferior sensitivity or difficulty in pattern formation. The coloring photosensitive composition which does not contain the coloring agent at high concentration has a problem in that color purity falls or color mixing occurs when a pattern is formed at the same film thickness as the coloring photosensitive resin composition containing a high concentration of coloring agent.

The present invention is to solve the problems of the prior art as described above, by using a colorant composed of a combination of pigments and dyes in the manufacture of a color filter of a solid-state imaging device using an ultra-short wavelength exposure device of 300nm or less, to prevent a decrease in transmittance To provide a colored photosensitive resin composition for producing a color filter of a solid-state imaging device using an ultra-short wavelength exposure device of 300nm or less capable of producing a color filter having excellent color purity, high sensitivity without color mixing, and ultrafine high resolution coloring pattern. There is this.

It is another object of the present invention to provide a color filter having an ultrafine high resolution coloring pattern.

Another object of the present invention is to provide a solid-state image sensor including the color filter.

In order to achieve the above object, the present invention provides a colored photosensitive resin composition for producing a color filter of a solid-state imaging device using a 300 nm or less ultra-short wavelength exposure device comprising a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent. The colorant comprises a pigment and a dye, and the photopolymerization initiator comprises a photopolymerization initiator other than the oxime ester photopolymerization initiator and the oxime ester photopolymerization initiator, the solid using an ultra-short wavelength exposure device of 300nm or less The coloring photosensitive resin composition for color filter manufacture of an imaging element is provided.

The dye is preferably selected from among C. I. Solvent.

In addition, the pigment is preferably selected from the color index pigment (C.I. Pigment).

In particular, when the colored photosensitive resin composition is a colored photosensitive resin composition colored with Green, the pigment includes color pigment pigment (CI Pigment) Green, and the dye is color index solvent (CI Solvent). ) Yellow is preferably included. In this case, the pigment is in the color index pigment (CI Pigment Green No. 7), the color index pigment (CI Pigment) Green No. 36 and the color index pigment (CI Pigment) Green No. 58 At least one selected, and the dye may include color index solvent Yellow (CI Solvent Yellow) 82.

In addition, when the colored photosensitive resin composition is a colored photosensitive resin composition that is colored red, the pigment comprises color pigment pigment (CI Pigment) red, and the dye is color index solvent (CI Solvent). ) May be included.

In addition, when the coloring photosensitive resin composition is a coloring photosensitive resin composition that is colored blue, the pigment comprises a color index pigment (CI Pigment) Blue, and the dye is a color index solvent (CI Solvent) ) May be included.

Other photopolymerization initiators other than the oxime ester photopolymerization initiator may be selected from an acetophenone photopolymerization initiator, a benzoin photopolymerization initiator, a benzophenone photopolymerization initiator, a thioxanthone photopolymerization initiator or a triazine photopolymerization initiator, and a sensitizer. And it is preferable that it is at least 1 sort (s) chosen from the group which consists of an acid generator.

The oxime ester photopolymerization initiator is contained in a weight fraction of 1 to 99% by weight based on the total amount of the photopolymerization initiator including the same, the photopolymerization initiator is preferably contained 1 to 50% by weight based on the solids content in the colored photosensitive resin composition.

It is preferable that the ultra-short wavelength exposure machine of 300 nm or less is a KrF scanner exposure machine (248 nm).

In order to achieve the other object of the present invention, the present invention provides a colored pattern formed by coating the colored photosensitive resin composition according to the present invention on a substrate and then exposing and developing in a predetermined pattern using an ultra-short wavelength exposure machine of 300 nm or less. It provides a color filter comprising a.

In order to achieve another object of the present invention, the present invention provides a solid-state imaging device comprising the color filter.

The coloring photosensitive resin composition for manufacturing a color filter of a solid-state imaging device using the ultra-short wavelength exposure machine of 300 nm or less according to the present invention is 0.8um or less while maintaining a fine colored pattern of 1.4 μm or less, especially a fine size of 1.0 μm or less, with low limit resolution. Even in the film thickness, a clean transmittance graph in which impurity peaks are reduced in a required wavelength band can be obtained, and color filters can be manufactured without disadvantages such as lack of color purity or color mixing due to no impurity peaks in a required wavelength band. Accordingly, the color filter may be usefully used for a solid state imaging device.

Hereinafter, the present invention will be described in detail.

The coloring photosensitive resin composition (henceforth simply called a "coloring photosensitive resin composition") of the color filter manufacture of the solid-state image sensor using the ultra short wavelength exposure machine of 300 nm or less which concerns on this invention is a coloring agent (A), binder resin (B), and a photopolymerizable compound. (C), a photoinitiator (D), and a solvent (E).

Colorant (A)

The colorant includes not only pigments generally used in the field of conventional coloring photosensitive resin compositions, but also dyes soluble in organic solvents. Therefore, it is excellent in dispersibility and color implementability compared with the conventional coloring agent which is a simple mixing form of a dispersing agent and a pigment. In particular, it is possible to effectively reduce the impurity peaks on the transmittance graph generated when only the pigment is used.

The pigment can be used without limiting the pigment which absorbs or transmits a specific color.

Organic or inorganic pigments may be used as the pigment, and may be a synthetic or natural pigment.

The inorganic pigments may be, for example, metal oxides, metal complex salts, inorganic salts of barium sulfate (constitution pigments), and the like.

If necessary, organic pigments can be finely granulated by rosin treatment, surface treatment using pigment derivatives having acidic or basic groups introduced therein, graft treatment on the surface of pigments using polymer compounds, etc., sulfuric acid fine granulation methods, and the like. Treatment or washing treatment with an organic solvent, water or the like can be performed to remove impurities.

The pigment may specifically use a compound classified as a pigment in the Color Index (published by The Society of Dyers and Colourists), specific examples of which may be listed as follows.

Specific examples of pigments that can be used include,

C.I. Pigment Yellow No. 1, C.I. Pigment Yellow 12, C.I. Pigment Yellow No. 13, C.I. Pigment Yellow No. 14, C.I. Pigment Yellow No. 15, C.I. Pigment Yellow No. 16, C.I. Pigment Yellow No. 17, C.I. Pigment Yellow No. 20, C.I. Pigment Yellow No. 24, C.I. Pigment Yellow No. 31, C.I. Pigment Yellow No. 53, C.I. Pigment Yellow No. 83, C.I. Pigment Yellow No. 86, C.I. Pigment Yellow 93, C.I. Pigment Yellow No. 94, C.I. Pigment Yellow No. 109, C.I. Pigment Yellow No. 110, C.I. Pigment Yellow No. 117, C.I. Pigment Yellow No. 125, C.I. Pigment Yellow No. 128, C.I. Pigment Yellow 137, C.I. Pigment Yellow 138, C.I. Pigment Yellow No. 139, C.I. Pigment Yellow No. 147, C.I. Pigment Yellow 148, C.I. Pigment Yellow No. 150, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 166, C.I. Pigment yellow 173,

C.I. Pigment Orange No. 13, C.I. Pigment Orange No. 31, C.I. Pigment Orange No. 36, C.I. Pigment Orange No. 38, C.I. Pigment Orange No. 40, C.I. Pigment Orange No. 42, C.I. Pigment Orange No. 43, C.I. Pigment Orange No. 51, C.I. Pigment Orange No. 55, C.I. Pigment Orange No. 59, C.I. Pigment Orange No. 61, C.I. Pigment Orange 64, C.I. Pigment Orange 65, C.I. Pigment Orange 71, C.I. Pigment Orange No. 73,

C.I. Pigment Red No. 9, C.I. Pigment Red No. 97, C.I. Pigment Red No. 105, C.I. Pigment Red No. 122, C.I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 176, C.I. Pigment Red No. 177, C.I. Pigment Red No. 180, C.I. Pigment Red 192, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red No. 254, C.I. Pigment Red No. 264, C.I. Pigment Red No. 265, C.I.

Pigment Blue No. 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Blue No. 60,

C.I. Pigment Violet No. 1, C.I. Pigment Purple No. 19, C.I. Pigment Purple No. 23, C.I Pigment Purple No. 29, C.I Pigment Purple No. 32, C.I Pigment Purple No. 36, C.I Pigment Purple No. 38,

C.I. Pigment Green No. 7, C.I. Pigment green 36,

C.I. Pigment Brown No. 23, C.I. Pigment brown No. 25, etc. are mentioned.

The pigments may be used alone or in combination of two or more.

The dye may use a compound classified as a salt in the Color Index (published by The Society of Dyers and Colourists), and in particular, a dye of the CI Solvent-based dyes listed in the following examples. Good to do.

Specific examples of dyes that can be used include,

C.I. Solvent Yellow No. 2, C.I. Solvent Yellow No. 14, C.I. Solvent Yellow No. 16, C.I. Solvent Yellow No. 33, C.I. Solvent Yellow No. 34, C.I. Solvent Yellow No. 44, C.I. Solvent Yellow No. 56, C.I. Solvent Yellow No. 82, C.I. Solvent Yellow No. 93, C.I. Solvent Yellow No. 94, C.I. Solvent Yellow No. 98, C.I. Solvent Yellow No. 116, C.I. Solvent yellow 135,

C.I. Solvent Orange No. 1, C.I. Solvent Orange No. 3, C.I. Solvent Orange No. 7, C.I. Solvent Orange 63,

C.I. Solvent Red No. 1, C.I. Solvent Red No. 2, C.I. Solvent Red No. 3, C.I. Solvent Red No. 8, C.I. Solvent Red No. 18, C.I. Solvent Red No. 23, C.I. Solvent Red No. 24, C.I. Solvent Red No. 27, C.I. Solvent Red No. 35, C.I. Solvent Red No. 43, C.I. Solvent Red No. 45, C.I. Solvent Red No. 48, C.I. Solvent Red No. 49, C.I. Solvent Red 91: 1, C.I. Solvent Red No. 119, C.I. Solvent Red No. 135, C.I. Solvent Red No. 140, C.I. Solvent Red No. 196, C.I. Solvent Red No. 197, C.I.

Solvent Violet No. 8, C.I. Solvent Purple No. 9, C.I. Solvent Purple No. 13, C.I. Solvent Purple No. 26, C.I. Solvent Purple No. 28, C.I. Solvent Purple No. 31, C.I. Solvent Purple No. 59,

C.I. Solvent Blue No. 4, C.I. Solvent Blue No. 5, C.I. Solvent Blue No. 25, C.I. Solvent Blue No. 35, C.I. Solvent Blue No. 36, C.I. Solvent Blue No. 38, C.I. Solvent Blue No. 70,

C.I. Solvent Green No. 3, C.I. Solvent Green No. 5, C.I. Solvent green 7 and the like.

The dyes may be used alone or in combination of two or more.

For example, when the colored photosensitive resin composition is a colored photosensitive resin composition colored with Green, the pigment is not limited, but the pigment includes color index Pigment Green, and the dye Color index solvent (CI Solvent) yellow may be included. In particular, the pigment may be used in the color index pigment (CI Pigment Green) No. 7, the color index pigment (CI Pigment) Green 36 and the color index pigment (CI Pigment) Green 58 At least one selected, and the dye may include color index solvent Yellow (CI Solvent Yellow) 82.

In addition, when the colored photosensitive resin composition is a colored photosensitive resin composition colored in red, the pigment includes a color pigment pigment (CI Pigment) red, and the dye is a color index solvent (CI Solvent). It may include.

In addition, when the colored photosensitive resin composition is a colored photosensitive resin composition colored in blue, the pigment includes color index pigment (CI Pigment) Blue, and the dye may use color index solvent (CI Solvent). It may include.

The content of the pigment and the dye in the colorant is not limited. Preferably, each of the pigment and the dye may be included in the weight ratio of 1 to 99% by weight based on the total amount of the colorant. When the content of the pigment and dye is included in the above range it is possible to effectively reduce the impurity peaks on the transmittance graph to obtain a color pattern without excellent color purity and color mixing. The usage-amount of the said coloring agent is 5 weight%-60 weight%, Preferably it is 10 weight%-50 weight% with respect to solid content in a coloring photosensitive resin composition. When the amount of the coloring agent is included in the above range on the basis of the above standard, the color density of the coloring pattern is sufficient, and it is possible to form a coloring pattern with sufficient mechanical strength.

In this case, the colorant may be used in the form of a dispersion liquid (hereinafter sometimes referred to as a mill base), which is previously mixed with a solvent and dispersed using a bead mill or the like until the average particle diameter of the colorant becomes 0.2 μm or less. The dispersion may further be dispersed by further adding a pigment dispersant in the dispersion process, or may be dispersed by mixing some or all of the binder resin according to the present invention to be described later.

When the dispersion is composed of a colorant and a solvent, the colorant is preferably 5 to 60 parts by weight, preferably 10 to 40 parts by weight, based on 100 parts by weight of the total amount of the colorant and the solvent.

When the pigment dispersant is further added to the dispersion, the pigment dispersant may be, for example, a polyester polymer dispersant, an acrylic polymer dispersant, a polyurethane polymer dispersant, a cationic surfactant, an anionic surfactant, or a nonionic interface. An activator etc. can be used, These can be used individually or in combination of 2 or more types, respectively.

In particular, commercially available surfactants may be used as the pigment dispersant. Examples of the above surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, and sorbitan fatty acid esters. , Fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines, and the like, as well as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (PolyFlow) ), EFTOP (manufactured by Tochem Products, Inc.), MEGAFAC (manufactured by Dainippon Ink & Chemicals Co., Ltd.), Florard (manufactured by Sumitomo 3M), Asahi guard And Suflon (above, manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (manufactured by Genka Corp.), EFKA (manufactured by EFKA Chemicals), PB 821 (manufactured by Ajinomoto Co., Ltd.), and the like.

The pigment dispersant is preferably 0.01 to 1 parts by weight, preferably 0.05 to 0.5 parts by weight based on 1 part by weight of the colorant, in consideration of dispersion of the colorant.

Solid content in a coloring photosensitive composition in this invention means the sum total of the component which removed the solvent.

Binder Resin (B)

The binder resin serves as a binder resin for the colorant, and any binder may be used as long as the polymer is soluble in the alkaline developer used in the developing step.

The binder resin may, for example, be a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the carboxyl group-containing monomer.

As said carboxyl group-containing monomer, For example, unsaturated monocarboxylic acid, unsaturated carboxylic acid, such as unsaturated polyhydric carboxylic acid which has 1 or more carboxyl groups in molecules, such as unsaturated dicarboxylic acid and unsaturated tricarboxylic acid, etc. Can be mentioned.

Here, as unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example.

As said unsaturated dicarboxylic acid, a maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example.

The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride and citraconic anhydride.

In addition, the unsaturated polyhydric carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester thereof, for example, monosuccinate mono (2-acryloyloxyethyl), monosuccinate mono (2-methacryloyloxy Ethyl), mono phthalate (2-acryloyloxyethyl), mono phthalate (2-methacryloyloxyethyl), and the like.

The unsaturated polyhydric carboxylic acid may be mono (meth) acrylate of the sock end dicarboxy polymer, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. have.

These carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively.

The other monomer copolymerizable with the carboxyl group-containing monomer is a monomer having a carbon-carbon unsaturated bond, and specific examples thereof include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene. Acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate Unsaturated amino alkyl carboxylate compounds such as acrylate, such as aminoethyl acrylate, unsaturated glycidyl carboxylate compounds such as glycidyl methacrylate, such as vinyl carboxylate compounds such as vinyl acetate, vinyl propio Vinyl cyanide compounds such as nate, such as arc Unsaturated oxetane carboxylate compounds such as ronitrile, methacrylonitrile, α-chloroacrylonitrile, such as 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxyethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, etc. are mentioned. These monomers can be used individually or in combination of 2 types or more, respectively.

Examples of the copolymer include 3-ethyl-3-methacryloxymethyloxetane / benzyl methacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryloxymethyloxetane / benzyl methacrylate / methacryl Acid / styrene copolymer, 3-ethyl-3-methacryloxymethyloxetane / methylmethacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryloxymethyloxetane / methylmethacrylate / methacryl Acid / styrene copolymer etc. are mentioned.

In the binder resin of the copolymer, the content of the monomer unit having a carboxyl group is preferably 5% by weight to 50% by weight, more preferably 10% by weight to 40% by weight. When content of the said carboxyl group-containing monomeric unit is in the said range, since the solubility to a developing solution is favorable and the coloring pattern at the time of image development is formed correctly, it is preferable.

In addition, the binder resin preferably has an acid value in the range of 20 to 200 (mgKOH / g). When the acid value is in the above range, the solubility in the developer is improved and the non-exposed portion is easily dissolved. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can usually be obtained by titration using an aqueous potassium hydroxide solution.

The binder resin preferably has a weight average molecular weight (MW) of 5000 to 400000, or 10000 to 300000, as measured by gel permeation chromatography (GPC) using polystyrene as a standard material. When the molecular weight is in the above range, it is preferable because the surface hardness of the colored pattern is improved, solubility of the non-exposed part is excellent, and resolution is improved.

The binder resin is preferably contained in a weight fraction of 5% by weight to 85% by weight, preferably 20% by weight to 70% by weight relative to the solid content in the colored photosensitive resin composition. When the binder resin is within the content range on the basis of the reference, the formation of the pattern is possible, and the resolution and the residual film ratio are improved.

Photopolymerizable Compound (C)

The said photopolymerizable compound is a compound which can superpose | polymerize with active radicals, an acid, etc. which generate | occur | produce from a photoinitiator by light irradiation, For example, the compound which has a polymerizable carbon-carbon unsaturated bond, etc. are mentioned. Such compounds may be monofunctional photopolymerizable compounds, bifunctional photopolymerizable compounds, or trifunctional or higher polyfunctional photopolymerizable compounds.

Examples of the monofunctional photopolymerizable compound include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-. Vinylpyrrolidone, etc. are mentioned.

Examples of the bifunctional photopolymerizable compound include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, neopentyl glycol diacrylate , Neopentyl glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol diacrylate, 3-methylpentane Diol dimethacrylate etc. are mentioned.

Examples of the trifunctional or higher polyfunctional photopolymerizable compound include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate The rate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. are mentioned.

The photopolymerizable compounds exemplified above may be used alone or in combination of two or more thereof. It is preferable to use the bifunctional or more photopolymerizable compound among the said photopolymerizable compounds.

The amount of the photopolymerizable compound used is 0.1 to 70% by weight, preferably 1 to 60% by weight, based on the weight of solids in the colored photosensitive resin composition. When the said photopolymerizable compound is contained in the said range on the basis of said reference | standard, the intensity | strength or smoothness of a coloring pattern will become favorable.

Photopolymerization Initiator (D)

As said photoinitiator, what consists of an oxime ester photoinitiator and the photoinitiator other than the said oxime ester photoinitiator is used. When the oxime ester photopolymerization initiator and other photopolymerization initiators are mixed and used as the photopolymerization initiator as described above, it is possible to form a high resolution ultrafine colored pattern with high sensitivity.

Specific examples of the oxime ester photopolymerization initiator include 1- (4-phenylthiophenyl) -1,2-octanedione-2- (O-benzoyloxime)) and 1- (4-methylsulfanyl-phenyl) -butane -1,2-butane-2-oxime-O-acetate, 1- (4-methylsulfanyl-phenyl) -butan-1-one oxime-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl ) -Ethyl acetate-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -ethyl acetate-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl- 4tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) etc. are mentioned.

The exemplified oxime photoinitiators can be used alone or in combination of two or more.

The other photopolymerization initiator is selected from the group consisting of an active radical generator, a sensitizer and an acid generator selected from acetophenone photopolymerization initiator, benzoin photopolymerization initiator, benzophenone photopolymerization initiator, thioxanthone photopolymerization initiator or triazine photopolymerization initiator. At least one selected can be used.

Examples of the acetophenone-based photopolymerization initiator are diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [2- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1 -On oligomers, etc. are mentioned.

Examples of the benzoin-based photopolymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.

Examples of the benzophenone-based photopolymerization initiator are benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (t -Butyl peroxycarbonyl) benzophenone, 2,4, 6-trimethyl benzophenone, etc. are mentioned.

Examples of the thioxanthone photopolymerization initiator include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4- Propoxy thioxanthone etc. are mentioned.

Examples of the triazine photoinitiator include 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.

Examples of the sensitizer include 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, methylphenylglyoxylate, titanocene compound and the like can also be used.

Examples of the acid generator include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p- Toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p- Toluene sulfonate, diphenyl iodonium hexafluoro antimonate, nitrobenzyl tosylate, benzoin tosylate, etc. are mentioned.

Among the above-mentioned compounds, there are also compounds which generate an acid together with generating an active radical as an active radical generator. For example, a triazine photoinitiator is used as an acid generator.

The photoinitiators illustrated above can be used individually or in combination of 2 types or more, respectively.

The said photoinitiator is contained 1-50 weight% in weight fraction with respect to solid content in colored photosensitive resin composition. If the photopolymerization initiator is less than 1 wt% based on the above criteria, there is a problem in that the sensitivity at the wavelength of 300 nm or less is insufficient to obtain an ultrafine colored pattern with excellent resolution. It is preferable to use a photoinitiator within the said range.

In addition, it is preferable that the said oxime ester type photoinitiator is contained 1 to 99 weight% by weight with respect to the photoinitiator whole quantity containing it. When the oxyester-based photopolymerization initiator is less than 1% by weight, there is a problem in that the sensitivity is not obtained to obtain an ultra-fine colored pattern with excellent resolution, and when the content exceeds 99% by weight, the resolution is lowered. It is preferable to use an oxime ester system photoinitiator within the range.

The photopolymerization initiator may be used together with a photopolymerization initiation aid to enhance the polymerization of the photopolymerizable compound.

As said photoinitiation start adjuvant, an amine photoinitiation start adjuvant, an alkoxy anthracene type photoinitiation start adjuvant, etc. are mentioned, for example.

Examples of the amine photopolymerization start adjuvant include triethanolamine, methyl diethanolamine, triisopropanolamine, methyl4-dimethylaminobenzoate, ethyl4-dimethylaminobenzoate, isoamyl4-dimethylaminobenzoate, 2-dimethylamino Ethylbenzoate, 2-ethylhexyl4-dimethylaminobenzoate, N, N-dimethyl p-toluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michaeller's ketone), 4 , 4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, and the like.

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

In the case of using such a photopolymerization initiation aid, the amount thereof is usually 10 mol or less, preferably 0.01 to 5 mol, per mol of the photopolymerization initiator. When the photopolymerization start adjuvant is used in such a content, it is preferable because the sensitivity of the colored photosensitive resin composition is higher and the productivity of the color filter is improved.

Solvent (E)

The solvent is not particularly limited, and various organic solvents used in the field of colored photosensitive resin compositions can be used.

Specific examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether and the like, and diethylene glycol dialkyl ethers such as diethylene glycol dimethyl. Ethylene glycol alkyl ether acetates such as ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, such as methyl cellosolve acetate and ethyl cellosolve acetate, and alkylene glycol alkyl ether acetate For example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate, methoxy pentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, etc. For example, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone and the like, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and the like, cyclic esters such as γ Butyrolactone etc. are mentioned. These solvents can be used individually or in combination of 2 types or more, respectively.

The solvent is preferably contained 50% by weight to 90% by weight, preferably 60% by weight to 85% by weight based on the total amount of the colored photosensitive resin composition including the same. When the content of the solvent is included in the range of 50% by weight to 90% by weight, it is preferable because the coating property is good.

Additive (F)

The colored photosensitive resin composition may further include an additive as necessary.

Examples of the additives include fillers, polymers other than binder resins, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents, organic acids, organic amino compounds, curing agents, and the like.

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

Examples of the other polymer include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, and the like.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane, etc. are mentioned.

Examples of the antioxidant include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and the like.

Examples of the ultraviolet absorber include 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.

Examples of the aggregation inhibitor include sodium polyacrylate and the like.

Examples of the organic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, capronic acid, diethylacetic acid, enanthic acid, caprylic acid, and the like. Such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, Aliphatic tricarboxylic acids such as methyl succinic acid, tetramethyl succinic acid, cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mezaconic acid, such as tricarboxylic acid, aconitic acid, camphoronic acid, etc. , Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumene acid, hemelitic acid, mesitylene acid, etc., aromatic dicarboxylic acids, phthalic acid, isophthalic acid, terephthalic acid, etc., aromatic polycarboxylic acids such as trimellitic acid, Mount Trimes, Melopanic acid, pyromellitic acid, and other acids.

Examples of such organic amino compounds include mono (cyclo) alkylamines such as n-propylamine, i-propylamine, n-butylamine, i-butylamine, s-butylamine, t-butyl amine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methylcyclohexylamine, 3- Methylcyclohexylamine, 4-methylcyclohexylamine and the like, di (cyclo) alkylamines such as methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, din-propylamine, dii- Propylamine, din-butylamine, dii-butylamine, dis-butylamine, dit-butylamine, din-pentylamine, din-hexylamine, methylcyclohexylamine, ethylcyclohexylamine, dicy Tri (cyclo) alkylamines such as clohexylamine, such as dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyldin-propyl Min, ethyldin-propylamine, trin-propylamine, trii-propylamine, trin-butylamine, trii-butylamine, tris-butylamine, trit-butylamine, trin-pentylamine Mono (cyclo) alkanolamines such as trin-hexylamine, dimethylcyclohexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine, such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 4-amino-1-cyclohexane Di (cyclo) alkanolamines, such as diethanolamine, din-propanolamine, dii-propanolamine, di n-butanolamine, dii-butanolamine, din-pentanolamine, din- Tri (cyclo) alkanolamines such as hexanolamine, di (4-cyclohexanol) amine, such as triethanolamine, trin-propanolamine, trii-propanolamine, trin-butanolamine, Amino (cyclo) alkanediols such as li-butanolamine, trin-pentanolamine, trin-hexanolamine, tri (4-cyclohexanol) amine, such as 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 4-amino-1,2-cyclohexanediol, 4-amino-1,3 -Cyclohexanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1, Amino group-containing cycloalkanethanols such as 3-propanediol, such as 1-aminocyclopentanonemethanol, 4-aminocyclopentanonmethanol, 1-aminocyclohexanonemethanol, 4-aminocyclohexanonemethanol, 4-dimethylaminocyclo Aminocarboxylic acids such as β-alanine, 2-amino, such as pentanemethanol, 4-diethylaminocyclopentanmethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol Tyrolic acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-amino valeric acid, 6-aminocaproic acid, 1-aminocyclopropanecarboxyl Aromatic amines such as acids, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid such as aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propyl Aniline, pi-propylaniline, pn-butylaniline, pt-butylaniline, 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, Aminobenzyl alcohols such as N-dimethylaniline, such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol and the like, aminophenols such as o Aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol, etc. Crude acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid and the like, and other acids.

The curing agent may be used for the purpose of curing the colored pattern by post-development heat treatment in patterning to improve its mechanical strength.

As said hardening | curing agent, the compound which can crosslink a binder resin by reacting with the carboxyl group in a binder polymer by heating, for example is mentioned, A coloring pattern is hardened by crosslinking a binder polymer. Moreover, the compound which can be homopolymerized by heating can also be used, A color pixel etc. are hardened by homopolymerization. As such a compound, an epoxy compound, an oxetane compound, etc. are mentioned, for example.

Examples of the epoxy compound include epoxy resins such as bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, besphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, novolac epoxy resins, other aromatic epoxy resins, Brominated derivatives of these epoxy resins such as cycloaliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidylamine resins, and epoxidized oils; Aliphatic, cycloaliphatic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof; The epoxidation material of the (co) polymer of butadiene, the epoxidation material of the (co) polymer of isoprene, the (co) polymer of glycidyl (meth) acrylate, a triglycidyl isocyanurate, etc. are mentioned.

Examples of the oxetane compound include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, cyclohexane dicarboxylic acid bis oxetane and the like.

When including the said hardening | curing agent in a coloring photosensitive resin composition, the compound which can cause ring-opening polymerization of the epoxy group in an epoxy compound, and the oxetane skeleton in an oxetane compound can be used together. As such a compound, polyhydric carboxylic acid, polyhydric carboxylic anhydride, etc. are mentioned, for example, These can be used individually or in combination of 2 or more types, respectively.

Examples of the polyhydric carboxylic acid include aromatic polyhydric carboxylic acids, such as phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimethyltriic acid, 1,4,5,8-naphthalenetetracarboxylic Aliphatic polyhydric carboxylic acids such as acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic Alicyclic polyhydric carboxylic acids such as acid, maleic acid, fumaric acid, itaconic acid, such as hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentane Tricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and the like.

Examples of the polyhydric carboxylic anhydride include aromatic polyhydric carboxylic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and the like. , Aliphatic polyhydric carboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarvallylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic acid Alicyclic polyhydric carboxylic anhydrides such as dianhydrides such as hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexane Ester group-containing carboxylic acids such as tricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic anhydride, nad anhydride radish Water, such as ethylene glycol bistrimellitic acid, glycerin tristrimellitic anhydride, and the like.

The colored photosensitive resin composition of this invention which has said composition can be manufactured by the following method, for example. The coloring agent (A) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the coloring material is about 0.2 µm or less. Under the present circumstances, a pigment dispersant is used as needed and some or all of binder resin (B) may be mix | blended. The remaining amount of the binder resin (B), the photopolymerizable compound (C) and the photopolymerization initiator (D), other components used if necessary, and additional solvents, if necessary, in the obtained dispersion (hereinafter sometimes referred to as a mill base). When (E) is added and fully mixed, the coloring photosensitive resin composition which concerns on this invention can be obtained.

This invention provides the color filter manufactured using the coloring photosensitive resin composition which has the above-mentioned composition which concerns on this invention.

Hereinafter, the method of manufacturing a color filter using the said coloring photosensitive resin composition is demonstrated.

The method for manufacturing a color filter according to the present invention includes a coating film forming step of forming a coating film by coating the colored photosensitive resin composition according to the present invention on a substrate, and using microwaves in a region where a coloring pattern of the coating film is to be formed. An exposure step of irradiating an ultra-short wavelength laser having a wavelength of 300 nm or less with a long exposure machine, and a developing step of forming a colored pattern by removing an unexposed coating area in the exposure step.

The coating film forming step is to form a coating film by coating a colored photosensitive resin composition on a substrate, the substrate is a glass substrate, a silicon wafer and a plastic substrate such as polyethersulfone (PES) or polycarbonate (PC) It may be a plate and the like, the kind is not particularly limited.

The coating may be carried out using a coating apparatus such as a roll coater, spin coater, slit and spin coater, slit coater (hereinafter also referred to as 'die coater'), inkjet, or the like.

The thickness at the time of coating can be formed in various thicknesses without limitation, it is preferable to coat at 0.5 ~ 1.0um, it is important to make the coating thickness uniform thickness over the entire surface. When the thickness at the time of the coating is included in the above range, the surface smoothness of the coating film is excellent, and the curing is faster, thereby improving the production speed.

When the coating of the colored photosensitive resin composition is completed, volatile components such as solvents are removed through preliminary drying to obtain a coating film. The preliminary drying may be performed at 100 to 120 ° C. for 1 to 30 minutes. When the pre-drying is made within the above range, volatile components such as solvents are quickly removed to obtain a good dry coating film.

The exposure step is a step of irradiating an ultrashort wavelength laser of 300 nm or less with an ultrashort wavelength exposure machine having a numerical aperture of 0.6 or more to a region where a colored pattern of the coating film is to be formed using a mask.

Lasers having a wavelength of less than 300 nm can mainly use known KrF (248 nm) scanners. The KrF scanner is an exposure machine in which a laser oscillated using a krypton fluoride source has a wavelength band of 248 nm.

When the exposure is performed to the region where the coloring pattern of the coating film formed in the above-described coating film forming step is to be formed using the mask, crosslinking and photocuring are caused by the photopolymerization initiator only at the portion where the light is transmitted by the mask.

The exposure is not necessarily limited, but the exposure dose is preferably 200 mJ / cm 2 or less, more preferably 50 to 150 mJ / cm 2. When the exposure amount exceeds 200mJ / cm 2, there is a disadvantage in that the overall process time due to the delay in the exposure process may be increased and the life of the exposure machine may be shortened due to distortion in the lens inside the exposure machine.

The developing step is a step of forming a colored pattern by removing the unexposed coating area in the exposing step.

The developing solution used to remove the non-exposure end coating region in the developing step may be one commonly used in the art, and is usually an aqueous solution containing an alkaline compound and a surfactant.

The alkaline compound contained in the developer 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, hydrogen carbonate Sodium, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like. In addition, specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine and the like. These inorganic and organic alkaline compounds can be used individually or in combination of 2 or more types, respectively.

It is preferable that the density | concentration of the alkaline compound in the said developing solution is 0.01 to 10 weight%, More preferably, it is 0.03 to 5 weight%.

As surfactant contained in the said developing solution, you may use any of a nonionic surfactant, anionic surfactant, or cationic surfactant. Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene-oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like. Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate; Alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; Alkyl aryl sulfonates, such as sodium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate, etc. are mentioned. Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or quaternary ammonium salts. These surfactant can be used individually or in combination of 2 or more types, respectively.

The concentration of the surfactant in the developer may be 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight.

After the development step, the color filter having a colored pattern may be subjected to post-drying for about 1 minute to 60 minutes at 150 to 230 ° C. The post-drying is to completely remove the residual solvent on the pattern and to harden the embodied pattern.

This invention provides the color filter manufactured by the manufacturing method of the color filter for solid-state image sensors mentioned above.

The color filter has a finely colored coloring pattern as the ultrashort plate exposure machine is used in its manufacturing process. In particular, the colored pattern obtained by the present invention can be significantly less than 1.4㎛, in particular less than 1.0㎛ than the current commercially available 2.2㎛, so that the color filter having the refined coloring pattern can be usefully applied to the solid-state image sensor have.

The present invention provides a solid state image pickup device including the color filter. The solid-state imaging device may adopt a configuration known to those skilled in the art, except that the solid-state imaging device is provided with the color filter according to the present invention.

Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by an Example. In addition, "%" and "part" which show content in a following example mean the weight% or weight part, unless there is particular notice.

≪ Example 1 >

The colored photosensitive resin composition is based on 100% of the total solids of the components excluding the solvent. Pigment GREEN 36 Pigment 31.50% and C.I. After obtaining a mill base consisting of 13.50% of Solvent Yellow Dye No. 82 and 9.07% of a polyester-based dispersant, a binder resin (method having a weight average molecular weight of 20,000 and an acid value of 120 mgKOH / g; 19% copolymer of benzyl methacrylate), 7.36% photopolymerizable compound (Dipentaerythritol pentaacrylate (manufactured by TOAGOSEI Co., Ltd.)), 7.36% pentaerythritol triacrylate (manufactured by Miwon Corporation), eta as photopolymerization initiator Non-1- [9-ethyl-6- (2-methyl-4tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02; Ciba Specialty Chemical Solvent) in 10%, 1-hydroxy cyclohexyl phenyl ketone (Irgacure 184; manufactured by Ciba Specialty Chemical) 2%, 0.22% of 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane as an adhesion promoter Phosphorus Propylene Glycol Methyl Ether Acetate Added and Mixed to Color Photosensitive Resin A hydrous product was prepared.

<Example 2>

The colored photosensitive resin composition is based on 100% of the total solids of the components excluding the solvent. Pigment GREEN 36 Pigment 20.12% and C.I. Pigment Yellow Dye No. 139 2.25%, C.I. After obtaining a mill base consisting of 13.50% of Solvent Yellow 82 and 9.07% of a polyester-based dispersant, methacrylic acid and benzyl having a binder resin (weight average molecular weight of 20,000 and an acid value of 120 mgKOH / g) were added to the mill base under stirring at 23 ° C. Copolymer of methacrylate) 19%, photopolymerizable compound (Dipentaerythritol pentaacrylate (manufactured by TOAGOSEI Co., Ltd.)) and 7.36% pentaerythritol triacrylate (manufactured by Miwon Corporation), ethanone as photopolymerization initiator -1- [9-ethyl-6- (2-methyl-4tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02; Ciba Specialty Chemical 10%, 1-hydroxy cyclohexyl phenyl ketone (Irgacure 184; manufactured by Ciba Specialty Chemical Co., Ltd.) 2%, solvent (2 (3,4epoxycyclohexyl) -ethyltrimethoxysilane 0.22% as an adhesion promoter) Propylene glycol methyl ether acetate is added, and then mixed to color the photosensitive resin composition It was prepared.

Comparative Example 1

The colored photosensitive resin composition is based on 100% of the total solids of the components excluding the solvent. After obtaining a millbase consisting of 45.00% Pigment GREEN No. 36 pigment, 10.08% polyester-based dispersant, and a binder resin (weight average molecular weight 20,000, acid value of 120mgKOH / g and methacrylic acid) Benzyl methacrylate copolymer) 15.00%, photopolymerizable compound (Dipentaerythritol pentaacrylate (manufactured by TOAGOSEI Corporation)) 8.67%, pentaerythritol triacrylate (manufactured by Miwon Corporation), eta as photopolymerization initiator Non-1- [9-ethyl-6- (2-methyl-4tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02; Ciba Specialty Chemical Solvent) in 10%, 1-hydroxy cyclohexyl phenyl ketone (Irgacure 184; manufactured by Ciba Specialty Chemical) 2%, 0.22% of 2- (3,4 epoxycyclohexyl) -ethyltrimethoxysilane as an adhesion promoter Phosphorus Propylene Glycol Methyl Ether Acetate Added and Mixed to Color Photosensitive Resin The composition was prepared.

Comparative Example 2

The colored photosensitive resin composition is based on 100% of the total solids of the components excluding the solvent. Pigment GREEN dye No. 36 31.50% and C.I. After obtaining a millbase consisting of 13.50% Pigment Yellow No. 150, 9.07% polyester-based dispersant, methacrylic acid and benzyl having a binder resin (weight average molecular weight of 20,000, acid value of 120mgKOH / g and benzyl) to the millbase under stirring at 23 ℃ Copolymer of methacrylate) 19%, photopolymerizable compound (Dipentaerythritol pentaacrylate (manufactured by TOAGOSEI Co., Ltd.)) and 7.36% pentaerythritol triacrylate (manufactured by Miwon Corporation), ethanone as photopolymerization initiator -1- [9-ethyl-6- (2-methyl-4tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02; Ciba Specialty Chemical 10%, 1-hydroxy cyclohexyl phenyl ketone (Irgacure 184; manufactured by Ciba Specialty Chemical Co., Ltd.) 2%, solvent (2 (3,4epoxycyclohexyl) -ethyltrimethoxysilane 0.22% as an adhesion promoter) Propylene glycol methyl ether acetate is added and mixed to form a colored photosensitive resin It was prepared.

Experimental Example

After applying the colored photosensitive composition obtained in the above Examples and Comparative Examples by spin coating on a surface of a 4 inch size Si-wafer in a clean room at 23 ° C., it was dried at 90 ° C. for 90 seconds to volatilize the volatile components. A colored photosensitive composition layer was formed. After cooling to 23 ° C., the formed colored photosensitive composition layer was exposed to light using a KrF scanner exposure machine (248 nm). Subsequently, the developer (aqueous solution containing 0.2 parts by weight of tetramethylammonium hydroxide) was developed for 60 seconds using a puddle at 23 ° C., washed with pure water, and then heated at 220 ° C. for 180 seconds to form a colored pattern.

The transmittance | permeability of the obtained coloring pattern is shown to FIGS. 1-4, respectively.

As shown in Figures 1 to 4, Figures 1 and 2 showing the results of Example 1 and Example 2 according to the present invention in Figures 3 and 4 showing the results of Comparative Example 1 and Comparative Example 2 In comparison, there are no disadvantages such as color purity or color mixing because there are no impurity peaks in the required wavelength range.

1 is a graph of transmittance of the colored photosensitive resin composition of Example 1. FIG.

2 is a graph of transmittance of the colored photosensitive resin composition of Example 2. FIG.

3 is a graph of transmittance of the colored photosensitive resin composition of Comparative Example 1. FIG.

4 is a graph of transmittance of the colored photosensitive resin composition of Comparative Example 2. FIG.

Claims (12)

As colored photosensitive resin composition for color filter manufacture using the ultra short wavelength exposure machine of 300 nm or less which consists of a coloring agent, binder resin, a photopolymerizable compound, a photoinitiator, and a solvent, The colorant comprises a pigment and a dye, The said photoinitiator contains the photoinitiator other than an oxime ester system photoinitiator and the said oxime ester system photoinitiator, The coloring photosensitive resin composition for manufacturing the color filter of the solid-state image sensor using the ultra short wavelength exposure machine of 300 nm or less characterized by the above-mentioned. The coloring photosensitive resin composition for manufacturing a color filter of a solid-state imaging device using an ultra-short wavelength exposure device of 300 nm or less, characterized in that the dye is selected from color index solvents (C.I. Solvent). The coloring photosensitive resin composition for manufacturing a color filter of a solid-state imaging device using an ultra-short wavelength exposure device of 300 nm or less, characterized in that the pigment is selected from color index pigments (C.I. Pigment). The method according to claim 1, wherein the colored photosensitive resin composition is a colored photosensitive resin composition colored with Green, the pigment comprises a color index pigment (CI Pigment) Green, the dye is a color index solvent ( CI Solvent) The coloring photosensitive resin composition for color filter manufacture of the solid-state image sensor using the ultra short wavelength exposure machine of 300 nm or less characterized by including yellow. The pigment of claim 1, wherein the pigment is CI Pigment Green No. 7, CI Pigment Green No. 36 and Color Index Pigment Green. At least one selected from No. 58, wherein the dye includes color index solvent (Yellow) 82; color for manufacturing color filters of a solid-state imaging device using an ultra-short wavelength exposure device of 300 nm or less. Photosensitive resin composition. The method according to claim 1, wherein the colored photosensitive resin composition is a colored photosensitive resin composition colored in red, the pigment comprises a color index pigment (CI Pigment) Red, the dye is a color index solvent ( CI Solvent), The coloring photosensitive resin composition for color filter manufacture of the solid-state image sensor using the ultra short wavelength exposure machine of 300 nm or less. The method according to claim 1, wherein the coloring photosensitive resin composition is a coloring photosensitive resin composition that is colored blue, the pigment comprises a color index pigment (CI Pigment) Blue, the dye is a color index solvent ( CI Solvent), The coloring photosensitive resin composition for color filter manufacture of the solid-state image sensor using the ultra short wavelength exposure machine of 300 nm or less. The method of claim 1, wherein the other photopolymerization initiator is an active radical generator, a sensitizer and an acid selected from acetophenone photopolymerization initiator, benzoin photopolymerization initiator, benzophenone photopolymerization initiator, thioxanthone photopolymerization initiator or triazine photopolymerization initiator. The coloring photosensitive resin composition for color filter manufacture of the solid-state image sensor using the ultra short wavelength exposure machine of 300 nm or less characterized by including at least 1 sort (s) chosen from the group which consists of a generator. The method according to claim 1, wherein the oxime ester photopolymerization initiator is contained in a weight fraction of 1 to 99% by weight based on the total amount of the photopolymerization initiator including the same, The said photoinitiator is 1-50 weight% with respect to solid content in a coloring photosensitive resin composition, The coloring photosensitive resin composition for color filter manufacture of the solid-state image sensor using the 300 nm or less ultrashort wavelength exposure machine characterized by the above-mentioned. The colored photosensitive resin composition for manufacturing a color filter of a solid-state imaging device using the ultra short wavelength exposure machine of 300 nm or less, wherein the ultra short wavelength exposure machine of 300 nm or less is a KrF scanner exposure machine (248 nm). A color filter comprising a colored pattern obtained by coating the colored photosensitive resin composition according to any one of claims 1 to 10 onto a substrate and then exposing and developing in a predetermined pattern using an ultra-short wavelength exposure device of 300 nm or less. The color image sensor of Claim 11 containing the color filter.

Images