KR102440063B1 - Colored photosensitive composition, color filter and imaging device - Google Patents

Abstract

The colored photosensitive composition of the embodiments of the present invention includes an alkali-soluble resin having an acid value of 40 to 80 mgKOH/g, a photopolymerizable compound, a photopolymerization initiator, a colorant, and a solvent. Using the colored photosensitive composition, it is possible to form a high-resolution, highly reliable color filter for an image pickup device through KrF exposure.

Description

A coloring photosensitive composition, a color filter, and an imaging element TECHNICAL FIELD

The present invention relates to a colored photosensitive composition, a color filter, and an image pickup device. More specifically, it relates to a colored photosensitive composition, a color filter formed therefrom, and an image pickup device including the color filter.

For example, in an image display device such as a liquid crystal display (LCD) device using a separate light source such as a backlight, a color filter is used to realize a desired color for each pixel. The color filter may be formed by applying and patterning a photosensitive composition including a colorant corresponding to each pixel of RGB.

In order to form the above-described color filter, the photosensitive resin composition including the colorant may be exposed to light, and for example, the unexposed portion may be removed through a developer (in the case of a negative tone composition). For example, for a developing process using an alkali solution, the photosensitive resin composition may include an alkali-soluble resin as a binder resin.

Meanwhile, even in the case of an imaging device (eg, a solid-state imaging device) that converts an image taken through light energy into electrical information, a color filter may be included under the lens. For example, in the case of a CMOS image sensor (CIS), a fine-pitch color filter patterned with a higher resolution than a color filter corresponding to a pixel of a general display device described above is employed.

In the case of the color filter for CIS, a light source having a shorter wavelength may be used for fine patterning. In this case, it is necessary to redesign the components in order to improve pattern characteristics such as residue or residual film characteristics, adhesiveness and degree of curing together with the developability of the photosensitive resin composition.

For example, Korean Patent Laid-Open Publication No. 10-2009-0072754 discloses a composition for a color filter including a pigment and a binder resin, but is difficult to be applied to the above-described color filter for an image pickup device.

Korean Patent Publication No. 10-2009-0072754

One object of the present invention is to provide a colored photosensitive composition having improved resolution and reliability and pattern reliability.

One object of the present invention is to provide a color filter formed from the colored photosensitive composition.

An object of the present invention is to provide an imaging device including the color filter.

1. Alkali-soluble resin having an acid value of 40 to 80 mgKOH/g; photopolymerizable compounds; photoinitiator; coloring agent; and a solvent, the colored photosensitive composition for KrF.

2. The colored photosensitive composition for KrF according to the above 1, wherein the alkali-soluble resin comprises a carboxylic acid-containing unit and a unit represented by the following Chemical Formula 1:

[Formula 1]

(In Formula 1, Ra is hydrogen or a methyl group).

3. The colored photosensitive composition for KrF according to the above 1, wherein the photopolymerizable compound contains an ethylene oxide (EO) linker and an ethylenically unsaturated polymerizable group.

4. The colored photosensitive composition for KrF according to the above 3, wherein the photopolymerizable compound comprises an ethoxylated (meth)acrylate-based compound.

5. In the above 4, the photopolymerizable compound is composed of ethoxylated pentaerythritol tetra (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate and ethoxylated dipentaerythritol hexa (meth) acrylate A colored photosensitive composition for KrF, comprising at least one compound selected from the group.

6. The method of 1 above, based on the total weight of the composition, 1 to 10 parts by weight of the alkali-soluble resin; 0.5 to 5 parts by weight of the photopolymerizable compound; 0.1 to 5 parts by weight of the photopolymerization initiator; 30 to 60 parts by weight of the colorant; and 30 to 60 parts by weight of the solvent, a colored photosensitive composition for KrF.

7. A color filter comprising a colored pattern formed of the colored photosensitive composition for KrF of any one of 1 to 6 above.

8. An imaging device including the color filter of 7 above.

9. The imaging device according to 8 above, including a CMOS image sensor (CIS).

The colored photosensitive composition according to the embodiments of the present invention includes an alkali-soluble resin having an acid value of about 40 to 80 mgKOH/g, and uses an alkali-soluble resin having a relatively low acid value to improve pattern remaining film characteristics and to perform exposure and development processes The residue can then be reduced.

In addition, the photosensitive composition is applied for ultra-short exposure of 300 nm or less, such as a KrF light source, so that developability of a relatively low acid value alkali-soluble resin can be secured.

In some embodiments, the colored photosensitive composition may include an ethylenically unsaturated photopolymerizable compound including an ethylene oxide (EO) group. Accordingly, it is possible to supplement the developability of the low acid value alkali-soluble resin and further improve pattern adhesion.

According to embodiments of the present invention, there is provided a colored photosensitive resin composition comprising an alkali-soluble resin having an acid value of about 40 to 80 mgKOH/g. The colored photosensitive composition is provided as a composition for KrF, so that a high-resolution color filter and image pickup device having improved developability and pattern characteristics can be manufactured.

Hereinafter, embodiments of the present invention will be described in detail.

<Colored photosensitive composition>

The colored photosensitive composition according to embodiments of the present invention may be a resin composition having developability. According to exemplary embodiments, the colored photosensitive composition includes an alkali-soluble resin having an acid value of about 40 to 80 mgKOH, a photopolymerizable compound, a photoinitiator, a colorant and a solvent, and may further include other additives.

Alkali-soluble resin

The colored photosensitive composition according to exemplary embodiments may be used to form a resin pattern through exposure and development processes, and may include an alkali-soluble resin that may be selectively removed by the developing process. The alkali-soluble resin is included to impart developing properties and may be provided as a binder resin of the colored photosensitive composition.

For example, the alkali-soluble resin may include a polymer of an ethylenically unsaturated monomer having a carboxy group. Non-limiting examples of the ethylenically unsaturated monomer having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids, such as fumaric acid, mesaconic acid, and itaconic acid, and these anhydrides; and polymer mono(meth)acrylates having a carboxyl group and a hydroxyl group at both terminals, such as ω-carboxypolycaprolactone mono(meth)acrylate. These may be used alone or in combination of two or more. In a preferred embodiment, acrylic acid and/or methacrylic acid may be used.

The ethylenically unsaturated monomer having a carboxy group may be copolymerized with other monomers to be described later and included in the alkali-soluble resin as a carboxylic acid-containing unit. For example, the acid value of the alkali-soluble resin may be adjusted by the content or molar ratio of the carboxylic acid-containing unit, so that the developability of the alkali-soluble resin may be adjusted.

The alkali-soluble resin may be polymerized by further using at least one additional monomer copolymerizable with the ethylenically unsaturated monomer having a carboxy group. Non-limiting examples of the other monomers include styrene, vinyltoluene, methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinyl aromatic vinyl compounds such as benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether; N-cyclohexyl maleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m -N-substituted maleimide compounds, such as methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, and N-p-methoxyphenylmaleimide; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth)acrylates such as sec-butyl (meth)acrylate and t-butyl (meth)acrylate; Alicyclic rings such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate group (meth)acrylates; aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane; 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. of unsaturated oxetane compounds; Unsaturated oxirane, such as glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and methylglycidyl (meth)acrylate compounds and the like. These can be used individually or in mixture of 2 or more types.

According to exemplary embodiments, the alkali-soluble resin may have an acid value of about 40 to 80 mgKOH/g. As used herein, the term "acid value" may mean a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer.

When the acid value of the alkali-soluble resin is less than about 40 mgKOH/g, developability is excessively lowered, so it may be difficult to form a pattern having a desired fine dimension, and pattern adhesion may be deteriorated. When the acid value of the alkali-soluble resin exceeds about 80 mgKOH/g, pattern residual film properties are deteriorated, and residues are generated around the exposed portion, making it difficult to implement high-resolution, fine-dimensional patterns as well.

Therefore, according to exemplary embodiments, the developability may be supplemented by adjusting the acid value within the above-described range, but using KrF (wavelength 248 nm) as a light source for exposure. Therefore, when the acid value exceeds about 80 mgKOH/g (for example, more than 100 mgKOH/g), film loss and residue phenomena are suppressed, but high-resolution, fine-dimensional patterns can be formed without pattern defects by using a microwave light source. .

Preferably, the acid value of the alkali-soluble resin may be adjusted to about 60 to 80 mgKOH/g in consideration of developability and pattern reliability.

Since the alkali-soluble resin is maintained at a relatively low acid value, the content or molar ratio of other repeating units (eg, derived from the above-described additional monomer) other than the carboxylic acid-containing unit may be relatively increased.

For example, the content of units related to pattern hardness and durability, such as aromatic units and heterocyclic units, may be relatively increased, so that mechanical reliability of a photocurable pattern or a colored pattern formed from the colored photosensitive resin composition may be further improved.

In some embodiments, the alkali-soluble resin may further include a unit represented by the following Chemical Formula 1 together with the carboxylic acid-containing unit.

[Formula 1]

In Formula 1, Ra may be hydrogen or a methyl group. As shown in Formula 1, the unit can supplement the developability of the alkali-soluble resin by including a hydroxyl group, and adhesion with the substrate can be further improved.

The carboxylic acid-containing unit and the unit represented by the following Chemical Formula 1 may each be included as a repeating unit of the copolymer.

The weight average molecular weight of the alkali-soluble resin (eg, measured by gel permeation chromatography (GPC) using polystyrene as a standard material) may be about 3,000 to 50,000, preferably 5,000 to 30,000. Within the molecular weight range, film loss in the developing process may be suppressed and pattern stability may be improved.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the alkali-soluble resin may be about 1.5 to 6.0, preferably about 1.8 to 3.0 in consideration of development and pattern stability.

The content of the alkali-soluble resin is not particularly limited, but, for example, may be about 1 to 10 parts by weight, preferably about 3 to 10 parts by weight, among 100 parts by weight of the total composition. Within the above range, coating properties and film stability of the composition may be sufficiently secured.

photopolymerizable compound

In some exemplary embodiments, the colored photosensitive composition is further cross-linked or polymerized by an exposure process to improve the mechanical properties of the colored pattern or further include a photopolymerizable compound to complement the developability of the alkali-soluble resin. You may.

According to exemplary embodiments, the photopolymerizable compound may include an ethylene oxide (EO) linker and an ethylenically unsaturated polymerizable group. For example, the photopolymerizable compound may include an ethoxylated (meth)acrylate-based compound. Preferably, the photopolymerizable compound may include a trifunctional or more ethoxylated (meth)acrylate-based compound.

As used herein, the term "(meth)acryl-" is used to refer to "methacryl-", "acryl-", or both.

The photopolymerizable compound may include, for example, a (meth)acrylate group radiated from the molecular center by the EO linker. For example, the photopolymerizable compound may include a plurality of (meth)acrylate groups, and the EO linker may be connected and emitted for each (meth)acrylate group.

Accordingly, the surface area to which the hydrophilic group of the photopolymerizable compound can be contacted increases, thereby supplementing the developability of the alkali-soluble resin. In addition, the adhesion to the substrate and the pattern profile (eg, pattern sidewall straightness) are improved, so that a photocurable pattern with high reliability can be formed.

In one embodiment, in consideration of the radiation effect of the (meth)acrylate group through the above-described EO linker, the photopolymerizable compound may include a tetrafunctional or more ethoxylated (meth)acrylate-based compound.

As a non-limiting example of the photopolymerizable compound described above, ethoxylated pentaerythritol tetra (meth) acrylate (eg, the following formula 2), ethoxylated trimethylol propane tri (meth) acrylate (eg, the following Formula 3), ethoxylated dipentaerythritol hexa(meth)acrylate (for example, following formula 4), etc. are mentioned. These may be used alone or in combination of two or more.

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 2 to 4, R ₁ may be hydrogen or a methyl group. R ₂ may be hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. The alkyl group may be substituted with a hydroxyl group. n may be an integer from 1 to 5.

In Formulas 2 to 4, R ₁ and n are described in common, but they do not mean the same, and each may be independently controlled.

In some embodiments, as the photopolymerizable compound, in addition to the ethoxylated (meth)acrylate-based compound, other monofunctional monomers, difunctional monomers or polyfunctional monomers having photopolymerization may be used, and sufficient curing properties are realized For this purpose, a bifunctional or more functional monomer may be used.

Examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone and the like. Examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bisphenol A of bis(acryloyloxyethyl)ether, 3-methylpentanediol di(meth)acrylate, and the like. Examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Erythritol hexa(meth)acrylate etc. are mentioned. These may be used alone or in combination of two or more.

In some embodiments, the photopolymerizable compound may be substantially composed of only the ethoxylated (meth)acrylate-based compound in order to improve the above-described developability and pattern characteristics.

The content of the photopolymerizable compound may be, for example, about 0.5 to 5 parts by weight based on 100 parts by weight of the total composition. Within the above range, the strength and mechanical reliability of the photocurable pattern or the coloring pattern may be improved without degrading the color reproducibility of the colorant.

photopolymerization initiator

When the above-mentioned photopolymerizable compound is included, the colored photosensitive composition may further include a photopolymerization initiator to crosslink or polymerize the photopolymerizable compound by an exposure process.

For example, the photopolymerization initiator may include at least one compound selected from an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a biimidazole-based compound, a thioxanthone-based compound, an oxime ester-based compound, and the like. have. Preferably, the photopolymerization initiator may include an oxime ester-based compound.

For example, the oxime ester compound is o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, 1,2-octadione,-1-(4-phenylthio)phenyl,- 2-(o-benzoyloxime), ethanone,-1-(9-ethyl)-6-(2-methylbenzoyl-3-yl)-,1-(o-acetyloxime), and the like; Products include CGI-124 (Chiba Geigisa), CGI-224 (Ciba Geigisa), Irgacure OXE-01 (BASF), Irgacure OXE-02 (BASF), N-1919 (Adecas), NCI-831 ( adecasa) and the like.

In one embodiment, in addition to the photopolymerization initiator, a photopolymerization initiator adjuvant may be used to improve composition sensitivity.

For example, as said photopolymerization initiation adjuvant, an amine compound, a carboxylic acid compound, or the organic sulfur compound which has a thiol group, etc. are mentioned.

Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethylamino 2-ethylhexyl benzoate, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler's ketone), 4,4'-bis(diethyl) amino) benzophenone; and the like.

Examples of the carboxylic acid compound include aromatic phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, Dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

Examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropanetris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyl rate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), and the like. .

The content of the photopolymerization initiator may be, for example, about 0.1 to 5 parts by weight of the total 100 parts by weight of the colored photosensitive composition. Within the above range, high resolution can be effectively implemented while improving crosslinking properties by exposure.

coloring agent

The colored photosensitive composition according to exemplary embodiments may include at least one pigment, a dye, or a mixture thereof as a colorant.

As the pigment, organic or inorganic pigments commonly used in the art may be used. For example, specific examples of the organic pigment include a water-soluble azo pigment, an insoluble azo pigment, a phthalocyanine pigment, a quinacridone pigment, an isoindolinone pigment, an isoindoline pigment, a perylene pigment, a perinone pigment, Dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, prabanthrone pigments, pyranthrone pigments, diketopyrroropyrrole A pigment etc. are mentioned.

The inorganic pigment may include a metal compound such as a metal oxide or a metal complex salt, for example, an oxide or complex of a metal such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, etc. A metal oxide etc. are mentioned.

As a specific example, the organic pigment and inorganic pigment may include compounds classified as pigments in the color index (published by The Society of Dyers and Colorists), and pigments of the color index (C.I.) numbers listed below may be used. have.

The above C.I. Among the pigment pigments, for example, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 122, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Violet 23, C.I. Pigment Blue 15:3, Pigment Blue 15:6, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58 or the like may be used. These may be used alone or in combination of two or more.

In some embodiments, a green-based pigment may be used as the colorant in consideration of the KrF light source.

In some embodiments, a pigment dispersant may be included together for uniform dispersion in the composition of the pigment. For example, the pigment may be dispersed in the pigment dispersant to form a pigment dispersion having a uniform particle size, and the pigment dispersion may be mixed with the colored photosensitive composition.

Examples of the above pigment dispersant include acrylate-based dispersants such as BMA (butyl methacrylate) or DMAEMA (N,N-dimethylaminoethyl methacrylate), polyester-based dispersants, polyamine-based dispersants, (meth)acrylic acid- and resin-type surfactants such as styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinyl pyrrolidone, and the like. These can be used individually or in combination of 2 or more types, respectively.

The dye may be selected in consideration of solubility in organic solvents and alkali developer, solvent resistance, and stability over time.

As the dye, acid dyes having an acidic group such as sulfonic acid or carboxylic acid or derivatives thereof, azo-based, xanthene-based, phthalocyanine-based acidic dyes, and derivatives thereof may be used.

The dye may include, for example, a compound classified as a dye in a color index (published by The Society of Dyers and Colorists), or a known dye described in a dyeing note (color dyes).

As a specific example of the dye, C.I. Solvent-based, also, C.I. Acid-based, C.I. Direct, C.I. Modanto-based dyes may be mentioned, and these may be used alone or in combination of two or more.

The content of the colorant is not particularly limited, but may be included in an amount of about 30 to 60 parts by weight, preferably 30 to 50 parts by weight, of a total of 100 parts by weight of the colored photosensitive resin composition. Desired color reproducibility may be realized without causing external leakage of the colorant within the above range.

other additives

In some embodiments, the colored photosensitive composition may further include an additive for improving film properties such as coatability, adhesion, and hardness. For example, a curing agent, a dispersing agent, a wetting agent, a silane coupling agent, an anti-agglomeration agent, and the like may be added.

The curing agent may be included to enhance strength through deep hardening of the coloring pattern, for example, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, or an oxetane compound.

As the dispersant, a silicone-based surfactant, a fluorine-based surfactant, a silicone-based surfactant having a fluorine atom, and the like may be used.

As the wetting agent, for example, glycerin, diethylene glycol, ethylene glycol and the like may be used.

As the silane coupling agent, for example, aminopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, or the like may be used.

Examples of the aggregation inhibitor include polyacrylic acid or a salt thereof.

The content of the additive is not particularly limited, but may be included in an amount of about 0.01 to 1 part by weight of the total 100 parts by weight of the colored photosensitive resin composition. Within the above range, it is possible to improve the pattern characteristics without impairing the curing and developing characteristics of the alkali-soluble resin and the photopolymerizable compound.

solvent

The solvent sufficiently dissolves the alkali-soluble resin and the photopolymerizable compound described above, and may include an organic solvent that does not cause precipitation of the colorant.

Examples of the solvent include glycol ether, alcohol (methanol, ethanol, isopropanol, butanol, propylene glycol, methoxy alcohol, etc.), ketone (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, diethyl ketone, etc.) propyl ketone, etc.), acetate (methyl acetate, ethyl acetate, butyl acetate, propylene glycol methoxy acetate, etc.), cellosolve (methyl cellosolve, ethyl cellosolve, propyl cellosolve, etc.), hydrocarbon-based (normal hexane, normal heptane, benzene, toluene, xylene, etc.) may be used, and these may be used alone or in combination of two or more.

For example, in consideration of applicability and dryness, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, 3-ethoxypropionate ethyl, etc. may be used. .

The solvent may be included in the remaining amount excluding the components of the above-described composition, for example, may be included in about 30 to 60 parts by weight of the total 100 parts by weight of the composition. When the above range is satisfied, the coating film may be easily formed through a coating method using a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater or a curtain flow coater), inkjet, or the like.

<Color filter and image pickup device>

A colored pattern may be formed using the above-described colored photosensitive composition, and the colored pattern may be used as, for example, a color filter of an imaging device, as will be described later.

Embodiments of the present invention also provide a method of manufacturing a color filter using the above-described colored photosensitive composition.

For example, the color photosensitive composition according to the above-described exemplary embodiments may be applied on a support and dried to form a preliminary colored film.

The support may include a photoelectric conversion device substrate (eg, a silicon substrate for CCD or CMOS) used in a solid-state image pickup device. The support may include a black matrix or black stripe for isolating each pixel.

The coating process may include, for example, a coating or printing process such as roll coating, spin coating, slit coating, and inkjet printing.

Thereafter, the color pattern corresponding to each pixel may be formed by exposing and developing the preliminary color layer.

The exposure process may include exposure to ultra-short wavelength laser of 300 nm or less using a mask selectively exposing the pixel region. Thereafter, the colored pattern may be formed by selectively removing the non-exposed area using a developer.

In example embodiments, the exposure process may include KrF (248 nm) exposure. Accordingly, remarkably improved resolution than the I-line exposure can be realized, and developability and pattern characteristics can be improved together through the design of the above-described alkali-soluble resin and photopolymerizable compound.

The developer may include, for example, an inorganic or organic alkaline compound. 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. Examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropyl An amine, diisopropylamine, ethanolamine, etc. are mentioned. These can be used individually or in combination of 2 or more types.

After the developing process, for example, a post-baking process may be performed at 150 to 230°C.

The colored pattern manufactured by the above-described process may act as a color filter of a solid-state imaging device such as a CIS.

According to exemplary embodiments, an imaging device including the color filter is provided. The imaging device may be, for example, a CIS device.

The imaging device may include a support including a semiconductor device or a photoelectric conversion device and a microlens, and the color filter may be disposed between the support and the microlens.

As with the CIS device, in the case of a high-resolution imaging device, short-wavelength exposure such as KrF needs to be performed, and since the dimensions of the color filter are miniaturized, pattern residue, adhesion, curability, etc. need to be more finely controlled.

As described above, since the colored photosensitive composition according to the exemplary embodiments includes an alkali-soluble resin having a relatively low acid value, film loss and residues are significantly reduced, and the content or molar ratio of repeating units other than the carboxylic acid-containing unit is It can be increased to represent a more improved hardness. In addition, developability can be supplemented through a combination of a KrF light source and a photopolymerizable compound.

Accordingly, mechanical reliability and uniform pattern characteristics can be secured together while realizing a high-resolution color filter with a fine pitch.

Hereinafter, experimental examples including specific examples and comparative examples are presented to aid understanding of the present invention, but these are merely illustrative of the present invention and do not limit the appended claims, the scope and spirit of the present invention It is obvious to those skilled in the art that various changes and modifications to the embodiments are possible within the scope, and it is natural that such variations and modifications fall within the scope of the appended claims.

Preparation of alkali-soluble resin

Preparation Example 1: Synthesis of alkali-soluble resin (A-1)

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L/min to make a nitrogen atmosphere, and 100 g of propylene glycol monomethyl ether acetate was added and heated to 70° C. while stirring. Next, 28.1 g (0.15 mol) of N-benzylmaleimide, 47.3 g (0.40 mol) of vinyltoluene, and 42.8 g (0.20 mol) of acrylic acid were dissolved in 200 g of propylene glycol monomethyl ether acetate to prepare a solution.

After the prepared solution was added dropwise into the flask using a dropping funnel, 27.9 g (0.11 mol) of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was added to 100 g of propylene glycol monomethyl ether acetate. The solution dissolved in was added dropwise into the flask over 4 hours using a separate dropping funnel. After the dropwise addition of the polymerization initiator solution was completed, the temperature was maintained at 70° C. for 4 hours, and then, 53.6 g (0.25 mol) of a mixed solution of acrylic acid and glycidyl methacrylate was added into the flask, and the reaction was continued at 110° C. for 6 hours. and unsaturated group-containing resin 1-1 having a solid content acid value of 53 mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 12700, and the molecular weight distribution (Mw/Mn) was 2.0.

Preparation Example 2: Synthesis of alkali-soluble resin (A-2)

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L/min to form a nitrogen atmosphere, and 100 g of propylene glycol monomethyl ether acetate was added and heated to 70° C. while stirring. Then, 6.6 g (0.30 mol) of tricyclodecanyl methacrylate, 49.8 g (0.27 mol) of 2-ethylhexyl acrylate, and 96.4 g (0.45 mol) of a mixture of acrylic acid and glycidyl methacrylate were mixed with propylene glycol monomethyl ether. It was dissolved in 200 g of acetate to prepare a solution.

The prepared solution was dropped into the flask using a dropping funnel, and then 27.9 g (0.11 mol) of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was added to 100 g of propylene glycol monomethyl ether acetate. The dissolved solution was dripped into the flask over 4 hours using a separate dropping funnel. After the dropwise addition of the polymerization initiator solution was completed, the temperature was maintained at 70° C. for 4 hours, and 90.6 g (0.25 mol) of a mixed solution of acrylic acid, glycidyl methacrylate and phthalic acid was added into the flask, and the reaction was continued at 110° C. for 6 hours. did.

By the above-described process, alkali-soluble resin (A-2) having a solid content and acid value of 68 mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 5900, and the molecular weight distribution (Mw/Mn) was 2.1.

Preparation Example 3: Synthesis of alkali-soluble resin (A-3)

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L/min to form a nitrogen atmosphere, 200 g of propylene glycol monomethyl ether acetate was introduced, and the temperature was raised to 100 ° C. Then 33.9 g (0.47) of acrylic acid mol), norbornene 4.7 g (0.05 mol), vinyltoluene 56.7 g (0.48 mol) and propylene glycol monomethyl ether acetate 150 g 2,2'-azobis (2,4-dimethylvaleronitrile) in a mixture The solution to which 3.6 g was added was added dropwise from the dropping funnel to the flask over 2 hours, followed by stirring at 100°C for 5 hours.

Then, the atmosphere in the flask was changed from nitrogen to air, and 42.6 g of glycidyl methacrylate [0.30 mol (64 mol% with respect to the acrylic acid used in this reaction)] was added into the flask, and the reaction was continued at 110° C. for 6 hours. did.

Alkali-soluble resin (A-3) having a solid content and acid value of 79 mgKOH/g was obtained by the above-described process. The weight average molecular weight in terms of polystyrene measured by GPC was 6,600, and the molecular weight distribution (Mw/Mn) was 1.9.

Preparation Example 4: Synthesis of alkali-soluble resin (A-4)

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L/min to form a nitrogen atmosphere, and 100 g of propylene glycol monomethyl ether acetate was added and heated to 70° C. while stirring. Next, 20.8 g (0.10 mol) of 2-(phenylthio)ethyl acrylate, 45.5 g (0.39 mol) of vinyltoluene, and 19.1 g (0.27 mol) of acrylic acid were dissolved in 200 g of propylene glycol monomethyl ether acetate to prepare a solution.

After the prepared solution was added dropwise into the flask using a dropping funnel, 27.9 g (0.11 mol) of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was added to 100 g of propylene glycol monomethyl ether acetate. The dissolved solution was dripped into the flask over 4 hours using a separate dropping funnel. After the addition of the polymerization initiator solution was completed, the temperature was maintained at 70° C. for 4 hours, and 53.6 g (0.25 mol) of a mixed solution of acrylic acid and glycidyl methacrylate was added into the flask, and the reaction was continued at 110° C. for 6 hours.

Alkali-soluble resin (A-4) having a solid content and acid value of 117 mgKOH/g was obtained by the above-described process. The weight average molecular weight in terms of polystyrene measured by GPC was 13,100, and the molecular weight distribution (Mw/Mn) was 2.01.

Preparation Example 5: Synthesis of alkali-soluble resin (A-5)

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L/min to form a nitrogen atmosphere, and 100 g of propylene glycol monomethyl ether acetate was added and heated to 70° C. while stirring. Next, 18.7 g (0.10 mol) of N-benzylmaleimide, 23.6 g (0.20 mol) of vinyltoluene, and 50.4 g (0.70 mol) of acrylic acid were dissolved in 200 g of propylene glycol monomethyl ether acetate to prepare a solution.

After the prepared solution was added dropwise into the flask using a dropping funnel, 27.9 g (0.11 mol) of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was added to 100 g of propylene glycol monomethyl ether acetate. The dissolved solution was dripped into the flask over 4 hours using a separate dropping funnel. After the addition of the polymerization initiator solution was completed, the temperature was maintained at 70 ° C for 4 hours, and 71.1 g of glycidyl methacrylate [0.50 mol (71 mol % with respect to the acrylic acid used in this reaction)] was added into the flask and heated at 110 ° C. The reaction was continued for 6 hours.

Alkali-soluble resin (A-5) having a solid content and acid value of 135 mgKOH/g was obtained by the above-described process. The weight average molecular weight in terms of polystyrene measured by GPC was 8,000, and the molecular weight distribution (Mw/Mn) was 2.01.

Preparation Example 6: Synthesis of alkali-soluble resin (A-6)

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L/min to make a nitrogen atmosphere, and 100 g of propylene glycol monomethyl ether acetate was added and heated to 70° C. while stirring. Next, 18.7 g (0.10 mol) of N-benzylmaleimide, 30.0 g (0.25 mol) of vinyltoluene, and 53.6 g (0.25 mol) of acrylic acid were dissolved in 200 g of propylene glycol monomethyl ether acetate to prepare a solution.

After the prepared solution was added dropwise into the flask using a dropping funnel, 27.9 g (0.11 mol) of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was added to 100 g of propylene glycol monomethyl ether acetate. The solution dissolved in was added dropwise into the flask over 4 hours using a separate dropping funnel. After the dropwise addition of the polymerization initiator solution was completed, the temperature was maintained at 70° C. for 4 hours, and then 85.7 g (0.40 mol) of a mixed solution of acrylic acid and glycidyl methacrylate was added into the flask, and the reaction was continued at 110° C. for 6 hours. and unsaturated group-containing resin 1-6 having a solid content acid value of 38 mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 7000, and the molecular weight distribution (Mw/Mn) was 1.8.

Examples and Comparative Examples

Example

The colored photosensitive compositions of Examples were prepared with the components and contents (parts by weight) shown in Tables 1 and 2 below.

Classification (parts by weight) Example One 2 3 4 5 6 7 8 9 Alkali-soluble resin
(A) A-1 3.78 3.78 3.78 - - - - - - A-2 - - - 4.08 4.08 4.08 - - - A-3 - - - 5.65 5.65 5.62 A-4 - - - - - - A-5 - - - - - - A-6 - - - - - - photopolymerizable compound
(B) B-1 0.8 - - 0.8 - - 0.8 - - B-2 - 0.80 - - 0.80 - - 0.80 - B-3 - - 0.80 - - 0.80 - - 0.80 B-4 - - - - - - - - - B-5 - - - - - - - - - photopolymerization initiator
(C) C-1 0.24 0.24 0.24 0.24 0.24 0.24 0.24 0.24 0.24 C-2 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 coloring agent D 52.47 52.47 52.47 52.47 52.47 52.47 52.47 52.47 52.47 additive E 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 solvent F 42.54 42.54 42.54 42.24 42.24 42.24 40.67 40.67 40.67

Classification (parts by weight) Example 10 11 12 13 14 15 Alkali-soluble resin
(A) A-1 3.78 3.78 - - - - A-2 - - 4.08 4.08 - - A-3 - - - - 5.65 5.65 A-4 - - - - - - A-5 - - - - - - A-6 - - - - - - photopolymerizable compound
(B) B-1 - - - - - - B-2 - - - - - - B-3 - - - - - - B-4 0.80 - 0.80 - 0.80 - B-5 - 0.80 - 0.80 - 0.80 photopolymerization initiator
(C) C-1 0.24 0.24 0.24 0.24 0.24 0.24 C-2 0.04 0.04 0.04 0.04 0.04 0.04 coloring agent D 52.47 52.47 52.47 52.47 52.47 52.47 additive E 0.13 0.13 0.13 0.13 0.13 0.13 solvent F 42.54 42.54 42.24 42.24 40.67 40.67

comparative example

Colored photosensitive compositions of Comparative Examples were prepared with the components and contents (parts by weight) shown in Tables 3 and 4 below.

Classification (parts by weight) comparative example One 2 3 4 5 6 7 8 Alkali-soluble resin
(A) A-1 - - - - - - - - A-2 - - - - - - - - A-3 - - - - - - - - A-4 4.39 4.39 4.39 4.39 4.39 - - - A-5 - - - - - 4.26 4.26 4.26 A-6 - - - - - - photopolymerizable compound
(B) B-1 0.8 - - - - 0.8 - - B-2 - 0.80 - - - - 0.80 - B-3 - - 0.80 - - - - 0.80 B-4 - - - 0.80 - - - - B-5 - - - - 0.80 - - - photopolymerization initiator
(C) C-1 0.24 0.24 0.24 0.24 0.24 0.24 0.24 0.24 C-2 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 coloring agent D 52.47 52.47 52.47 52.47 52.47 52.47 52.47 52.47 additive E 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 solvent F 41.93 41.93 41.93 41.93 41.93 42.06 42.06 42.06

Classification (parts by weight) comparative example 9 10 11 12 13 14 15 Alkali-soluble resin
(A) A-1 - - - - - - - A-2 - - - - - - - A-3 - - - - - - - A-4 - - - - - - - A-5 4.26 4.26 - - - - - A-6 - - 4.40 4.40 4.40 4.40 4.40 photopolymerizable compound
(B) B-1 - - 0.8 - - - - B-2 - - - 0.80 - - - B-3 - - - - 0.80 - - B-4 0.80 - - - - 0.80 - B-5 - 0.80 - - - - 0.80 photopolymerization initiator
(C) C-1 0.24 0.24 0.24 0.24 0.24 0.24 0.24 C-2 0.04 0.04 0.04 0.04 0.04 0.04 0.04 coloring agent D 52.47 52.47 52.47 52.47 52.47 52.47 52.47 additive E 0.13 0.13 0.13 0.13 0.13 0.13 0.13 solvent F 42.06 42.06 41.92 41.92 41.92 41.92 41.92

Specific components listed in Tables 1 to 4 above are as follows.

A-1) Alkali-soluble resin of Preparation Example 1

A-2) Alkali-soluble resin of Preparation Example 2

A-3) Alkali-soluble resin of Preparation Example 3

A-4) Alkali-soluble resin of Preparation Example 4

A-5) Alkali-soluble resin of Preparation Example 5

A-6) Alkali-soluble resin of Preparation Example 6

B-1) Ethoxylated Pentaerythritol Tetraacrylate

B-2) Ethoxylated trimethylolpropane triacrylate

B-3) Ethoxylated dipentaerythritol hexaacrylate (NK ESTER A-DPH-12E; manufactured by Shin-Nakamura Chemical)

B-4) Pentaerythritol triacrylate + pentaerythritol tetraacrylate mixture (NK ESTER A-TMM-3LM-N; Shin- Nakamura Chemical)

B-5) DPHEA (Dipentaerythritol Hexa Acrylate) (ARONIX M-520, manufactured by TOAGOSEI)

C-1) Irgacure OXE-02 (BASF Korea)

C-2) Irgacure 184 (BASF Korea)

D) Green pigment (C.I. Pigment Green 58)

E) SH-8400 (Dow Corning Korea)

F) PGMEA (Propylene glycol methyl ether acetate)

Experimental Example 1: Evaluation of color pattern characteristics through KrF exposure

Color pattern manufacturing

The colored photosensitive compositions obtained in Examples and Comparative Examples were coated on the surface of a 6-inch silicon wafer in a clean room at 23° C. by spin coating, and then dried at 100° C. for 90 seconds to form a pre-colored layer. . After cooling to 23° C., the pre-colored layer was exposed to light using a KrF (248 nm) scanner. The wafer with the exposed coating film was developed with a 0.2 wt% tetramethylammonium hydroxide (TMAH) aqueous solution, and heated (post-baked) at 220° C. for 180 seconds to form a colored pattern. The thickness of all the formed coloring patterns was 0.5 micrometer, and the line|wire width was 0.9 micrometer.

1) Remaining film rate evaluation

Using a film thickness measuring device (DEKTAK3; Nippon Vacuum Technology Co., Ltd.), the residual film ratio was calculated through Equation 1 below, and the residual film characteristics were added through the following evaluation criteria.

[Formula 1]

Remaining film ratio (%) = (film thickness after development) / (film thickness before development) X 100 (%)

5: Remaining film rate exceeds 80%

4: Remaining film ratio of 70% or more and less than 80%

3: Remaining film ratio of 60% or more and less than 70%

2: Remaining film ratio of 50% or more and less than 60%

1: Remaining film ratio less than 50%

2) Residue generation evaluation

After the development process, it was evaluated through the following evaluation criteria by observing whether a development residue was generated between neighboring colored patterns through a CD-SEM image.

5: No residue observed between coloring patterns

4: Distribution of residues greater than 0% and less than 10% relative to the total area between the colored patterns

3: Distribution of residues of 10% or more and less than 20% of the total area between the colored patterns

2: Distribution of residues of 20% or more and less than 30% of the total area between the colored patterns

1: Distribution of residues over 30% of the total area between the colored patterns

3) Pattern adhesion evaluation

The defect (desorption) of the colored patterns formed after the development process was observed through the CD-SEM image and evaluated through the following evaluation criteria.

5: No pattern defect observed

4: Residual more than 90% of the colored patterns

3: 70% or more and less than 90% residual of the coloring patterns

2: 50% or more and less than 70% residual of the colored patterns

1: Residual less than 50% of the colored patterns

4) Pattern straightness evaluation

The straightness of the sidewalls of the colored patterns formed after the development process was evaluated as follows through the CD-SEM image.

5: All four sidewalls of the pattern are straight

4: pattern four sidewalls contain some protrusions but are substantially straight

3: some sidewalls of the four sidewalls of the pattern are substantially concave-convex

2: All four sidewalls of the pattern are substantially concave-convex

1: Non-formation of uniform pattern shape

The evaluation results are shown in Tables 5 and 6 below.

division remaining film rate residue generation adhesion pattern straightness Example 1 5 5 4 4 Example 2 5 5 4 4 Example 3 5 5 4 5 Example 4 5 5 5 5 Example 5 5 5 5 4 Example 6 5 5 5 5 Example 7 5 5 5 5 Example 8 5 5 4 4 Example 9 5 5 5 5 Example 10 5 3 3 4 Example 11 5 3 4 4 Example 12 5 4 3 4 Example 13 5 4 4 4 Example 14 5 3 3 4 Example 15 5 3 4 4

Referring to Table 5, the examples in which alkali-soluble resins having an acid value of 40 to 80 mgKOH/g were used showed overall excellent residual film ratio, development characteristics, adhesion and pattern straightness. On the other hand, better evaluation results were obtained in Examples 1 to 9 in which a photopolymerizable compound including an EO linker was used together.

division remaining film rate residue generation adhesion pattern straightness Comparative Example 1 4 4 4 3 Comparative Example 2 4 3 4 3 Comparative Example 3 4 4 4 4 Comparative Example 4 4 3 4 3 Comparative Example 5 4 3 4 3 Comparative Example 6 4 3 3 3 Comparative Example 7 3 3 3 2 Comparative Example 8 4 3 3 3 Comparative Example 9 3 3 3 2 Comparative Example 10 3 3 3 2 Comparative Example 11 3 4 2 2 Comparative Example 12 2 4 2 2 Comparative Example 13 3 4 2 2 Comparative Example 14 3 3 2 2 Comparative Example 15 3 3 2 2

Referring to Table 6, in the case of Comparative Examples in which a resin outside the acid value range of 40 to 80 mgKOH/g was used, overall development characteristics and pattern characteristics were deteriorated compared to the Examples.

Experimental Example 2: I-line exposure through the color pattern characteristics evaluation

Characteristics of the coloring pattern formed using the compositions of Examples 1 to 9 were evaluated in the same manner as in Experimental Example 1 except that exposure was performed with an I-line light source (365 nm) instead of a KrF light source. The evaluation results are shown in Table 7 below.

division remaining film rate residue generation adhesion pattern straightness Example 1 4 2 4 3 Example 2 4 2 3 2 Example 3 4 2 4 3 Example 4 3 2 3 3 Example 5 3 2 3 2 Example 6 3 2 3 3 Example 7 3 2 3 3 Example 8 3 2 2 2 Example 9 3 2 3 3

Referring to Table 7, it can be seen that when the I-line is used as the exposure light source, the development characteristics and the pattern characteristics are significantly deteriorated compared to that of Experimental Example 1.

Claims (9)

alkali-soluble resin having an acid value of 40 to 80 mgKOH/g;
a photopolymerizable compound comprising a tetrafunctional or higher ethoxylated (meth)acrylate-based compound;
photoinitiator;
coloring agent; and
containing a solvent;
The content of the alkali-soluble resin in the total 100 parts by weight of the composition is 1 to 10 parts by weight, the content of the photopolymerizable compound is 0.5 to 5 parts by weight, the content of the photopolymerizable compound is smaller than the content of the alkali-soluble resin, A colored photosensitive composition for KrF, comprising:
The KrF colored photosensitive composition was applied by spin coating on the surface of a 6-inch size silicon wafer in a clean room at 23° C., dried at 100° C. for 90 seconds to form a pre-colored layer, and cooled to 23° C. After that, the pre-colored layer was exposed using a KrF (248 nm) scanner, and the wafer on which the exposed coating was formed was developed with a 0.2 wt% tetramethylammonium hydroxide (TMAH) aqueous solution, and a film thickness measuring device (DEKTAK3; Nippon Vacuum Technology). A colored photosensitive composition for KrF in which the film thickness before and after development measured using ) and the remaining film ratio calculated through the following Equation 1 exceed 80%:
[Formula 1]
Remaining film ratio (%) = (film thickness after development)/(film thickness before development) X 100 (%).
The colored photosensitive composition for KrF according to claim 1, wherein the alkali-soluble resin comprises a carboxylic acid-containing unit and a unit represented by the following Chemical Formula 1:
[Formula 1]

(In Formula 1, Ra is hydrogen or a methyl group).
delete delete The coloring for KrF according to claim 1, wherein the photopolymerizable compound comprises at least one compound selected from the group consisting of ethoxylated pentaerythritol tetra (meth) acrylate and ethoxylated dipentaerythritol hexa (meth) acrylate. photosensitive composition.
The method according to claim 1, in total 100 parts by weight of the composition,
The content of the photoinitiator is 0.1 to 5 parts by weight, the content of the colorant is 30 to 60 parts by weight, the content of the solvent is 30 to 60 parts by weight, KrF colored photosensitive composition.
A color filter comprising a colored pattern formed of the colored photosensitive composition for KrF according to claim 1 .
An imaging device comprising the color filter of claim 7.
The imaging device according to claim 8, comprising a CMOS image sensor (CIS).