KR20230127065A - Photosensitive resin composition, photosensitive resin layer using the same and color filter - Google Patents

Abstract

(상기 각 치환기는 명세서의 정의에 따른다.)The present disclosure relates to a photosensitive resin composition, a photosensitive resin film and a color filter prepared using the photosensitive resin composition.
Specifically, one embodiment is (A) a photopolymerizable compound; (B) a photopolymerization initiator; (C) a colorant; and (D) a solvent, wherein the photopolymerizable compound includes a tetrafunctional compound and a hexafunctional compound, wherein the tetrafunctional compound is a compound represented by Formula 1 below:
[Formula 1]

(Each substituent follows the definition of the specification.)

Description

Photosensitive resin composition, photosensitive resin film and color filter manufactured using the same

The present disclosure relates to a photosensitive resin composition, a photosensitive resin film and a color filter prepared using the photosensitive resin composition.

An image sensor corresponds to a semiconductor that converts photons into electrons to be displayed on a display or stored in a storage device.

The image sensor is classified into a charge coupled device (CCD) image sensor and a complementary metal oxide semiconductor (CMOS) image sensor according to a manufacturing process and an application method.

The complementary metal oxide semiconductor image sensor (CMOS Image Sensor, CIS) is a non-memory semiconductor that converts an image received by a camera into a digital signal, and is a collection of pixels such as color filters, photodiodes, and amplifiers.

The color filter includes a filter segment of additive and mixed primary colors of red, green, and blue, and a pigment dispersion method is known as one of the methods for manufacturing the filter segment.

The pigment dispersion method is to form a photosensitive resin film by coating a photosensitive resin composition containing a colorant on a substrate, exposing and developing a pattern of a form to be formed, and thermally curing through a post bake, This is a method of manufacturing a color filter by repeating a series of processes.

In this way, in the process of manufacturing the color filter, it is required that the reduction in the residual film rate during thermal curing is minimized and that pattern residues are formed in a small amount during development. However, it is very difficult to satisfy both of these requirements.

One embodiment is to provide a photosensitive resin composition capable of minimizing pattern residue while suppressing a decrease in remaining film rate during the manufacturing process of a color filter.

Another embodiment is to provide a photosensitive resin film prepared using the photosensitive resin composition.

Another embodiment is to provide a color filter manufactured using the photosensitive resin film.

One embodiment is (A) a photopolymerizable compound; (B) a photopolymerization initiator; (C) a colorant; and (D) a solvent, wherein the photopolymerizable compound includes a tetrafunctional compound and a hexafunctional compound, wherein the tetrafunctional compound is a compound represented by Formula 1 below:

[Formula 1]

In Formula 1, X ¹ is O or S; L ¹ and L ² are each independently a single bond or a substituted or unsubstituted alkylene having 1 to 10 carbon atoms; R ¹ to R ⁴ are each independently represented by Formula 2 below;

[Formula 2]

In Formula 2, L ³ and L ⁴ are each independently a single bond, a substituted or unsubstituted alkylene having 1 to 10 carbon atoms, or *-O(CH ₂ ) ₂ -*; R ⁵ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

R ¹ to R ⁴ may each independently be a substituent represented by any one of Formulas 2-1 to 2-4 below:

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

.

.

R ¹ and R ³ may be substituents represented by Formula 2-1 or 2-2.

R ² and R ⁴ may be substituents represented by Formula 2-3 or 2-4.

The tetrafunctional compound may be any one selected from the group consisting of:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

.

.

The hexafunctional compound may be a compound represented by Formula 3 below:

[Formula 3]

In Formula 3, X ² is O or S; L ⁵ and L ⁶ are each independently a single bond or a substituted or unsubstituted alkylene having 1 to 10 carbon atoms; R ⁷ to R ¹¹ are each independently represented by Formula 4 below;

[Formula 4]

In Formula 4, L ⁷ is a single bond or a substituted or unsubstituted alkylene having 1 to 10 carbon atoms; R ¹² is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

R ⁶ to R ¹⁰ may each independently be a substituent represented by Formula 4-1 or 4-2 below:

[Formula 4-1]

[Formula 4-2]

.

.

The hexafunctional compound may be any one selected from the group consisting of:

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

.

.

The weight ratio of the tetrafunctional compound and the hexafunctional compound may be 5:5 to 3:7.

The content of the tetrafunctional compound in the total amount of the photosensitive resin composition may be 0.1% by weight to 2% by weight.

The content of the hexafunctional compound in the total amount of the photosensitive resin composition may be 0.5% by weight to 4% by weight.

The colorant may include a pigment.

The pigment may include a yellow pigment, a green pigment, or a combination thereof.

The photosensitive resin composition, based on the total amount of the photosensitive resin composition, the (A) photopolymerizable compound 0.1% to 5% by weight; 0.1% to 5% by weight of the (B) photopolymerization initiator; 15% to 95% by weight of the (C) colorant; and (D) the remaining amount of the solvent.

The photosensitive resin composition may be used for a CMOS image sensor.

Another embodiment provides a photosensitive resin film prepared using a photosensitive resin composition.

Another embodiment provides a color filter including the photosensitive resin film.

Another embodiment provides a CMOS image sensor including the color filter.

The specific details of other aspects of the present invention are included in the detailed description below.

As the photosensitive resin composition according to an embodiment includes the tetrafunctional compound represented by Chemical Formula 1 in addition to the hexafunctional compound, it is possible to suppress a decrease in film remaining rate and minimize pattern residue when manufacturing a color filter. .

1 is a 0.8 μm pattern CD-SEM photograph of a color filter pattern specimen prepared using the photosensitive resin composition of Example 1.
2 is a 0.8 μm pattern CD-SEM photograph of a color filter pattern specimen prepared using the photosensitive resin composition of Example 2.
3 is a 0.8 μm pattern CD-SEM photograph of a color filter pattern specimen prepared using the photosensitive resin composition of Comparative Example 1.
4 is a 0.8 μm pattern CD-SEM photograph of a color filter pattern specimen prepared using the photosensitive resin composition of Comparative Example 2.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.

Unless otherwise specified herein, "substitution" means that at least one hydrogen atom in a compound is a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, No group, azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, ether group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt. , C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocycloalkyl group , A C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, or a substituent of a combination thereof.

Unless otherwise specified herein, "heterocycloalkyl group", "heterocycloalkenyl group", "heterocycloalkynyl group" and "heterocycloalkylene group" mean cycloalkyl, cycloalkenyl, cycloalkynyl and cycloalkyl, respectively. It means that at least one N, O, S or P heteroatom exists in the ring compound of ene.

Unless otherwise specified herein, "(meth)acrylate" means both "acrylate" and "methacrylate".

Unless otherwise defined in the chemical formula within this specification, if a chemical bond is not drawn at a position where a chemical bond is to be drawn, it means that a hydrogen atom is bonded to the position.

(Photosensitive Resin Composition)

One embodiment is (A) a photopolymerizable compound; (B) a photopolymerization initiator; (C) a colorant; and (D) a solvent, wherein the photopolymerizable compound includes a tetrafunctional compound and a hexafunctional compound, wherein the tetrafunctional compound is a compound represented by Formula 1 below:

[Formula 1]

In Formula 1, X ¹ is O or S; L ¹ and L ² are each independently a single bond or a substituted or unsubstituted alkylene having 1 to 10 carbon atoms; R ¹ to R ⁴ are each independently represented by Formula 2 below;

[Formula 2]

In Formula 2, L ³ and L ⁴ are each independently a single bond, substituted or unsubstituted alkylene having 1 to 10 carbon atoms, or *-O(CH ₂ ) ₂ -*.

The hexafunctional compound is a compound having a high degree of curing as the number of functional groups is large, and is thermally cured to an excellent level in a post-bake process, thereby contributing to suppressing a decrease in film remaining rate of the color filter. However, since the hexafunctional compound has a high degree of curing, it increases the degree of shrinkage of the photosensitive resin film in the developing process, preventing the photosensitive resin film from being removed in the developing process and increasing the pattern residue of the color filter. there is.

On the other hand, the tetrafunctional compound represented by Formula 1 has a lower degree of curing as the number of functional groups is lower than that of the hexafunctional compound, which is partially disadvantageous in reducing the remaining film rate, but lowers the degree of shrinkage of the photosensitive resin film in the developing process. can In particular, as the tetrafunctional compound represented by Formula 1 includes O or S as a central element, the removal effect in the development process is excellent compared to the tetrafunctional compound in which the central element is substituted with C in Formula 1, , which is advantageous for significantly reducing the pattern residue of the color filter.

Therefore, as the photosensitive resin composition according to the embodiment includes the tetrafunctional compound represented by Chemical Formula 1 in addition to the hexafunctional compound, the disadvantages of the two compounds are supplemented and the advantages are taken, so that the color filter is manufactured. It is possible to suppress a decrease in remaining film rate and at the same time minimize pattern residue.

Hereinafter, each component included in the photosensitive resin composition will be described in detail.

(A) photopolymerizable compound

As mentioned above, the photosensitive resin composition according to the embodiment includes a tetrafunctional compound represented by Chemical Formula 1 in addition to the hexafunctional compound.

First, the tetrafunctional compound represented by Formula 1 will be described.

In Formula 1, X ¹ is O or S. That is, the tetrafunctional compound represented by Chemical Formula 1 may include O or S as a central element.

L ¹ and L ² are each independently, and L ¹ and L ² are each independently a single bond or a substituted or unsubstituted alkylene having 1 to 10 carbon atoms. Specifically, L ¹ and L ² may each independently be a substituted or unsubstituted alkylene having 1 to 5 carbon atoms. For example, both L ¹ and L ² may be alkylene having 1 carbon atom (ie, methylene).

R ¹ to R ⁴ are each independently an acrylate-based substituent represented by Formula 2 above. That is, the tetrafunctional compound represented by Chemical Formula 1 includes four acrylate-based substituents represented by Chemical Formula 2, and thus can exhibit excellent heat resistance.

In Formula 2, L ³ and L ⁴ are each independently a single bond, substituted or unsubstituted alkylene having 1 to 10 carbon atoms, or *-O(CH ₂ ) ₂ -*. Specifically, L ³ and L ⁴ may each independently be a single bond, a substituted or unsubstituted alkylene having 1 to 5 carbon atoms, or *-O(CH ₂ ) ₂ -*. For example, L ³ and L ⁴ may each independently represent a single bond, an alkylene having 1 carbon atom (ie, methylene), or *-O(CH ₂ ) ₂ -*.

In addition, R ⁵ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group. Specifically, R ⁵ may be a hydrogen atom or an alkyl group having 1 carbon atom (ie, a methyl group).

More specifically, R ¹ to R ⁴ may each independently be a substituent represented by any one of Formulas 2-1 to 2-4 below:

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

.

.

For example, R ¹ and R ³ may be substituents represented by Formula 2-1 or 2-2. In addition, R ² and R ⁴ may be substituents represented by Formula 2-3 or 2-4.

Representative examples of the above tetrafunctional compounds are as follows:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

.

.

Next, the hexafunctional compound is described.

The hexafunctional compound may be a compound represented by Formula 3 below:

[Formula 3]

In Formula 3, X ² is O or S. That is, the hexafunctional compound represented by Chemical Formula 2 may include O or S as a central element.

L ⁵ and L ⁶ are each independently a single bond or a substituted or unsubstituted alkylene having 1 to 10 carbon atoms. Specifically, L ⁵ and L ⁶ may each independently be a single bond or a substituted or unsubstituted alkylene having 1 to 5 carbon atoms. For example, both L ⁵ and L ⁶ may be alkylene having 1 carbon atom (ie, methylene).

The R ⁷ to R ¹¹ are each independently represented by Formula 4 below:

[Formula 4]

In Formula 4, L ⁷ is a single bond or a substituted or unsubstituted alkylene having 1 to 10 carbon atoms; R ¹² is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

Specifically, L ⁷ may be a single bond or a substituted or unsubstituted alkylene having 1 to 10 carbon atoms. For example, L ⁷ may be an alkylene having 1 carbon atom (ie, methylene).

In addition, R ¹² may be a hydrogen atom or a substituted or unsubstituted C1 to C5 alkyl group. For example, R ¹² may be a hydrogen atom or an alkyl group having 1 carbon atom (ie, a methyl group).

More specifically, R ⁷ to R ¹¹ may each independently be a substituent represented by Formula 4-1 or 4-2 below:

[Formula 4-1]

[Formula 4-2]

.

.

Representative examples of the hexafunctional compounds are as follows:

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

.

.

The weight ratio of the tetrafunctional compound and the hexafunctional compound may be 6:4 to 2:8, specifically 5:5 to 3:7. Within this range, the synergistic effect of simultaneously using the two compounds can be maximized.

The content of each compound in the total amount of the photosensitive resin composition may be controlled while satisfying the weight ratio.

Of the total amount of the photosensitive resin composition, the content of the tetrafunctional compound may be 0.1% to 2% by weight, specifically 0.5% to 1.5% by weight; The content of the hexafunctional compound may be 0.5 wt% to 4 wt%, specifically 1 wt% to 2 wt%.

As the photopolymerizable compound, in addition to the above two compounds, a monofunctional or multifunctional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond may be additionally used.

The added photopolymerizable compound has the ethylenically unsaturated double bond, so that it can form a pattern having excellent heat resistance, light resistance and chemical resistance by causing sufficient polymerization during exposure in the pattern forming process.

Specific examples of the added photopolymerizable compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neo Pentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate Acrylates, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri( meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy(meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, trimethylol propane Tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, novolac epoxy (meth)acrylate, etc. are mentioned.

Examples of commercially available products of the added photopolymerizable compound are as follows. Examples of monofunctional esters of (meth)acrylic acid include Aronix M- ^101® , M- ^111® , and M- ^114® from Toagosei Chemical Industry Co., Ltd.; KAYARAD TC-110S ^® of Nippon Kayaku Co., Ltd., the same TC-120S ^® , etc.; Osaka Yuki Kagaku Kogyo Co., Ltd.'s V- ^158® , V- ^2311® , etc. are mentioned. Examples of the bifunctional ester of (meth)acrylic acid include Aronix M- ^210® , M- ^240® , and M- ^6200® of Toagosei Chemical Industry Co., Ltd.; KAYARAD HDDA ^® from Nippon Kayaku Co., Ltd., HX-220 ^® , R-604 ^® , etc.; Examples include V- ^260® , V- ^312® , and V-335 ^HP® of Osaka Yuki Kagaku Kogyo Co., Ltd. Examples of the trifunctional ester of (meth)acrylic acid include Aronix M- ^309® , M- ^400® , M- ^405® , M- ^450® , and M from Toagosei Chemical Industry Co., Ltd. -710 ^® , M-8030 ^® , M-8060 ^® , etc.; KAYARAD TMPTA ^® from Nippon Kayaku Co., Ltd., Copper DPCA-20 ^® , Copper-30 ^® , Copper-60 ^® , Copper-120 ^® , etc.; V-295 ^® , Dong-300 ^® , Dong-360 ® , Dong-GPT ^® , Dong-3PA ^® , Dong-400 ^® and ^the like of Osaka Yuki Kayaku Kogyo Co., Ltd. These products may be used alone or in combination of two or more.

The added photopolymerizable compound may be used after being treated with an acid anhydride to impart better developability.

The photopolymerizable compound may be included in an amount of 0.1 wt % to 5 wt %, specifically 1 wt % to 4 wt %, for example, 2 wt % to 3 wt %, based on the total amount of the photosensitive resin composition. When the photopolymerizable compound is included within the above range, sufficient curing occurs during exposure in the pattern forming process, resulting in excellent reliability and excellent developability with an alkaline developer.

(B) photopolymerization initiator

The photopolymerization initiator is an initiator generally used in photosensitive resin compositions, for example, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, an oxime-based compound, or a combination thereof. can be used

Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyltrichloro acetophenone, p-t -Butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc. are mentioned.

Examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4 '-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

Examples of the thioxanthone-based compound include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chlorothioxanthone etc. are mentioned.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyldimethylketal.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3', 4'- Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4, 6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis (trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, and the like.

Examples of the oxime-based compound include O-acyloxime-based compounds, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyloxime) )-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one etc. can be used. Specific examples of the O-acyloxime compound include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane- 1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione 2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione 2 -Oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1-one oxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O- Acetate etc. are mentioned.

As the photopolymerization initiator, a carbazole-based compound, a diketone compound, a sulfonium borate-based compound, a diazo-based compound, an imidazole-based compound, a biimidazole-based compound, a fluorene-based compound, and the like may be used in addition to the above compounds.

The photopolymerization initiator may be used together with a photosensitizer that causes a chemical reaction by absorbing light, becoming excited, and then transferring the energy thereto.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, and the like. can be heard

The photopolymerization initiator may be included in an amount of 0.1 wt % to 5 wt %, specifically 0.5 wt % to 4 wt %, for example, 0.1 wt % to 3 wt %, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, excellent reliability can be obtained due to sufficient curing during exposure in the pattern forming process, excellent heat resistance, light resistance and chemical resistance of the pattern, excellent resolution and adhesion, and due to the unreacted initiator A decrease in transmittance can be prevented.

(C) colorant

The colorant may include a pigment, and in this case, the resin composition of one embodiment may be a pigment-type composition. As the pigment, a red pigment, a green pigment, a blue pigment, a yellow pigment, a black pigment, or the like may be used.

Examples of the red pigment include C.I. Red Pigment 254, C.I. Red Pigment 255, C.I. Red Pigment 264, C.I. Red Pigment 270, C.I. Red Pigment 272, C.I. Red Pigment 177, C.I. Red pigment 89 etc. are mentioned. Examples of the green pigment include C.I. Green Pigment 7, C.I. Green Pigment 36, C.I. Green Pigment 58, C.I. Green pigment 59 etc. are mentioned. Examples of the blue pigment include C.I. blue pigment 15:6, C.I. Blue Pigment 15, C.I. blue pigment 15:1, C.I. blue pigment 15:2, C.I. blue pigment 15:3, C.I. blue pigment 15:4, C.I. blue pigment 15:5, C.I. and copper phthalocyanine pigments such as blue pigment 16 and the like. Examples of the yellow pigment include C.I. isoindoline-based pigments such as yellow pigment 139, C.I. quinophthalone pigments such as yellow pigment 138, C.I. nickel complex pigments such as Yellow Pigment 150 and the like; and the like. Examples of the black pigment include aniline black, perylene black, titanium black, and carbon black. The above pigments may be used alone or in combination of two or more thereof. For example, a yellow pigment, a green pigment, or a mixture thereof may be used as the pigment.

The pigment may be included in the photosensitive resin composition for color filters in the form of a dispersion. The pigment dispersion may be composed of the pigment, a solvent, a dispersing agent, and a dispersing resin. The solid pigment may be included in an amount of 5 wt % to 20 wt %, for example, 8 wt % to 15 wt %, based on the total amount of the pigment dispersion.

Ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc. may be used as the solvent, and among these, propylene glycol methyl ether acetate is preferably used. can

The dispersant helps to uniformly disperse the pigment in the dispersion, and each of a nonionic, anionic or cationic dispersant may be used. Specifically, polyalkylene glycol or its ester, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid salt, alkyl amide alkylene oxide adduct Water, alkyl amine, etc. may be used, and these may be used alone or in combination of two or more.

As the dispersion resin, an acrylic resin containing a carboxyl group may be used, which may improve stability of the pigment dispersion and also improve pixel patternability.

The colorant may further include a dye while including the pigment, and in this case, the resin composition of one embodiment may be a hybrid composition. In addition, the dye is not particularly limited, but may include a metal complex dye.

The metal complex "dye" can use a compound having maximum absorbance in the wavelength range of 200 nm to 650 nm, and if the compound has absorbance in the above range to match the color coordinates to the combination of dyes, the metal complex "dye of all colors that dissolves in an organic solvent" can be used

Specifically, the metal complex dye is a green dye having maximum absorbance in a wavelength range of 530 nm to 680 nm, a yellow dye having maximum absorbance in a wavelength range of 200 nm to 400 nm, and a maximum absorbance in a wavelength range of 300 nm to 500 nm. An orange "dye" having, a red "dye" having maximum absorbance in a wavelength range of 500 nm to 650 nm, or a combination thereof may be used.

The metal complex dyes are direct dyes, acid dyes, basic dyes, acid mordant dyes, sulfur dyes, reducing dyes, azoic dyes, disperse dyes, reactive dyes, oxide dyes, useful dyes, azo dyes, anthraquinone dyes, indigo dyes , carbonium ion "dye," phthalocyanine "dye, nitro" dye, quinoline "dye, cyanine" dye, polymethine "dye" or a combination thereof may be used.

The metal complex/dye may include at least one metal ion selected from the group consisting of Mg, Ni, Cu, Co, Zn, Cr, Pt, Pd, and Fe.

The metal complex dye is C.I. C.I. solvents such as greens 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 solvents and dyes; C.I. Acid “Green” 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109, etc. C.I. acid dyes; C.I. Direct 　 Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 C.I. Direct dye, C.I. C.I. such as Basic, Green, and 1. Basic dyes; C.I. The C.I. Mordant Dye, C.I. Green pigments, such as Pigment "Green" 7, 36, and 58; Solvent Yellow 19, Solvent Yellow 21, Solvent Yellow 25, Solvent Yellow 79, Solvent Yellow 82, Solvent Yellow 88, Solvent Orange 45, Solvent Orange 54, Solvent Orange 62, Solvent Orange 99, Solvent Red 8, Solvent Red 32, Solvent Red A complex of at least one selected from the group consisting of Solvent Red 109, Solvent Red 112, Solvent Red 119, Solvent Red 124, Solvent Red 160, Solvent Red 132, and Solvent Red 218 and the metal ion may be used.

The dye containing the metal complex may have a solubility of 5 or more, specifically 5 to 10, in a solvent used in the photosensitive resin composition according to an embodiment, that is, a solvent to be described later. The solubility can be obtained by the amount (g) of the dye dissolved in 100 g of the solvent. When the solubility of the dye containing the metal complex is within the above range, compatibility with other components constituting the photosensitive resin composition according to an embodiment and coloring power may be secured, and precipitation of the dye may be prevented.

The solvent is, for example, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), ethylene glycol ethyl acetate (EGA), cyclohexanone (cyclohexanone), 3-methoxy-1-butanol, or a combination thereof may be used.

As it has the above specific range, it can be usefully used for color filters such as LCDs and LEDs that express high luminance and high contrast ratio in a desired color coordinate.

The dye containing the metal complex may be included in an amount of 0.01 wt% to 1 wt%, for example, 0.01 wt% to 0.5 wt%, based on the total amount of the photosensitive resin composition. When the dye containing the metal complex is used in the above range, high luminance and contrast ratio can be expressed in a desired color coordinate.

When the dye and the pigment are mixed and used, they may be mixed at a weight ratio of 0.1:99.9 to 99.9:0.1, specifically, 1:9 to 9:1. When mixed in the above weight ratio range, chemical resistance and maximum absorption wavelength can be controlled within an appropriate range, and high luminance and contrast ratio can be expressed in a desired color coordinate.

The colorant may be included in an amount of 15 wt % to 95 wt %, specifically 20 wt % to 70 wt %, for example, 30 wt % to 65 wt %, based on the total amount of the photosensitive resin composition. When the colorant is included within the above range, the coloring effect and developability are excellent.

(D) solvent

As the solvent, materials that have compatibility with the colorant, the binder resin, the photopolymerizable compound, and the photopolymerization initiator but do not react may be used.

Examples of the solvent include alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates, such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons, such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone ; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; lactic acid esters such as methyl lactate and ethyl lactate; oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; Alkoxy acetic acid alkyl esters, such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-oxy propionic acid alkyl esters such as 3-oxy methyl propionate and 3-oxy ethyl propionate; 3-alkoxy propionic acid alkyl esters such as 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy ethyl propionate, and 3-ethoxy methyl propionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate; 2-alkoxy propionic acid alkyl esters such as 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-ethoxy ethyl propionate, and 2-ethoxy methyl propionate; 2-oxy-2-methyl propionic acid esters such as 2-oxy-2-methyl methyl propionate, 2-oxy-2-methyl ethyl propionate, 2-methoxy-2-methyl methyl propionate, 2-ethoxy-2- monooxy monocarboxylic acid alkyl esters of 2-alkoxy-2-methyl alkyl propionate such as methyl ethyl propionate; esters such as 2-hydroxy ethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate, and 2-hydroxy-3-methyl methyl butanoate; ketonic acid esters such as ethyl pyruvate, etc., and also N-methylformamide, N,N-dimethylformamide, N-methylformanilad, N-methylacetamide, N,N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid and high boiling point solvents such as ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among these, considering compatibility and reactivity, ketones such as cyclohexanone; glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as 2-hydroxy ethyl propionate; carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate, and ketones such as cyclohexanone may be used.

The solvent may be included in a balance amount, for example, 5 wt% to 70 wt%, for example, 10 wt% to 50 wt%, based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, it is possible to obtain a coating film having excellent coatability of the photosensitive resin composition and excellent flatness.

(E) binder resin

The photosensitive resin composition may further include a binder resin, and the binder resin may include an acrylic resin.

The acrylic resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and includes one or more acrylic repeating units.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

The first ethylenically unsaturated monomer may be included in an amount of 5 wt % to 50 wt %, for example, 10 wt % to 40 wt %, based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, or vinylbenzylmethyl ether; Methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy butyl (meth)acrylate, benzyl (meth)acrylate, unsaturated carboxylic acid ester compounds such as cyclohexyl (meth)acrylate and phenyl (meth)acrylate; Unsaturated carboxylic acid amino alkyl ester compounds, such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate; vinyl cyanide compounds such as (meth)acrylonitrile; unsaturated amide compounds such as (meth)acrylamide; and the like, and these may be used alone or in combination of two or more.

Specific examples of the acrylic resin include (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate late copolymers, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymers, and the like, but are not limited thereto, and may be used alone or in combination of two or more. .

The binder resin may include an epoxy-based binder resin.

The binder resin may improve heat resistance by further including an epoxy-based binder resin. The epoxy-based binder resin may include, for example, a phenol novolak epoxy resin, a tetramethyl biphenyl epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, an alicyclic epoxy resin, or a combination thereof, but is limited thereto It is not.

Furthermore, the binder resin including the epoxy-based binder resin secures dispersion stability of a colorant such as a pigment, which will be described later, and helps to form a pixel having a desired resolution during a developing process.

The epoxy-based binder resin may be included in an amount of 1 wt % to 10 wt %, for example, 5 wt % to 10 wt %, based on the total amount of the binder resin. When the epoxy-based binder resin is included in the above range, film remaining rate and chemical resistance may be greatly improved.

The epoxy equivalent weight of the epoxy-based binder resin may be 150 g/eq to 200 g/eq. When an epoxy-based binder resin having an epoxy equivalent within the above range is included in the binder resin, there is an advantageous effect in improving the curing degree of the formed pattern and fixing the colorant in the patterned structure.

The binder resin may be dissolved in a solvent to be described later in a solid form to form a photosensitive resin composition. In this case, the binder resin in the solid form may be about 10% to 50% by weight, for example, 20% to 40% by weight based on the total amount of the binder resin solution dissolved in the solvent.

The binder resin may be included in an amount of 1 wt % to 20 wt %, specifically 3 wt % to 15 wt %, for example, 5 wt % to 10 wt %, based on the total amount of the photosensitive resin composition. When the binder resin is included within the above range, it is possible to obtain excellent surface smoothness due to excellent developability and improved crosslinking property during manufacture of the color filter.

(F) other additives

The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A coupling agent containing a vinyl group or a (meth)acryloxy group; leveling agent; Surfactants; And it may further include at least one additive selected from a radical polymerization initiator.

The additives can be easily adjusted according to desired physical properties.

The coupling agent may be a silane-based coupling agent, and examples of the silane-based coupling agent include trimethoxysilyl benzoic acid, γ methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ Isocyanate propyl triethoxysilane, (gamma) glycidoxy propyl trimethoxysilane, (beta) epoxycyclohexyl) ethyl trimethoxysilane, etc. are mentioned, These can be used individually or in mixture of 2 or more types.

The silane-based coupling agent may be specifically used in an amount of 0.01 part by weight to 1 part by weight based on 100 parts by weight of the photosensitive resin composition.

In addition, the photosensitive resin composition for color filters may further include a surfactant, for example, a fluorine-based surfactant, if necessary.

Examples of the fluorine-based surfactant include, but are not limited to, DIC's F-482, F-484, and F-478.

The surfactant is preferably included in an amount of 0.01% to 5% by weight and more preferably in an amount of 0.01% to 2% by weight based on the total amount of the photosensitive resin composition. If it is out of the above range, it is not preferable to cause a problem in that foreign substances are generated after development.

In addition, a certain amount of other additives such as antioxidants and stabilizers may be added to the photosensitive resin composition within a range that does not impair physical properties.

The photosensitive resin composition may be applied to a photosensitive resin composition for a color filter of a CMOS image sensor, specifically a photosensitive resin composition for a green color filter of a CMOS image sensor.

(Photosensitive resin film, color filter and CMOS image sensor)

According to another embodiment, a photosensitive resin film prepared using the photosensitive resin composition according to the embodiment is provided.

According to another embodiment, a color filter manufactured using the photosensitive resin composition described above is provided.

A method of manufacturing the color filter is as follows.

A photosensitive resin composition layer is formed on a glass substrate by applying the photosensitive resin composition to a thickness of, for example, 0.5 μm to 10 μm using an appropriate method such as spin coating, roller coating, or spray coating.

Subsequently, light is irradiated to form a pattern required for a color filter on the substrate on which the photosensitive resin composition layer is formed. As a light source used for irradiation, UV, electron beam, or X-ray may be used, and for example, UV in a range of 190 nm to 450 nm, specifically, 200 nm to 400 nm may be irradiated. In the irradiation step, a photoresist mask may be further used. After performing the irradiation step in this way, the photosensitive resin composition layer irradiated with the light source is treated with a developing solution. At this time, the unexposed portion of the photosensitive resin composition layer is dissolved to form a pattern required for the color filter. By repeating this process according to the number of colors required, a color filter having a desired pattern can be obtained. In addition, when the image pattern obtained by development in the above process is heated again or cured by irradiation with actinic rays, etc., crack resistance, solvent resistance, and the like can be improved.

According to another embodiment, a CMOS image sensor including the color filter is provided.

Hereinafter, the present invention will be described in more detail with reference to examples, but the following examples are only preferred examples of the present invention and the present invention is not limited to the following examples.

(Preparation of photosensitive resin composition)

Examples 1 to 6 and Comparative Examples 1 to 3

A photosensitive resin composition was prepared by mixing the compositions shown in Tables 1 and 2.

Specifically, after dissolving the photopolymerization initiator in a solvent, the mixture was stirred at room temperature for 30 minutes, and then a photopolymerizable compound was added thereto and stirred at room temperature for 60 minutes. Subsequently, a dye and a pigment dispersion as a colorant were added to the obtained reactant and stirred at room temperature for 30 minutes. In addition, solvent and additives were added and stirred at room temperature for 30 minutes. Subsequently, a photosensitive resin composition was prepared by filtering the product twice to remove impurities.

(Unit: % by weight) ingredient material name solid content
(%) Example 1 Example 2 Example 3 Example 4 Example 5 (A) photopolymerizable compound A-1 100 1.479 1.232 0.986 0.705 0.493 A-2 100 0.986 1.233 1.479 1.760 1.972 A-3 100 - - - - - (B) photopolymerization initiator B-1 100 2.663 2.663 2.663 2.663 2.663 (C) colorant C-1 100 45.173 45.173 45.173 45.173 45.173 C-2 10 35.838 35.838 35.838 35.838 35.838 (D) solvent D-1 - 13.464 13.464 13.464 13.464 13.464 (F) additives F-1 10 0.2 0.2 0.2 0.2 0.2 F-1 10 0.197 0.197 0.197 0.197 0.197

(Unit: % by weight) ingredient material name solid content
(%) Comparative Example 1 Comparative Example 2 Comparative Example 3 (A) photopolymerizable compound A-1 100 - 2.465 - A-2 100 2.465 - 1.233 A-3 100 - - 1.232 (B) photopolymerization initiator B-1 100 2.663 2.663 2.663 (C) colorant C-1 100 45.173 45.173 45.173 C-2 10 35.838 35.838 35.838 (D) solvent D-1 - 13.464 13.464 13.464 (F) additives F-1 10 0.2 0.2 0.2 F-1 10 0.197 0.197 0.197

Each component used in Tables 1 and 2 is as follows.

(A) photopolymerizable compound

(A-1) A tetrafunctional compound represented by the following formula 1-1 (product name: DGE-4A, manufacturer: Kongyeongsa)

[Formula 1-1]

(A-2) A hexafunctional compound represented by the following formula 3-1 (product name: dipentaerythritol hexaacrylate (DPHA), manufacturer: Nippon Explosives)

[Formula 3-1]

(A-3) A hexafunctional compound represented by the following formula A (product name: DGE-4A manufacturer: Kongyeongsa)

[Formula A]

(B) photopolymerization initiator

(B-1) oxime initiator (OXE-01, manufacturer: BASF)

(C) colorant

(C-1) green pigment dispersion (G58, manufacturer: ENF)

(C-2) yellow pigment dispersion (Y138, manufacturer: ENF)

(D) solvent

(D-1) Propylene glycol monomethyl ether acetate (PGMEA, manufacturer: Sigma-Aldrich)

(F) additives

(F-1) Fluorine-based surfactant (F-554, manufacturer: DIC (using 10% diluted solution))

(F-2) Silane-based coupling agent (S-510, manufacturer: CHISSO)

(evaluation)

Evaluation Example 1: Evaluation of residual film rate

The “photosensitive” resin compositions according to Examples 1 to 5 and Comparative Examples 1 to 3 were coated on a glass substrate to a thickness of 3 μm using a spin coater (Mikasa, Opticoat MS-A150), respectively, and then a hot-plate was applied. Soft-baking was performed at 80° C. for 120 seconds, and exposure was performed with a power of 60 mJ using an exposure machine (Ushio Co., ghi broadband). Subsequently, it was developed with a 0.2% by weight potassium hydroxide (KOH) aqueous solution using a developing machine (SVS, SSP-200). Thereafter, hard-baking was performed in a convection oven at 150° C. for 30 minutes, and additional curing was performed at 200° C. for 30 minutes.

Using Tencor's profiler equipment, the pattern height (H _a ) immediately after the coating and the pattern height (H _b ) after completing the additional process were measured, respectively. The remaining film rate was calculated by substituting each of the measured values into Equation 1 below, and the results are shown in Table 3 below.

[Equation 1]

Remaining film rate (%) = 100 (%)*H _b /H _a

In Equation 1 above,

H _a is the pattern height immediately after the coating,

H _b is the pattern height after completion of the above additional steps.

remaining film rate Example 1 73% Example 2 74.5% Example 3 76.3% Example 4 78.1% Example 5 79% Comparative Example 1 80% Comparative Example 2 66% Comparative Example 3 69%

According to Table 3, Comparative Example 2 using only the tetrafunctional compound represented by Formula 1 as the photopolymerizable compound had a significantly reduced film remaining rate compared to Comparative Example 1 using only the hexafunctional compound as the photopolymerizable compound. it can be seen that

In addition, Comparative Example 3 using a tetrafunctional compound not represented by Formula 1 together with a hexafunctional compound as a photopolymerizable compound had a partially improved film remaining rate compared to Comparative Example 2, but significantly lower residue than Comparative Example 1. showed a deadlock.

On the other hand, Examples 1 to 5 using the tetrafunctional compound represented by Formula 1 together with the hexafunctional compound as the photopolymerizable compound have levels close to those of Comparative Example 1 using the hexafunctional compound alone as the photopolymerizable compound. showed residual rates.

From this, it can be seen that when the tetrafunctional compound represented by Chemical Formula 1 is used together with the hexafunctional compound as the photopolymerizable compound, the decrease in film remaining rate can be suppressed.

Evaluation Example 2: Pattern Residue Evaluation

The “photosensitive” resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 3 were coated on a glass substrate to a thickness of 3 μm using a spin coater (Mikasa, Opticoat MS-A150), respectively, and then a hot-plate was applied. Soft-baking was performed at 80° C. for 120 seconds, and exposure was performed with a power of 60 mJ using an exposure machine (Ushio Co., ghi broadband). Subsequently, it was developed with a 0.2% by weight potassium hydroxide (KOH) aqueous solution using a developing machine (SVS, SSP-200). Thereafter, hard-baking was performed in a convection oven at 100 ° C. for 30 minutes, and additional curing was performed at 200 ° C. for 30 minutes. After the coating, exposure, development, hard-baking, and additional curing, a 0.8 μm pattern CD was measured using a CD-SEM device to determine whether the surrounding residues were improved according to the following criteria.

Residue characterization criteria

◎: Pattern and surrounding floor residue very good

○: pattern residue good level

△: Among pattern residues

X: pattern residue thirteen levels

In addition, representatively the 0.8 μm pattern CD measurement results of Examples 1 to 2 and Comparative Examples 1 to 2 are shown in FIGS. 1 to 4 . Specifically, FIG. 1 relates to Example 1, FIG. 2 relates to Example 2, FIG. 3 relates to Comparative Example 1, and FIG. 4 relates to Comparative Example 2.

residue Example 1 ○ Example 2 ○ Example 3 ○ Example 4 ○ Example 5 △ Comparative Example 1 ◎ Comparative Example 2 X Comparative Example 3 △

According to Table 4, Comparative Example 1 using only the hexafunctional compound as the photopolymerizable compound had significantly inferior pattern residues compared to Comparative Example 2 using only the tetrafunctional compound represented by Formula 1 as the photopolymerizable compound. you can see what it did

In addition, in Comparative Example 3 using a tetrafunctional compound not represented by Formula 1 together with a hexafunctional compound as a photopolymerizable compound, pattern residues were partially improved compared to Comparative Example 1, but significantly inferior to Comparative Example 2. showed pattern residue.

On the other hand, Examples 1 to 5 using the tetrafunctional compound represented by Formula 1 together with the hexafunctional compound as the photopolymerizable compound have a level close to that of Comparative Example 2 using the tetrafunctional compound alone as the photopolymerizable compound. It showed a good pattern residue.

From this, it can be seen that pattern residues can be minimized by using the tetrafunctional compound represented by Chemical Formula 1 together with the hexafunctional compound as a photopolymerizable compound.

Taking Tables 2 and 3 together, suppressing the remaining film rate reduction and minimizing pattern residues are in a trade-off relationship, represented by Formula 1 together with a hexafunctional compound as a photopolymerizable compound. If a tetrafunctional compound is used, it is possible to strike a balance between suppressing the remaining film rate decrease and minimizing pattern residues.

In particular, while using the tetrafunctional compound represented by Formula 1 together with the hexafunctional compound as a photopolymerizable compound, increasing the content of the tetrafunctional compound represented by Formula 1 is advantageous in minimizing pattern residue. do.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and it is possible to carry out various modifications within the scope of the claims and detailed description of the invention and the accompanying drawings, and this also It goes without saying that it falls within the scope of the invention.

Claims (19)

(A) a photopolymerizable compound;
(B) a photopolymerization initiator;
(C) a colorant; and
(D) solvent
including,
The photopolymerizable compound includes a tetrafunctional compound and a hexafunctional compound,
The photosensitive resin composition wherein the tetrafunctional compound is a compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
X ¹ is O or S;
L ¹ and L ² are each independently a single bond or a substituted or unsubstituted alkylene having 1 to 10 carbon atoms;
R ¹ to R ⁴ are each independently represented by Formula 2 below;
[Formula 2]

In Formula 2,
L ³ and L ⁴ are each independently a single bond, substituted or unsubstituted alkylene having 1 to 10 carbon atoms or *-O(CH ₂ ) ₂ -*;
R ⁵ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.
According to claim 1,
The photosensitive resin composition wherein R ¹ to R ⁴ are each independently a substituent represented by any one of Formulas 2-1 to 2-4:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

.
According to claim 2,
The photosensitive resin composition wherein R ¹ and R ³ are substituents represented by Formula 2-1 or 2-2.
According to claim 2,
The photosensitive resin composition wherein R ² and R ⁴ are substituents represented by Formula 2-3 or 2-4.
According to claim 1,
The photosensitive resin composition wherein the tetrafunctional compound is any one selected from the group consisting of:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

.
According to claim 1,
The photosensitive resin composition wherein the hexafunctional compound is a compound represented by Formula 3 below:
[Formula 3]

In Formula 3,
X ² is O or S;
L ⁵ and L ⁶ are each independently a single bond or a substituted or unsubstituted alkylene having 1 to 10 carbon atoms;
R ⁷ to R ¹¹ are each independently represented by Formula 4 below;
[Formula 4]

In Formula 4,
L ⁷ is a single bond or a substituted or unsubstituted alkylene having 1 to 10 carbon atoms;
R ¹² is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.
According to claim 6,
The photosensitive resin composition wherein R ⁷ to R ¹¹ are each independently a substituent represented by Formula 4-1 or 4-2:
[Formula 4-1]

[Formula 4-2]

.
According to claim 6,
The photosensitive resin composition wherein the hexafunctional compound is any one selected from the group consisting of:
[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

.
According to claim 1,
A weight ratio of the tetrafunctional compound and the hexafunctional compound is 5:5 to 3:7 photosensitive resin composition.
According to claim 1,
The photosensitive resin composition wherein the content of the tetrafunctional compound in the total amount of the photosensitive resin composition is 0.1% by weight to 2% by weight.
According to claim 1,
The photosensitive resin composition wherein the content of the hexafunctional compound in the total amount of the photosensitive resin composition is 0.5% to 4% by weight.
According to claim 1,
The colorant is a photosensitive resin composition containing a pigment.
According to claim 12,
The pigment is a photosensitive resin composition comprising a yellow pigment, a green pigment, or a mixture thereof.
According to claim 1,
The photosensitive resin composition, relative to the total amount of the photosensitive resin composition,
0.1% to 5% by weight of the (A) photopolymerizable compound;
0.1% to 5% by weight of the (B) photopolymerization initiator;
15% to 95% by weight of the (C) colorant; and
The remaining amount of the above (D) solvent
Photosensitive resin composition comprising a.
According to claim 1,
The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A coupling agent containing a vinyl group or a (meth)acryloxy group; leveling agent; fluorine-based surfactants; And a photosensitive resin composition further comprising at least one additive selected from a radical polymerization initiator.
According to claim 1,
The photosensitive resin composition is a photosensitive resin composition for a CMOS image sensor.
A photosensitive resin film prepared using the photosensitive resin composition of claim 1.
A color filter comprising the photosensitive resin film of claim 17 .
A CMOS image sensor comprising the color filter of claim 18 .