KR20230125639A - Colored photosensitive resin composition, color filter and solid-state imaging element using the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition comprising a pigment dispersion (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), an additive (E), and a solvent (F) and having excellent adhesion and heat resistance without a phenomenon of lifting between substrates, a color filter manufactured using the same, and a solid-state imaging device, wherein the additive (E) includes 0.05 to 0.50 wt% of a compound represented by chemical formula 1 based on 100 wt% of solid content of the colored photosensitive resin composition. Accordingly, by applying the color filter according to the present invention, a high quality device can be provided.

Description

Colored photosensitive resin composition, color filter and solid-state imaging device manufactured using the same

The present invention relates to a colored photosensitive resin composition, a color filter and a solid-state imaging device manufactured using the same.

Color filters are widely used in various display devices such as imaging devices and liquid crystal displays (LCDs), and their application range is rapidly expanding. The color filter used in the imaging device, the liquid crystal display device, etc. consists of a coloring pattern of three colors of red, green, and blue, or yellow, magenta, and cyan ( Cyan) is composed of three color coloring patterns.

Each color pattern of the color filter is generally formed using a colored photosensitive resin composition containing a color material such as a pigment or dye, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. Color pattern processing using the colored photosensitive resin composition is usually performed through a lithography process.

The colored photosensitive resin composition is an essential material for color filters, liquid crystal display materials, organic light emitting devices, displays and the like. For example, in a color filter of a color liquid crystal display, a light blocking layer using a black photosensitive composition is formed at a boundary between colored layers in order to enhance contrast and color development of red, green, and blue. Also, recently, it is required to be positioned on an array substrate to form spacers for maintaining a cell gap as well as a role of a black matrix so that various roles can be performed at once. Accordingly, not only an optical effect for basic light blocking, but also a good elastic modulus and reliability are required.

On the other hand, Korean Patent Laid-open Publication No. 10-2012-0014728 includes an additive represented by a specific chemical formula, thereby providing an ultra-fine high-resolution coloring pattern having excellent adhesive strength, and Korean Patent Publication No. 10-2233483 A photosensitive resin composition comprising a compound containing a disulfide structure as a composition of the resin reduces yellowing, has an excellent film remaining rate, and prevents the formation of a reverse tapered pattern, but the problem of insufficient adhesion between substrates this can happen

Republic of Korea Patent Publication No. 10-2012-0014728 Republic of Korea Patent Registration No. 10-2233483

In order to solve the above-mentioned problems, an object of the present invention is to provide a color filter and a solid-state imaging device having excellent heat resistance and excellent adhesion between substrates, which are manufactured using the colored photosensitive resin composition according to the present invention.

However, the problem to be solved by the present invention is not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

In order to solve the above problems, the present invention includes (A) a pigment dispersion, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) an additive and (F) a solvent, (E) the additive is characterized in that it comprises 0.05 to 0.50% by weight of the compound represented by Formula 1 based on 100% by weight of the solid content of the colored photosensitive resin composition A colored photosensitive resin composition is provided.

[Formula 1]

In Formula 1, R and R' are each independently a carboxy group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, and a carbo group having 3 to 12 carbon atoms. A yl group, an aromatic substituent having 3 to 12 carbon atoms, or a heteroaromatic substituent having 3 to 12 carbon atoms, and n may be each independently an integer of 1 to 5.

In the present invention, Formula 1 may be at least one selected from Formulas 1-1 to 1-9 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

In the present invention, (A) the pigment dispersion may contain at least one pigment.

In the present invention, the photopolymerizable compound may contain at least one or more of a monofunctional monomer and a bifunctional or higher functional monomer.

The present invention may include one or more selected from the group consisting of other polymer compounds, curing agents, surfactants, adhesion accelerators, antioxidants, ultraviolet absorbers, and aggregation inhibitors.

In addition, the present invention relates to a color filter comprising a colored pattern manufactured using the colored photosensitive resin composition.

Further, the present invention relates to a solid-state imaging device including the color filter.

A color filter and a solid-state imaging device manufactured using the colored photosensitive resin composition according to the present invention can improve adhesion between substrates and heat resistance. Therefore, a robust and high-quality device can be provided by applying the color filter according to the present invention.

The present invention includes a pigment dispersion, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, an additive, and a solvent, wherein the additive includes a compound represented by the following formula (1), thereby providing a colored photosensitive resin composition with excellent adhesion and the same Hereinafter, a color filter and a display device manufactured using the above will be described in detail.

[Formula 1]

In Formula 1, R and R' are each independently a carboxy group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, and a carbo group having 3 to 12 carbon atoms. A yl group, an aromatic substituent having 3 to 12 carbon atoms, or a heteroaromatic substituent having 3 to 12 carbon atoms, and n is each independently an integer of 1 to 5.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, these examples are only presented as an example to explain the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples. will be.

<Colored photosensitive resin composition>

The colored photosensitive resin composition of the present invention contains (A) a pigment dispersion, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) an additive and (F) a solvent, and E) The additive is characterized in that it includes a compound represented by Formula 1, and, if necessary, other additives selected from the group consisting of other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-aggregation agents. It may include one or more species that are.

[Formula 1]

In Formula 1, R and R' are each independently a carboxy group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, and a carbo group having 3 to 12 carbon atoms. A yl group, an aromatic substituent having 3 to 12 carbon atoms, or a heteroaromatic substituent having 3 to 12 carbon atoms, and n is each independently an integer of 1 to 5.

(A) pigment dispersion

The pigment dispersion according to the present invention contains one or more types of pigments, and may further include one or more types of dyes or pigment dispersants as needed.

(a1) pigment

As the pigment, organic or inorganic pigments generally used in the art may be used. As the organic pigment, various pigments used in printing ink, inkjet ink, etc. may be used. Specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, iso Indoline pigments, ferylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, pravanthrone pigments, A pyranthrone pigment, a diketopyrroropyrrole pigment, etc. are mentioned. Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and specifically, metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black. oxides or composite metal oxides; and the like. In particular, the organic and inorganic pigments include compounds classified as pigments in color index (published by The Society of Dyers and Colourists), more specifically, the following color index (C.I.) numbers Although a pigment can be mentioned, it is not necessarily limited to these.

C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185;

C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71;

C.I. Pigment Red 9, 97, 105, 122, 123, 139, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264;

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;

C.I. Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64 and 76;

C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58;

C.I Pigment Brown 28;

C.I Pigment Black 1 and 7 and the like.

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

The above exemplified C.I. Among the pigment pigments, 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 139, 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. A pigment selected from Pigment Green 58 can be preferably used.

The content of the pigment is in the range of 10 to 50% by weight, preferably 15 to 45% by weight, based on the total solid content of the pigment dispersion. When the content of the pigment is in the range of 15 to 40% by weight based on the above, the viscosity is low, the storage stability is excellent, and the dispersion efficiency is high, so it is effective in increasing the contrast ratio, so it is preferable.

(a2) dye

The dye may be used without limitation as long as it has solubility in organic solvents. Preferably, it is preferable to use a dye capable of securing reliability such as solubility in an alkaline developing solution, heat resistance, and solvent resistance while having solubility in organic solvents.

As the dye, acid dyes having an acid group such as sulfonic acid or carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof may be used. Acid dyes of the system and their derivatives can also be selected.

Preferably, the dye may include a compound classified as a dye in the color index (published by The Society of Dyers and Colourists) or a known dye described in a dyeing note (color dyeing thread), but is not limited thereto.

Specific examples of the dye include C.I. As a solvent dye,

C.I. yellow dyes such as Solvent Yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163;

C.I. red dyes such as Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179;

C.I. orange dyes such as Solvent Orange 2, 7, 11, 15, 26, 41, 45, 56, 62;

C.I. blue dyes such as Solvent Blue 5, 35, 36, 37, 44, 59, 67, and 70;

C.I. violet dyes such as Solvent Violet 8, 9, 13, 14, 36, 37, 47, 49;

C.I. and green dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35.

C.I. Among solvent dyes, C.I. Solvent Yellow 14, 16, 21, 56, 151, 79, 93; C.I. Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; C.I. Solvent Orange 41, 45, 62; C.I. Solvent Blue 35, 36, 44, 45, 70; C.I. Solvent Violet 13 is preferred and the dual C.I. Solvent Yellow 21, 79; C.I. Solvent Red 8, 122, 132; C.I. Solvent Orange 45, 62 are more preferred.

Also, C.I. As an acid dye,

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 ; 184 , 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251, etc. ;

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217 ,227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346, 349 , 382, 383, 394, 401, 412, 417, 418, 422, 426 and the like red dyes;

orange dyes such as C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

C.I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1 blue dyes such as , 335 and 340;

violet dyes such as C.I. Acid Violet 6B, 7, 9, 17, 19, 66;

and green dyes such as C.I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, and 109.

Among acid dyes, C.I. Acid Yellow 42 having excellent solubility in organic solvents; C.I. Acid Red 92; C.I. Acid Blue 80, 90; C.I. Acid Violet 66; C.I. Acid Green 27 is preferred.

Also as a C.I. direct dye,

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , 136, 138, yellow dyes such as 141;

C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

orange dyes such as C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 ; 189 ,190,192,193,194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247, 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, blue dyes such as 293;

violet dyes such as C.I. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Green dyes, such as C.I. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. are mentioned.

Also, C.I. As a modanto dye,

yellow dyes such as C.I. Modanto Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C.I. Modanto Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, red dyes such as 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

C.I. Orange such as Modanto Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48 dyes;

C.I. Modanto Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, blue dyes such as 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;

violet dyes such as C.I. Modanto Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

green dyes such as C.I. Modanto Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53; and the like.

These dyes can be used individually or in combination of two or more types, respectively, as needed.

The content of the dye in the pigment dispersion is preferably 0.5 to 80% by weight, more preferably 0.5 to 60% by weight, and particularly preferably 1 to 50% by weight based on 100% by weight of the solid content in the pigment dispersion. . When the content of the dye in the pigment dispersion is within the above range based on the above standards, it is possible to prevent a decrease in reliability in which the dye is eluted by an organic solvent after pattern formation, and it is preferable because the sensitivity is excellent.

(a3) pigment dispersant

It is preferable to use a pigment dispersant in which the particle size is uniformly dispersed as the pigment. One example of a method for uniformly dispersing the particle size of the pigment is a method of dispersing treatment by containing a pigment dispersant, and according to this method, a pigment dispersion in which the pigment is uniformly dispersed in the composition can be obtained.

Specific examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine surfactants, which may be used alone or in combination of two or more. .

The pigment dispersant is added to maintain the deagglomeration and stability of the pigment, and those generally used in the art may be used without limitation. Preferably, it is good to contain an acrylate-based dispersant (hereinafter referred to as an acrylic dispersant) containing BMA (butyl methacrylate) or DMAEMA (N,N-dimethylaminoethyl methacrylate). At this time, it is preferable to apply the acrylic dispersant prepared by the living control method as suggested in Korean Patent Publication No. 2004-0014311, and the commercial product of the acrylate-based dispersant prepared through the living control method is DISPER BYK- 2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150. The above-exemplified acrylic dispersants may be used alone or in combination of two or more.

As the pigment dispersant, other resin-type pigment dispersants may be used in addition to the above-described acrylic dispersant. The other resin-type pigment dispersants include known resin-type pigment dispersants, particularly polycarboxylic acid esters represented by polyurethanes and polyacrylates, unsaturated polyamides, polycarboxylic acids, and (partial) polycarboxylic acids. Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and modified products thereof, free carboxyl groups oily dispersants such as amides formed by the reaction of a polyester with a poly(lower alkylenimine) or salts thereof; water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; modified polyacrylate; adducts of ethylene oxide/propylene oxide, phosphate esters, and the like. As the cationic resin dispersant for the above-described resin type dispersant, for example, DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK (Big) Chemie Co., Ltd. BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF's EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; SOLSPERSE-24000, SOLSPERSE-32550, NBZ-4204/10 from Lubrizol; HINOACT T-6000, HINOACT T-7000, and HINOACT T-8000 from Kawaken Fine Chemical; AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823 from Ajinomoto; FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44 and the like available from Kyoeisha Chemical Co., Ltd. In addition to the above acrylic dispersant, other resin type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with an acrylic dispersant.

The amount of the pigment dispersant is in the range of 5 to 60% by mass, more preferably 15 to 50% by mass, based on 100% by mass of the solid content of the pigment used. If the content of the pigment dispersant exceeds 60% by mass based on the above, the viscosity may increase, and if it is less than 5% by mass, it may be difficult to atomize the pigment or cause problems such as gelation after dispersion.

The content of the pigment dispersion is 5 to 80% by weight, preferably 10 to 70% by weight based on 100% by weight of the solid content in the colored photosensitive resin composition. When the pigment dispersion is contained in an amount of 5 to 80% by weight based on the above, the color density of pixels is sufficient even when a thin film is formed, and the omission of non-pixel parts is not reduced during development, so that residues are hardly generated.

In the present invention, the total solid content in the colored photosensitive resin composition means the total content of the remaining components except for the solvent in the colored photosensitive resin composition.

(B) alkali soluble resin

The alkali-soluble resin is a component that imparts solubility to an alkali developing solution used in the developing process when forming a pattern, and generally used in the art may be used without limitation, and preferably contains an unsaturated double bond. It may include a repeating unit derived from a monomer having

The type of the monomer containing the unsaturated double bond is not particularly limited, and examples thereof include styrene, vinyltoluene, α-methylstyrene, 4-methylstyrene, p-chlorostyrene, o-methoxystyrene, m- Methoxy styrene, p-methoxy styrene, o-vinylbenzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p -Aromatic vinyl compounds such as vinylbenzyl glycidyl ether; N-cyclohexylmaleimide, 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; and 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane , 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane and unsaturated oxetane-based compounds such as the like.

The monomers containing the unsaturated double bond may be used alone or in combination of two or more.

The content of the monomer containing the unsaturated double bond is not particularly limited, but is preferably included in an amount of 5 to 50 mol% based on 100 mol% of the entire repeating unit constituting the alkali-soluble resin.

The acid value of the alkali-soluble resin is preferably 30 to 150 mgKOH / g.

When the acid value of the alkali-soluble resin is within the above range, the colored photosensitive resin composition can secure a sufficient developing rate, and the adhesion between the substrate and the colored photosensitive resin composition is reduced to prevent short circuiting of the pattern, The compatibility with the pigment dispersion is excellent, and the precipitation of the pigment dispersion can be prevented. In addition, it is possible to prevent an increase in viscosity by preventing a phenomenon in which the storage stability of the colored photosensitive resin composition is lowered.

In addition, the weight average molecular weight in terms of polystyrene (hereinafter simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; using tetrahydrofuran as an elution solvent) is 3,000 to 100,000, preferably 5,000 to 50,000. Alkali-soluble resins are preferred. When the molecular weight is within the above range, the hardness of the coating film is improved, the residual film rate is high, the solubility of the non-exposed portion in the developing solution is excellent, and the resolution tends to be improved, which is preferable.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the alkali-soluble resin is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of 1.5 to 6.0 is preferable because developability is excellent.

The alkali-soluble resin may be included in an amount of 10 to 80% by weight, preferably 10 to 70% by weight based on 100% by weight of the solid content in the colored photosensitive resin composition. When the alkali-soluble resin is included within the above range, pattern formation is easy due to sufficient solubility in the developing solution, and film reduction of the pixel portion of the exposed portion is prevented during development, so that non-pixel portion omission may be improved.

(C) photopolymerizable compound

The photopolymerizable compound is a compound that can be polymerized by the action of the following photopolymerization initiator, and a monofunctional monomer or a bifunctional or higher functional monomer may be used, preferably a bifunctional or higher multifunctional monomer.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate or N-vinyl group. Rolidone and the like, but are not limited thereto.

Specific examples of the bifunctional monomer include 1,6-hexanedioldi(meth)acrylate, ethylene glycoldi(meth)acrylate, neopentylglycoldi(meth)acrylate, and triethylene glycoldi(meth)acrylate. , bis(acryloyloxyethyl) ether of bisphenol A or 3-methylpentanediol di(meth)acrylate, and the like, and specific examples of the trifunctional or higher functional monomer include trimethylol propane tri(meth)acrylate, ethoxyl Rated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta( meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, or dipentaerythritol hexa(meth)acrylate, but are not limited thereto no.

The photopolymerizable compound is preferably included in an amount of 5 to 45% by weight based on 100% by weight of the solid content in the colored photosensitive resin composition, and more preferably 7 to 45% by weight. When the photopolymerizable compound is contained in an amount of 5 to 45% by weight based on the above, it is preferable because the strength and smoothness of the pixel portion become good.

(D) photopolymerization initiator

The photopolymerization initiator may be used without particular limitation as long as it can polymerize a photopolymerizable compound. In particular, the photopolymerization initiator is an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a biimidazole-based compound, an oxime compound, and a thioxanthone-based compound from the viewpoint of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, etc. It is preferable to use at least one compound selected from the group consisting of compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxyl) Roxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1 -one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc. are mentioned.

Examples of the benzophenone-based compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra ( tert-butyl peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 -(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2- yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl )-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine; and the like.

Specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro). Phenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole , 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2-bis(2,6-dichlorophenyl)-4, 4'5,5'-tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4,4',5,5' position is substituted with a carboalkoxy group; and the like. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4' ,5,5'-tetraphenylbiimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4'5,5'-tetraphenyl-1,2'-biimidazole are preferably used do.

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and OXE01 and OXE02 from BASF are typical commercial products.

Examples of the thioxanthone-based compounds include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. there is

In addition, the photopolymerization initiator may further include a photopolymerization initiator to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition according to the present invention contains a photopolymerization initiation auxiliary, so that the sensitivity is further increased and productivity can be improved.

As the photopolymerization initiation aid, for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group may be preferably used.

As the amine compound, it is preferable to use an aromatic amine compound, specifically, an aliphatic amine compound such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Isoamyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler's ketone) ), 4,4'-bis (diethylamino) benzophenone, etc. can be used.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

Specific 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), pentaerythritoltetrakis(3-mercaptobutyl rate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), etc. can

The photopolymerization initiator may be included in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight, based on 100% by weight of the solid content of the colored photosensitive resin composition of the present invention. When the photopolymerization initiator is included in the content range, the colored photosensitive resin composition is highly sensitive and the exposure time is shortened, which is preferable because productivity is improved and high resolution can be maintained. In addition, the strength of the pixel portion formed using the composition under the above-described conditions and the smoothness of the surface of the pixel portion may be improved. In addition, in the case of the photopolymerization initiation aid, 10 to 90% by weight, preferably 20 to 90% by weight, of the total photopolymerization initiator. When the ratio of the photopolymerization initiation aid in the total photopolymerization initiator is less than 10% by weight, the decrease in sensitivity due to the dye cannot be overcome and the pattern short circuit is likely to occur during the developing process.

In addition, when the photopolymerization initiation auxiliary agent is further used, the photopolymerization initiation auxiliary agent is preferably 0.1 to 40% by weight based on the total solid weight of the colored photosensitive resin composition of the present invention based on the content of the alkali-soluble resin and the photopolymerizable compound. may be included in an amount of 1 to 30% by weight. When the amount of the above is within the range of 0.1 to 40% by weight, the sensitivity of the colored photosensitive resin composition is further increased, and the productivity of a color filter formed using the composition is improved.

(E) additives

Compound represented by Formula 1

In one embodiment of the present invention, in order to improve the adhesion problem between substrates, the colored photosensitive resin composition is characterized in that it contains a compound represented by the following formula (1) as an additive.

The compound represented by Chemical Formula 1 includes -S-S- bonds in the structure, and has a structure in which they are connected to R and R' through one or more hydrocarbons. According to this structure, it contributes to the effect of enhancing adhesion when forming micropatterns. Specifically, the surface crosslinking density of the cured resin composition increases as the -S-S- bond of Chemical Formula 1 is broken due to the energy irradiated during UV or thermal curing, thereby increasing the fineness of the cured resin composition. The degree of curing and adhesion are improved during pattern production.

[Formula 1]

In Formula 1, R and R' are each independently a carboxy group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, and a carbo group having 3 to 12 carbon atoms. It may be a yl group, an aromatic substituent having 3 to 12 carbon atoms, or a heteroaromatic substituent having 3 to 12 carbon atoms.

n is each independently an integer of 1 to 5.

Preferably, R and R' are each independently an alkyl group having 1 to 4 carbon atoms, a heteroaromatic substituent having 3 to 6 carbon atoms, a substituted or unsubstituted vinyl group, a carboxy group, a hydroxyl group, a benzoyl group, a phenyl group, a furyl group Or it may be a phenol group, more preferably a vinyl group or a carboxy group.

The colored photosensitive resin composition may contain a small amount of the compound represented by Formula 1 in an amount of 0.05 to 0.50% by weight based on 100% by weight of the solid content of the composition, and more preferably in an amount of 0.10 to 0.40% by weight, improving the lifting phenomenon of the micropattern. effective in doing When included below or in excess of the above range, the adhesion enhancing effect in the micropattern tends to decrease. This is because the -S-S- bond of Formula 1 is broken due to the energy irradiated during ultraviolet or heat curing, and the surface crosslinking density of the cured resin composition increases by combining with other functional groups in the pattern surface and composition, thereby increasing the curing rate during micropattern production. and adhesion is improved.

In addition, in the compound represented by Formula 1, as the number of repeating units n increases, hydrophobicity increases, and binding property in the composition also increases.

Specifically, Chemical Formula 1 may be one or more selected from Chemical Formulas 1-1 to 1-9.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

Other Additives

Other additives may be selectively added as needed, and include, for example, a polymer compound, a curing agent, a surfactant, an adhesion accelerator, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor.

Specific examples of the polymer compound include curable resins such as epoxy resin and maleimide resin, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. can

The curing agent is used for deep curing and increasing mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, and the like.

Specific examples of the epoxy compound in the curing agent include bisphenol A-based epoxy resins, hydrogenated bisphenol A-based epoxy resins, bisphenol F-based epoxy resins, hydrogenated bisphenol F-based epoxy resins, noblock type epoxy resins, other aromatic epoxy resins, and alicyclic epoxy resins. , glycidyl ester-based resins, glycidylamine-based resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co)polymer epoxides, isoprene ( Co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, etc. are mentioned.

Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like.

The curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerization of an epoxy group of an epoxy compound and an oxetane skeleton of an oxetane compound together with the curing agent. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators. The polyhydric carboxylic acid anhydrides may be commercially available as epoxy resin curing agents. Specific examples of the epoxy resin curing agent include a product name (Adeka Hadona EH-700, manufactured by Adeka Industrial Co., Ltd.), a product name (Rikashiddo HH, manufactured by Shin Nippon Ewha Co., Ltd.), a product name (MH-700, Shin Nippon Ewha Co., Ltd.) production), etc. The curing agents exemplified above may be used alone or in combination of two or more.

The surfactant may be used to further improve the film formation of the photosensitive resin composition, and a fluorine-based surfactant or a silicone-based surfactant may be preferably used.

The silicone-based surfactants include, for example, DC-3PA, DC-7PA, SH-11PA, SH-21PA, SH-8400 of Dow Corning Toray Silicon Co., Ltd. as commercial products, and TSF-4440, TSF-4300, TSF of GE Toshiba Silicone Co., Ltd. -4445, TSF-4446, TSF-4460, TSF-4452, etc. Examples of the fluorine-based surfactant include Megapiece F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink and Chemicals Co., Ltd. as commercial products. The surfactants exemplified above may be used alone or in combination of two or more.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-( 3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethyne Toxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, etc. are mentioned. Adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be included in a weight fraction of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the solid content of the colored photosensitive resin composition.

Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like.

Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotyriazole, alkoxybenzophenone, and the like.

Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

(F) solvent

As long as the solvent is effective in dissolving other components included in the colored photosensitive resin composition, solvents used in conventional colored photosensitive resin compositions may be used without particular limitation, and in particular, ethers, aromatic hydrocarbons, ketones, alcohols, and esters. or amides are preferred.

The solvent is specifically ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, Alkylene glycol alkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, methyl ethyl ketone , acetone, methyl amyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, 3- Cyclic esters, such as esters, such as methoxy methyl propionate, and (gamma)-butyrolactone, etc. are mentioned.

The solvent is preferably an organic solvent having a boiling point of 100 ℃ to 200 ℃ in terms of coating and drying properties, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butalak tate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like can be used.

Each of the above-exemplified solvents may be used alone or in combination of two or more, and may be included in an amount of 20 to 90% by weight, preferably 30 to 85% by weight, based on the total weight of the colored photosensitive resin composition of the present invention. When the solvent is in the range of 20 to 90% by weight, the coating property is good when applied with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), an inkjet, or the like. provides a disengagement effect.

<Color filter and display device>

Further, the present invention provides a color filter made of the colored photosensitive resin composition according to the present invention and a solid-state imaging device including the color filter. The color filter and the solid-state imaging device of the present invention may not include a polarizing plate, and including a polarizing plate also falls within the scope of the present invention.

The solid-state imaging device may include, but is not limited to, a CCD (Charge-Coupled Device) image sensor and a CMOS (complementary metal-oxide-semiconductor) image sensor, and all displays known in the applicable field device can be exemplified.

The color filter may be prepared by coating the colored photosensitive resin composition of the present invention described above on a substrate, and photocuring and developing to form a pattern.

First, by applying the colored photosensitive resin composition to a substrate and then heating and drying, volatile components such as solvents are removed to obtain a smooth coating film.

As the coating method, for example, spin coating, casting coating, roll coating, slit and spin coating, or slit coating may be used. After application, heat drying (prebaking) or drying under reduced pressure is followed by heating to volatilize volatile components such as solvents. Here, the heating temperature is usually 70 to 200°C and preferably 80 to 130°C. The coating film thickness after drying by heating is about 0.1 to 8 μm. The coating film obtained in this way is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper so that parallel light rays are uniformly irradiated to the entire exposure area and accurate positioning of the mask and the substrate is performed. When irradiated with ultraviolet rays, the portion irradiated with ultraviolet rays is cured.

As the ultraviolet rays, g-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm), and the like may be used. The irradiation amount of ultraviolet rays can be appropriately selected as needed, and is not limited thereto in the present invention. When the cured coating film is contacted with a developing solution to dissolve the unexposed portion and develop, a desired pattern shape can be formed.

As the developing method, any of a liquid addition method, a dipping method, a spray method, and the like may be used. Further, the substrate may be tilted at an arbitrary angle during development. The developing solution is usually an aqueous solution containing an alkaline compound and a surfactant. Any of inorganic and organic alkaline compounds may be sufficient as the said alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate , sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like. Further, specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine, etc. are mentioned.

These inorganic and organic alkaline compounds can be used individually or in combination of two or more types, respectively. The concentration of the alkaline compound in the alkaline developing solution is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight.

As the surfactant in the alkali developer, at least one selected from the group consisting of nonionic surfactants, anionic surfactants, and cationic surfactants may be used.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate or sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate, dodecylbenzenesulfonic acid Alkylaryl sulfonic acid salts, such as sodium and sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the cationic surfactant include amine salts or quaternary ammonium salts such as stearylamine hydrochloride or lauryltrimethylammonium chloride. These surfactants can be used alone or in combination of two or more.

The concentration of the surfactant in the developing solution is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, and more preferably 0.1 to 5% by weight.

After development, it is washed with water and, if necessary, post-baked at 80 to 230°C, preferably at 80 to 120°C for 10 to 60 minutes.

Hereinafter, the present invention will be described in more detail based on examples, but the embodiments of the present invention disclosed below are only examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention has been indicated in the claims, and furthermore contains all changes within the meaning and range equivalent to the written claims. In the following Examples and Comparative Examples, "%" and "parts" indicating content are based on mass unless otherwise specified.

Preparation Example 1: Preparation of pigment dispersion a-1

As a pigment, C.I. 14.0% by weight of Pigment Red 254, 6.0% by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, and 80.0% by weight of propylene glycol methyl ether acetate as a solvent were mixed/dispersed for 12 hours by a bead mill to obtain a pigment dispersion a-1 was manufactured.

Preparation Example 2: Preparation of pigment dispersion a-2

As a pigment, C.I. 14.5% by weight of Pigment Yellow 139, 5.0% by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, and 80.5% by weight of propylene glycol methyl ether acetate as a solvent were mixed/dispersed by a bead mill for 12 hours to obtain a pigment dispersion a-2 was manufactured.

Preparation Example 3: Synthesis of alkali-soluble resin

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

Next, the atmosphere in the flask was changed from nitrogen to air, and 42.6 g of glycidyl methacrylate (0.30 mol (64 mol% based on the acrylic acid used in this reaction)) was introduced into the flask, and the reaction was continued at 110 ° C. for 6 hours. , an unsaturated group-containing resin A-1 having a solid acid value of 79 mgKOH/g was obtained. 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.

Examples 1 to 4 and Comparative Examples 1 to 7: Preparation of colored photosensitive resin composition

A colored photosensitive resin composition was prepared using the ingredients and contents of Table 1 below.

- a-1: Pigment dispersion according to Preparation Example 1

- a-2: Pigment dispersion according to Preparation Example 2

- Alkali-soluble resin (B): Alkali-soluble resin according to Preparation Example 3

- Photopolymerizable compound (C): KAYARAD DPHA (manufactured by Nippon Kayaku)

- Photopolymerization initiator (D): Irgacure OXE-01 (BASF)

- e-1: SH-8400 (Dow Corning Korea Co., Ltd.)

- e-2: (Sigma-Aldrich)

-e-3: (Sigma-Aldrich)

- e-4: (Sigma-Aldrich)

-e-5: 3-methacryloyloxy propyltrimethoxy silane (Shin-Etsu Co., Ltd.)

- Solvent (F): Propylene glycol methyl ether acetate (KH NEOCHEM CO., LTD.)

Experimental example

(1) Evaluation of pattern adhesion

On the surface of a 6-inch Si-wafer in a clean room at 23 ° C, the photosensitive composition obtained in the above Examples and Comparative Examples was applied by spin coating, and then dried at 100 ° C for 90 seconds to volatilize the volatile components, thereby forming a photosensitive composition. A composition layer was formed. After cooling to 23° C., the formed photosensitive composition layer was exposed to light using an i-line stepper. The wafer on which the exposed coating film was formed was developed with a 0.2% by weight aqueous solution of tetramethylammonium hydroxide (TMAH), and then heated at 220° C. for 180 seconds to form pixels. The obtained pixel thickness was 0.5 μm. The resolutions of the formed pixels were 1.5, 1.0, and 0.5 μm. It was confirmed through CD-SEM Image that 100% of the remaining without the lifting obtained above. The results are shown in Table 2 below.

<Evaluation Criteria>

1: Less than 40% of the formed pattern remains

2: More than 40% and less than 60% of the formed pattern remains

3: More than 60% and less than 80% of the formed pattern remains

4: More than 80% and less than 100% of the formed pattern remains

5: The formed pattern remains 100% without lifting

(2) Heat resistance evaluation

The photosensitive composition obtained in Examples and Comparative Examples was applied by spin coating on the surface of a 4-inch glass wafer in a clean room at 23 ° C., and then dried at 100 ° C. for 90 seconds to volatilize the volatile components, thereby forming the photosensitive composition. layer was formed. After cooling to 23° C., the formed photosensitive composition layer was exposed to light using MA6. The wafer on which the exposed coating film was formed was developed with a 0.2% by weight aqueous solution of tetramethylammonium hydroxide (TMAH), and then heated at 220° C. for 180 seconds to form a coating film. The thickness of the obtained coating film was all 0.5 micrometer. The heat resistance test was conducted at 230° C. for 1 hour. The prepared substrates were compared and evaluated by calculating color changes before and after evaluation. The equation used at this time was calculated by Equation 1 below, which represents the color change in the three-dimensional colorimetric system defined by L ^* , a ^* , b ^* , and the results are shown in Table 3 below.

[Equation 1]

ΔEab(L ^* , a ^* , b ^* ) = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2

○: Less than ΔEab ^* 3.0,

△: ΔEab ^* 3.0 or more and less than 4.0

×: greater than ΔEab ^* 4.0

Referring to the experimental data in Tables 2 and 3, in the case of Examples 1 to 4 prepared including the colored photosensitive resin composition according to an embodiment of the present invention, the observation results at each pattern size of 1.5, 1.0 and 0.5 μm, While the formed pattern remained 100% without lifting and showed excellent results in the heat resistance test, Comparative Examples 1 to 7, in which the colored photosensitive resin composition was out of the present invention, showed lifting of the pattern, especially at each pattern size of 1.0 and 0.5 μm. It was observed, and the heat resistance was lower than that of the examples.

In particular, compared to Comparative Examples 2 to 5 in which the compound represented by Formula 1 is out of the range of 0.05 to 0.50% by weight based on 100% by weight of the solid content of the colored photosensitive resin composition, Comparative Examples that do not contain the compound represented by Formula 1 at all In the case of 1, 6 and 7, it was observed that the adhesiveness and heat resistance of the pattern were further deteriorated.

Therefore, it was confirmed that the colored photosensitive resin composition according to the present invention and the color filter and solid-state imaging device manufactured using the same have excellent adhesion and heat resistance without lifting of the pattern.

Claims (7)

(A) a pigment dispersion, (B) an alkali soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) an additive and (F) a solvent;
The (E) additive comprises 0.05 to 0.50% by weight of the compound represented by Formula 1 based on 100% by weight of the solid content of the colored photosensitive resin composition, colored photosensitive resin composition:
[Formula 1]

In Formula 1,
R and R' are each independently a carboxy group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a carbonyl group having 3 to 12 carbon atoms, and a carbon atom having 3 to 10 carbon atoms. An aromatic substituent of 12 or a heteroaromatic substituent of 3 to 12 carbon atoms;
n is each independently an integer of 1 to 5. The method of claim 1,
Chemical Formula 1 is one or more selected from the following Chemical Formulas 1-1 to 1-9, the colored photosensitive resin composition.
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]
The method of claim 1,
The (A) pigment dispersion contains at least one pigment, the colored photosensitive resin composition. The method of claim 1,
The photopolymerizable compound is a colored photosensitive resin composition comprising at least one of a monofunctional monomer and a bifunctional or higher functional monomer. The method of claim 1,
The additive is a colored photosensitive resin composition comprising at least one selected from the group consisting of a polymer compound, a curing agent, a surfactant, an adhesion accelerator, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor. A color filter comprising a colored pattern made of the colored photosensitive resin composition according to any one of claims 1 to 5. A solid-state imaging device comprising the color filter according to claim 6.