KR102338255B1 - A colored photosensitive resin composition, color filter and image display device produced using the same - Google Patents

Abstract

The colored photosensitive resin composition according to the present invention includes at least one photopolymerization initiator satisfying Formulas 1 and 2, and after pre-bake, transmittance at 365 nm wavelength is 0.1% or more, and transmittance at 405 nm wavelength is 0.4 % or more.
[Equation 1]
ε 405 > 0.1
[Equation 2]
(ε 405 × 10 / ε 365) > 0.1
(In Equations 1 and 2 above,
ε 365 is the molar extinction coefficient for the wavelength of 365 nm of the photopolymerization initiator,
ε 405 is the molar extinction coefficient for the 405 nm wavelength of the photopolymerization initiator).
The colored photosensitive resin composition according to the present invention has excellent adhesion, can suppress peeling of the pattern during the development process, and has excellent solvent resistance.

Description

Colored photosensitive resin composition, color filter and image display device manufactured using the same

The present invention relates to a colored photosensitive resin composition, a color filter manufactured using the same, and an image display device.

Color filters are widely used in imaging devices, liquid crystal displays (LCDs), and the like, and their application range is rapidly expanding. A color filter used in a color liquid crystal display device or an image pickup device is a color photosensitive resin composition containing a pigment corresponding to each color of red, green, and blue is applied uniformly by spin coating on a substrate on which a black matrix is patterned. After that, the coating film formed by heating and drying (hereinafter, sometimes referred to as “pre-firing”) is exposed and developed, and, if necessary, further heat-hardening (hereinafter, “post-firing”) for each color. It is manufactured by repeatedly forming pixels of each color. Here, the black matrix on which the pattern is formed is usually formed of a black photosensitive resin composition.

As such a colored photosensitive resin composition, a composition containing a photopolymerizable compound and a photoinitiator together with a pigment and a binder resin is widely used. When the adhesion to the underlying substrate is insufficient, the pattern is peeled off during the developing process, resulting in display defects. The development of a colored photosensitive resin composition capable of suppressing the phenomenon is somewhat generated is required.

Korean Patent Laid-Open No. 2014-0039019 relates to a novel compound, a photopolymerizable composition, a color filter, a method for manufacturing a color filter, a solid-state imaging device, and a lithographic printing plate, and discloses the application of a compound having high absorbance as an initiator.

However, when the absorbance of the initiator is increased as in the prior art, additional problems such as an enlarged line width may occur to some extent.

Republic of Korea Patent Publication No. 2014-0039019 (2014.03.31)

An object of the present invention is to provide a colored photosensitive resin composition capable of suppressing the occurrence of display defects due to pattern peeling during the developing process by increasing adhesion to a lower substrate, a color filter and an image display device manufactured using the same is to provide

The present invention relates to a photopolymerization initiator satisfying the following formulas 1 and 2; a colored photosensitive resin containing at least one type, and having a transmittance of 0.1% or more at a wavelength of 365 nm after prebake, and a transmittance of at least 0.4% at a wavelength of 405 nm A composition is provided.

[Equation 1]

ε 405 > 0.1

[Equation 2]

(ε 405 × 10 / ε 365) > 0.1

In Equations 1 and 2 above,

ε 365 is the molar extinction coefficient for the wavelength of 365 nm of the photopolymerization initiator,

ε 405 is the molar extinction coefficient for the 405 nm wavelength of the photopolymerization initiator.

In addition, the present invention provides a color filter comprising a cured product of the above-described colored photosensitive resin composition.

In addition, the present invention provides an image display device including the above-described color filter.

The colored photosensitive resin composition according to the present invention has excellent adhesiveness, can suppress peeling of the pattern during the development process, and has excellent solvent resistance.

In addition, a color filter and an image display device manufactured using the colored photosensitive resin composition according to the present invention have excellent adhesion and solvent resistance, and thus have excellent driving performance.

Hereinafter, the present invention will be described in more detail.

In the present invention, when a member is said to be located "on" another member, this includes not only a case in which a member is in contact with another member but also a case in which another member is present between the two members.

In the present invention, when a part "includes" a certain component, this means that other components may be further included, rather than excluding other components, unless otherwise stated.

<Colored photosensitive resin composition>

One aspect of the present invention includes at least one type of photopolymerization initiator satisfying the following formulas 1 and 2, and after pre-bake, transmittance at 365 nm wavelength is 0.1% or more, and transmittance at 405 nm wavelength is 0.4% It relates to the above colored photosensitive resin composition.

[Equation 1]

ε 405 > 0.1

[Equation 2]

(ε 405 × 10 / ε 365) > 0.1

In Equations 1 and 2 above,

ε 365 is the molar extinction coefficient for the wavelength of 365 nm of the photopolymerization initiator,

ε 405 is the molar extinction coefficient for the 405 nm wavelength of the photopolymerization initiator.

The colored photosensitive resin composition according to the present invention has a transmittance of 0.1% or more at a wavelength of 365 nm after prebaking, and a transmittance of 0.4% or more at a wavelength of 405 nm, so that the transmittance of the exposure light to the coating film is high, so that the exposure light to the lower part of the coating film is easily There is an advantage in that the sensitivity and reliability of the coating film are improved because photocuring of the lower film is easily achieved.

The colored photosensitive resin composition according to the present invention may further include, in addition to the photopolymerization initiator, a colorant, alkali-soluble resin, photopolymerizable compound, solvent, additive, and the like, which can be included in the colored photosensitive resin composition and used in the art.

light curing initiator

The colored photosensitive resin composition according to the present invention includes at least one photopolymerization initiator satisfying the following formulas 1 and 2.

[Equation 1]

ε 405 > 0.1

[Equation 2]

(ε 405 × 10 / ε 365) > 0.1

In Equations 1 and 2 above,

ε 365 is the molar extinction coefficient for the wavelength of 365 nm of the photopolymerization initiator,

ε 405 is the molar extinction coefficient for the 405 nm wavelength of the photopolymerization initiator.

Since the colored photosensitive resin composition according to the present invention contains the photopolymerization initiator satisfying Equations 1 and 2, adhesion with the lower substrate is increased, thereby preventing the pattern from peeling off during the development process and causing display defects. In addition, the reverse taper phenomenon can be prevented, and thereby, there is an advantage of excellent adhesion.

In the present invention, the molar extinction coefficient may be measured by the following method. For example, a solution obtained by dissolving a photopolymerization initiator in a solvent such as propylene glycol monomethyl ether acetate at a concentration of 0.1% (1 g/1 L) is prepared, and absorbance is measured for this solution using an ultraviolet and visible spectrophotometer. In this case, the ultraviolet and visible spectrophotometer may be, for example, a UV-2550 equipment manufactured by SHIMADZU, but is not limited thereto. The molar extinction coefficient can be calculated by dividing the measured absorbance by the molar concentration (mol/L) of each photopolymerization initiator.

As the photopolymerization initiator, any photoinitiator commonly used in the art may be used without limitation as long as it satisfies Equations 1 and 2.

Specifically, the photopolymerization initiator may include at least one compound selected from the group consisting of a triazine-based compound, an acetophenone-based compound, a biimidazole-based compound, and an oxime compound. In this case, the colored photosensitive resin composition is highly sensitive and , which is preferable because it tends to improve the strength and patternability of the pixel portion.

The triazine-based compound is, for example, 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 etc. are mentioned.

The acetophenone-based compound is diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyethoxy) )phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 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 An oligomer etc. are mentioned.

The biimidazole-based compound is, for example, 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, phenyl group carboalkoxy at 4,4',5,5' position The imidazole compound etc. which are substituted by group are mentioned. Among them, 2,2'bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4', 5,5'-tetraphenylbiimidazole is preferably used.

The oxime-based compound is, for example, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(4-methylsulfanyl-phenyl)-butane-1 ,2-Butane-2-oxime-O-acetate, 1-(4-methylsulfanyl-phenyl)-butan-1-oneoxime-O-acetate, hydroxyimino-(4-methylsulfanyl-phenyl)- and ethyl acetate-O-acetate and hydroxyimino-(4-methylsulfanyl-phenyl)-ethyl acetate-O-benzoate.

In addition, in the range that does not impair the effects of the present invention, other photopolymerization initiators commonly used in this field may be further included. As another photoinitiator, a benzoin type compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound, etc. are mentioned, for example. These can be used individually or in combination of 2 or more types, respectively.

As a benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenyl benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra (tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-di(N,N'-dimethylamino)-benzophenone, etc. are mentioned.

Examples of the thioxanthone compound include 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone. and the like.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. can be heard

Others 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl, a titanocene compound, etc. are mentioned as another photoinitiator.

The photopolymerization initiator may be used in combination with a photopolymerization initiation auxiliary agent, and in this case, the colored photosensitive resin composition becomes more sensitive to improve productivity when forming a color filter, which may be preferable.

At least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and the like may be preferably used as the photopolymerization initiation adjuvant that can be used in combination with the photopolymerization initiator in the present invention.

Specific examples of the amine compound in the photopolymerization initiation aid include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-Dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler's ketone), 4,4'- and aromatic amine compounds such as bis(diethylamino)benzophenone. As the amine compound, an aromatic amine compound is preferably used.

Carboxylic acid compounds include, for example, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, and aromatic heteroacetic acids such as dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

Commercially available products of the photopolymerization initiator may include, but are not limited to, TR-PBG-327 (manufactured by BASF), NCI-831E (manufactured by ADEKA), and N-1919 (manufactured by ADEKA).

In one embodiment of the present invention, the photopolymerization initiator is preferably included in an amount of 0.1 to 20 parts by weight, more preferably 1 to 12 parts by weight, based on 100 parts by weight of the total solid content of the colored photosensitive resin composition. When the amount of the photopolymerization initiator used is included within the above range, the photosensitive resin composition is highly sensitive, and thus the strength of the pixel portion and smoothness on the surface of the pixel portion are excellent.

In addition, the amount of the photopolymerization initiation adjuvant is preferably included in an amount of 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the total solid content of the colored photosensitive resin composition. When the amount of the photopolymerization initiation adjuvant is included within the above range, the sensitivity efficiency of the photosensitive resin composition may be further increased, and productivity of a color filter formed using the composition may be improved.

coloring agent

In another embodiment of the present invention, the colored photosensitive resin composition is C.I. a green pigment comprising Pigment Green 59; and C.I. Pigment Blue 15:6, 15:3, 15:4 and 15:6 a colorant comprising at least one blue pigment selected from the group consisting of; may further include.

Specifically, the colored photosensitive resin composition according to the present invention is C.I. a green pigment comprising Pigment Green 59; and C.I. Pigment Blue 15:6, 15:3, 15:4 and 15:6 by including a colorant containing at least one blue pigment selected from the group consisting of, the transmittance at a wavelength of 365nm in the target spectrum of the coating film is 0.1% or more, , 405 nm transmittance is 0.4% or more, and there is an advantage in that it is possible to manufacture a colored pattern layer capable of high color reproduction.

In another embodiment of the present invention, the colorant may further include a yellow pigment.

When the colorant further includes a yellow pigment, it is preferable because colorability is improved to realize a wide color gamut.

More preferably, the colorant uses a ternary mixed pigment including a green pigment, a blue pigment, and a yellow pigment, thereby increasing the transmittance of 365 nm and 405 nm of the coating film to improve the optical efficiency of the photopolymerization initiator, thereby exhibiting excellent pattern formability.

The yellow pigment is, for example, 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 , 185 and 231 may include one or more selected from the group consisting of.

The colorant may further include organic or inorganic pigments commonly used in the art in addition to the aforementioned pigments.

As the pigment, various pigments used in printing inks, inkjet inks, etc. may be used, and specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline Pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, pravanthrone pigments, pyranthrone (pyranthrone) pigment, diketopyrroropyrrole pigment, etc. are mentioned.

Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and specifically, oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black Or a composite metal oxide etc. are mentioned. In particular, the organic and inorganic pigments include compounds classified as pigments in the color index (published by The Society of Dyers and Colorists), and more specifically, the color index (CI) number of pigments, but are not necessarily limited thereto.

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, 144, 149, 166, 168, 176, 177, 180, 192, 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 21, 28, 60, 64 and 76

C.I. Pigment Green 7, 10, 15, 25, 36, 47, 62 and 63

C.I Pigment Brown 28

C.I Pigment Black 1 and 7 etc.

Each of the above pigments may be used alone or in combination of two or more.

The above-exemplified C.I. Among the pigment pigments, C.I. Pigment Orange 38, C.I. Pigment Red 122, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Violet 23, C.I. A pigment selected from Pigment Blue 15:3 and Pigment Blue 15:6 may be preferably used.

The pigment may be used in the form of a colorant dispersion in which particle diameters are uniformly dispersed, but is not limited thereto. An example of a method for uniformly dispersing the particle size of the pigment includes a method of dispersing and dispersing a pigment dispersant. do.

The pigment dispersant may be further added separately from the dispersing agent containing the triazine-based compound described above, for example, cationic, anionic, nonionic, amphoteric, polyester-based, polyamine-based surfactants, and the like. , Each of these may be used alone or in combination of two or more, but is not limited thereto.

In addition, the colorant dispersion may further include a dispersion medium.

The dispersion medium is added for 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) including BMA (butyl methacrylate) or DMAEMA (N,N-dimethylaminoethyl methacrylate). In this case, it is preferable to apply the acrylic dispersant prepared by the living control method as presented in Korean Patent Application Laid-Open No. 2004-0014311. As a commercial product of the acrylate-based dispersant manufactured through the living control method, DISPER BYK- 2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, and the like.

The acrylic dispersants exemplified above may be used alone or in combination of two or more.

As the dispersion medium, a pigment dispersant of a resin type other than the acrylic dispersant may be used. The pigment dispersants of other resin types include known resin type pigment dispersants, in particular polyurethane, polycarboxylic acid esters typified by polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids (partially) amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamidephosphate salts, esters of hydroxyl-containing polycarboxylic acids and their modifications, or free ) oily dispersants such as amides or salts thereof formed by the reaction of a polyester having a carboxyl group with poly(lower alkyleneimine); 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 polyvinylpyrrolidone; Polyester; modified polyacrylates; and ethylene oxide/propylene oxide adducts and phosphate esters. As a commercially available product of the above-mentioned resin type dispersant, as a cationic resin dispersant, for example, BYK (Big) Chemi Corporation's brand names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK- 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF's trade names: 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; Trade names from Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Trade names of Kawaken Fine Chemicals: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Trade names of Ajinomoto Corporation: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Trade names of Kyoeisha Chemical Corporation: FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, fluorene DOPA-44, etc. are mentioned. Pigment dispersants of other resin types other than the above acrylic dispersants may be used alone or in combination of two or more, or may be used in combination with an acrylic dispersant.

The pigment dispersant may be included in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, more preferably 1 to 2 parts by weight based on 100 parts by weight of the total amount of the colored photosensitive resin composition. When the content of the pigment dispersant satisfies the above range, contrast and stability may be improved.

In another embodiment of the present invention, the colorant is included in an amount of 0.1 to 45 parts by weight, preferably 10 to 40 parts by weight, more preferably 15 to 35 parts by weight based on 100 parts by weight of the total solid content of the colored photosensitive resin composition. may be, but is not limited thereto. However, when the colorant is included within the above range, it is preferable because the viscosity is low, the storage stability is excellent, and the dispersion efficiency is high, so that it is effective in increasing the contrast ratio.

The green pigment may be included in an amount of 0.1 to 45 parts by weight, preferably 1 to 35 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the total solid content of the colored photosensitive resin composition, in this case I (365 nm wavelength) ) and H (405 nm wavelength) have the advantage of increasing the transmittance to increase the sensitivity, which is preferable.

The blue pigment may be included in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 7 parts by weight, more preferably 0.5 to 4 parts by weight, based on 100 parts by weight of the total solid content of the colored photosensitive resin composition, in which case the colorability of the coating film It is preferable because it has the advantage of being able to use a small amount of the colorant of the colored photosensitive resin composition by raising it.

In another embodiment of the present invention, the colored photosensitive resin composition may further include at least one selected from the group consisting of alkali-soluble resins, photopolymerizable compounds, solvents and additives.

alkali-soluble resin

The alkali-soluble resin is a component that imparts solubility to an alkali developer used in the developing treatment step at the time of forming a pattern, and the alkali-soluble resin may be polymerized by including an ethylenically unsaturated monomer having a carboxyl group.

The ethylenically unsaturated monomer having a carboxyl group is not particularly limited, and examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids, such as fumaric acid, mesaconic acid, and itaconic acid, and these anhydrides; and mono(meth)acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals, such as ω-carboxypolycaprolactone mono(meth)acrylate, and preferably acrylic acid and methacrylic acid. These can be used individually or in mixture of 2 or more types.

Specifically, the alkali-soluble resin according to the present invention may be polymerized by further including at least one other monomer copolymerizable with the monomer. For example, styrene, vinyltoluene, methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p- aromatic vinyl compounds such as vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm -N-substituted maleimide compounds, such as methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth)acrylates such as sec-butyl (meth)acrylate and t-butyl (meth)acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, such as alicyclic (meth)acrylates; aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane; 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. of unsaturated oxetane compounds. These can be used individually or in mixture of 2 or more types.

As used herein, (meth)acrylate means acrylate or methacrylate.

The content of the alkali-soluble resin according to the present invention is not particularly limited, and for example, it is preferably included in an amount of 5 to 80 parts by weight, more preferably in an amount of 10 to 70 parts by weight, based on 100 parts by weight of the total solid content of the colored photosensitive resin composition. do. When the content of the alkali-soluble resin is within the above range, the solubility in the developer is sufficient to facilitate pattern formation, and the film reduction of the pixel portion of the exposed portion is prevented during development, thereby improving the omission of the non-pixel portion. .

photopolymerization compound

The photopolymerizable compound contained in the coloring photosensitive resin composition of this invention is a compound which can superpose|polymerize by the action|action of light and the photoinitiator mentioned later, A monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned.

The type of the monofunctional monomer is not particularly limited, for example, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acryl Late, N-vinylpyrrolidone, etc. are mentioned.

The type of the bifunctional monomer is not particularly limited, and for example, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene Glycol di(meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc. are mentioned.

The type of the polyfunctional monomer is not particularly limited, and for example, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth) ) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are mentioned.

Commercially available products of the photopolymerizable compound include, for example, KAYARAD DPHA (manufactured by Nippon Kayaku), A-9550 (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), A-9570 (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.) , A-TMPT (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.) may be used, but the present invention is not limited thereto.

The photopolymerizable compound is preferably included in an amount of 5 to 50 parts by weight, more preferably 7 to 48 parts by weight, based on 100 parts by weight of the total solid content of the colored photosensitive resin composition. When the content of the photopolymerizable compound is within the above range, the intensity or smoothness of the pixel portion may be improved.

solvent

The solvent in particular contained in the coloring photosensitive resin composition of this invention is not restrict|limited, Various organic solvents used in the field|area of the coloring photosensitive resin composition can be used.

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; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Cyclic esters, such as (gamma)-butyrolactone, etc. are mentioned.

In terms of coating properties and drying properties, the solvent preferably includes an organic solvent having a boiling point of 100°C to 200°C in the solvent, more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxypropionic acid and esters such as ethyl and 3-methoxy methyl propionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy propionate ethyl, 3-methyl and methyl toxypropionate. These solvents can be used individually or in mixture of 2 or more types, respectively.

The content of the solvent in the colored photosensitive resin composition of the present invention is preferably 60 to 90 parts by weight, more preferably 65 to 85 parts by weight, based on 100 parts by weight of the total amount of the colored photosensitive resin composition. When the content of the solvent is included within the above range, the applicability may be improved when applied with an application 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, etc. .

additive

The additive may be selectively added as needed, and may include, for example, at least one selected from the group consisting of other high molecular compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-aggregation agents. have.

Moreover, it is most preferable to contain surfactant among the said additives.

Specific examples of the other high molecular compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. can be heard

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

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins , glycidyl ester-based resins, glycidylamine-based resins, or brominated derivatives of the above epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxides, isoprene ( A co)polymer epoxidized product, a glycidyl (meth)acrylate (co)polymer, triglycidyl isocyanurate, etc. are mentioned.

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

The curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent.

The curing auxiliary compound includes, for example, polyhydric carboxylic acids, polyhydric carboxylic acid anhydrides, and acid generators. As the polyhydric carboxylic acid anhydrides, commercially available epoxy resin curing agents may be used. Examples of the commercially available products include ADEKAHADONA EH-700 (manufactured by Adeka Industrial Co., Ltd.), Rikashiddo HH (manufactured by New Nippon Ewha Co., Ltd.), and MH-700 (manufactured by Nippon Ewha Co., Ltd.). 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 colored photosensitive resin composition, and silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric, and the like surfactants may be preferably used.

The silicone-based surfactants include, for example, DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 manufactured by Dow Corning Toray Silicone as commercially available products, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, and TSF from GE Toshiba Silicone. -4460 and TSF-4452.

The fluorine-based surfactant includes, for example, Megapiece F-470, F-471, F-475, F-482 and F-489 manufactured by Dainippon Ink Chemical Co., Ltd. as a commercially available product.

In addition, other commercially available products include KP (Shin-Etsu Chemical Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (Tochem Products), and MEGAFAC. (Dainippon Ink Chemical High School Co., Ltd.), Florad (Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (above, Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol) , EFKA (EFKA Chemicals), PB 821 (Ajinomoto), Disperbyk-series (BYK-chemi), and the like.

The cationic surfactant includes, for example, amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or quaternary ammonium salts.

The anionic surfactant is, for example, higher alcohol sulfate salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate and alkylarylsulfonates such as sodium dodecylnaphthalenesulfonate.

The nonionic surfactant is, for example, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymer, sorbitan fatty acid ester , polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester and polyoxyethylene alkylamine.

Each of the surfactants exemplified above may be used alone or in combination of two or more.

The type of the adhesion promoter is not particularly limited, and specific examples of the adhesion promoter that can be used 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-methacryloxy Propyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, etc. are mentioned.

The adhesion promoters illustrated above can be used individually or in combination of 2 or more types, respectively. The adhesion promoter may be included in an amount of 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the total weight of the solid content in the colored photosensitive resin composition.

The type of the antioxidant is not particularly limited, and examples thereof include 2,2'-thiobis(4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol. .

The type of the ultraviolet absorber is not particularly limited, but specific examples that can be used include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzothiazole, alkoxybenzophenone, and the like. .

The type of the aggregation inhibitor is not particularly limited, and specific examples that can be used include sodium polyacrylate.

The additive can be used by adding an appropriate amount within a range that does not impair the purpose of the present invention. For example, the additive may be included in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the total amount of the colored photosensitive resin composition, but is not limited thereto.

The colored photosensitive resin composition according to the present invention has an advantage of high transmittance for I-rays and H-rays when forming a coating film. Specifically, after prebaking, the colored photosensitive resin composition according to the present invention has a transmittance of 0.1% or more at a wavelength of 365 nm and a transmittance of 0.4% or more at a wavelength of 405 nm. There is an advantage in that the sensitivity and reliability of the coating film are improved because the exposure light easily reaches the photocuring of the lower film, and the reverse taper phenomenon can be prevented because the photopolymerization initiator satisfying Equations 1 and 2 is included. This has excellent advantages.

<Color filter>

Another aspect of this invention relates to the color filter containing the hardened|cured material of the above-mentioned colored photosensitive resin composition.

The color filter includes a substrate and a colored pattern layer formed on the substrate.

The substrate may be a substrate of the color filter itself, or may be a portion in which a color filter is located in a display device, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The colored pattern layer is a layer including the colored photosensitive resin composition of the present invention, and may be a layer formed by applying the colored photosensitive resin composition and then exposing, developing, and thermosetting the colored photosensitive resin composition in a predetermined pattern. The pattern layer may be formed by performing a method commonly known in the art.

The color filter including the substrate and the colored pattern layer as described above may further include a barrier rib formed between each pattern, and may further include a black matrix, but is not limited thereto.

In addition, it may further include a protective layer formed on the pattern layer of the color filter.

<Image display device>

In addition, another aspect of the present invention relates to an image display device including the above-described color filter.

The color filter of the present invention can be applied to various image display devices, such as an electroluminescence display device, a plasma display device, and a field emission display device, as well as a general liquid crystal display device.

The image display device may include other components that can be included in a conventional image display device, such as a light emitting device such as a light source, a light guide plate, and an image display unit including a color filter according to the present invention, but the present invention is not limited thereto. does not

A color filter and an image display device manufactured using the colored photosensitive resin composition according to the present invention have excellent solvent resistance and excellent adhesion due to suppressed reverse taper phenomenon.

Hereinafter, examples will be given to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present specification to those of ordinary skill in the art. In addition, "%" and "part" indicating the content hereinafter are based on weight unless otherwise specified.

Synthesis example : Synthesis of alkali-soluble resin B-1

A flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen introduction tube was prepared, and as a monomer dropping funnel, 74.8 g (0.20 mole) of benzylmaleimide, 43.2 g (0.30 mole) of acrylic acid, and 118.0 of vinyltoluene were prepared. g (0.50 mol), t-butylperoxy-2-ethylhexanoate 4g, propylene glycol monomethyl ether acetate (PGMEA) 40g, prepared by stirring and mixing, and as a chain transfer agent dropping tank, n-dodecanthiol 6g, PGMEA 24g was put and stirred and mixed was prepared. Thereafter, 395 g of PGMEA was introduced into the flask, and the atmosphere in the flask was substituted from air to nitrogen, and the temperature of the flask was raised to 90° C. while stirring. Then, the monomer and the chain transfer agent were started dripping from the dropping lot. The dripping was carried out for 2 hours while maintaining 90° C., and after 1 hour, the temperature was raised to 110° C. and maintained for 3 hours. Bubbling started. Next, 28.4 g of glycidyl methacrylate [(0.10 mol), (33 mol% based on the carboxyl group of acrylic acid used in this reaction)], 2,2'-methylenebis(4-methyl-6-t-butylphenol ) 0.4 g and 0.8 g of triethylamine were put into the flask, and the reaction was continued at 110° C. for 8 hours to obtain Resin B-1 having a solid content acid value of 70 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 16,000, and the molecular weight distribution (Mw/Mn) was 2.3.

production example : Preparation of pigment dispersion

production example 1: Preparation of pigment dispersion M1

As a pigment, C.I. Pigment Green 59 12.0 parts by weight, 4.0 parts by weight of DISPER BYK-2001 (manufactured by BYK) as a pigment dispersant, and 84 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion M1 did

production example 2: Preparation of pigment dispersion M2

As a pigment, C.I. Pigment Blue 15:4 12.0 parts by weight, 4.0 parts by weight of DISPER BYK-2001 (manufactured by BYK) as a pigment dispersant, and 84 parts by weight of propylene glycol methyl ether acetate as a solvent Mixing and dispersing with a bead mill for 12 hours, pigment dispersion M2 was prepared.

production example 3: Preparation of pigment dispersion M3

As a pigment, C.I. Pigment Blue 16 12.0 parts by weight, 4.0 parts by weight of DISPER BYK-2001 (manufactured by BYK) as a pigment dispersant, and 84 parts by weight of propylene glycol methyl ether acetate as a solvent are mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion M3 did

production example 4: Preparation of pigment dispersion M4

As a pigment, C.I. Pigment Yellow 138 12.0 parts by weight, 4.0 parts by weight of DISPER BYK-2001 (manufactured by BYK) as a pigment dispersant, and 84 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion M4 did

production example 5: Preparation of pigment dispersion M5

As a pigment, C.I. Pigment Yellow 231 12.0 parts by weight, 4.0 parts by weight of DISPER BYK-2001 (manufactured by BYK) as a pigment dispersant, and 84 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion M5 did

production example 6: Preparation of pigment dispersion M6

As a pigment, C.I. Pigment Green G58 12.0 parts by weight, 4.0 parts by weight of DISPER BYK-2001 (manufactured by BYK) as a pigment dispersant, and 84 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion M6 did

Example and comparative example : Preparation of colored photosensitive resin composition

Colored photosensitive resin compositions according to Examples and Comparative Examples were prepared according to the configurations and compositions of Tables 1 and 2 below.

(Unit: parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Pigment Dispersion 1 34.9 31.5 23.5 30.0 30.0 21.9 21.9 21.9 22.7 Pigment Dispersion 2 1.5 2.4 4.3 - - - - - 2.1 Pigment Dispersion 3 - - - 2.3 2.3 4.1 4.1 4.1 2.1 Pigment Dispersion 4 2.5 2.4 2.1 2.3 2.3 2.1 2.1 2.1 2.1 pigment dispersion 5 10.3 11.2 12.8 11.3 11.3 13.1 13.1 13.1 13.0 Pigment Dispersion 6 - - - - - - - - - Alkali-soluble resin 16.6 17.0 18.2 17.4 17.4 18.5 18.5 18.5 18.4 Photopolymerizable compound 1 2.5 2.6 2.7 2.6 2.6 2.8 2.8 2.8 2.8 Photopolymerizable compound 2 2.5 2.6 2.7 2.6 2.6 2.8 2.8 2.8 2.8 Photoinitiator 1 1.0 1.0 1.1 1.0 - 1.1 - - 1.1 Photoinitiator 2 - - - - 1.0 - 1.1 - - Photoinitiator 3 - - - - - - - 1.1 - Photoinitiator 4 - - - - - - - - - Photoinitiator 5 - - - - - - - - - solvent 28 29.1 32.4 30.3 30.3 33.4 33.4 33.4 32.7 additive 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 all 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Pigment dispersion 1: Pigment dispersion M1 obtained through the preparation of Preparation Example 1
Pigment dispersion 2: Pigment dispersion M2 obtained through the preparation of Preparation Example 2
Pigment dispersion 3: Pigment dispersion M3 obtained through the preparation of Preparation Example 3
Pigment dispersion 4: Pigment dispersion M4 obtained through the preparation of Preparation Example 4
Pigment dispersion 5: Pigment dispersion M5 obtained through the preparation of Preparation Example 5
Pigment dispersion 6: Pigment dispersion M6 obtained through the preparation of Preparation Example 6
Alkali-soluble resin: alkali-soluble resin B-1 obtained through the synthesis of the above synthesis example
Photopolymerizable compound 1: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerizable compound 2: A-TMPT (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.)
Photoinitiator 1: TR-PBG-327 (manufactured by BASF)
Photoinitiator 2: NCI-831E (manufactured by ADEKA)
Photoinitiator 3: N-1919 (made by ADEKA)
Photoinitiator 4: Irgacure 369 (manufactured by BASF)
Photoinitiator 5: Irgacure 907 (manufactured by BASF)
Solvent: propylene glycol monomethyl ether acetate
Additive: SH-8400 (Dow Corning)

(Unit: parts by weight) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Pigment Dispersion 1 42.1 34.9 30.0 34.9 - Pigment Dispersion 2 - 1.5 - 1.5 6.5 Pigment Dispersion 3 - - 2.3 - - Pigment Dispersion 4 2.7 2.5 2.3 2.5 3.2 Pigment Dispersion 5 9.1 10.3 11.3 10.3 9.8 Pigment Dispersion 6 - - - - 45.3 Alkali-soluble resin 15.5 16.6 17.4 16.6 12.8 Photopolymerizable compound 1 2.3 2.5 2.6 2.5 1.9 Photopolymerizable compound 2 2.3 2.5 2.6 2.5 1.9 Photoinitiator 1 0.9 - - - 0.8 Photoinitiator 2 - - - - - Photoinitiator 3 - - - - - Photoinitiator 4 - 1.0 1.0 - - Photoinitiator 5 - - - 1.0 - solvent 24.9 28 30.3 28 17.6 additive 0.2 0.2 0.2 0.2 0.2 all 100.0 100.0 100.0 100.0 100.0 Pigment dispersion 1: Pigment dispersion M1 obtained through the preparation of Preparation Example 1
Pigment dispersion 2: Pigment dispersion M2 obtained through the preparation of Preparation Example 2
Pigment dispersion 3: Pigment dispersion M3 obtained through the preparation of Preparation Example 3
Pigment dispersion 4: Pigment dispersion M4 obtained through the preparation of Preparation Example 4
Pigment dispersion 5: Pigment dispersion M5 obtained through the preparation of Preparation Example 5
Pigment dispersion 6: Pigment dispersion M6 obtained through the preparation of Preparation Example 6
Alkali-soluble resin: alkali-soluble resin B-1 obtained through the synthesis of the above synthesis example
Photopolymerizable compound 1: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerizable compound 2: A-TMPT (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.)
Photoinitiator 1: TR-PBG-327 (manufactured by BASF)
Photoinitiator 2: NCI-831E (manufactured by ADEKA)
Photoinitiator 3: N-1919 (made by ADEKA)
Photoinitiator 4: Irgacure 369 (manufactured by BASF)
Photoinitiator 5: Irgacure 907 (manufactured by BASF)
Solvent: propylene glycol monomethyl ether acetate
Additive: SH-8400 (Dow Corning)

Experimental example 1. Mall extinction coefficient measurement

The molar extinction coefficient of the photopolymerization initiator used in Examples and Comparative Examples was measured as follows.

Prepare a solution in which each of the photopolymerization initiators is dissolved in a propylene glycol monomethyl ether acetate solution at a concentration of 0.1% (1 g/1 L), and UV-2550 equipment from SHIMADZU is used for this solution. to measure the absorbance. The molar extinction coefficient was calculated by dividing the measured absorbance by the molar concentration (mol/L) of each photopolymerization initiator, and is shown in Table 3 below.

Experimental example 2. Measurement of transmittance

Each of the colored photosensitive resin compositions prepared in Examples and Comparative Examples was applied to a glass of 5 × 5 cm, dried, and then coated to a thickness of 2.8 μm. Thereafter, after drying (pre-baking) in an oven at 100° C. for 3 minutes to remove the solvent, transmittances of 365 nm and 405 nm of the coating film of the color filter were measured using a UV-2550 device from SHIMADZU, and are shown in Table 3 below.

Experimental example 3. Adhesion evaluation

Each of the colored photosensitive resin compositions prepared in Examples and Comparative Examples was applied to a glass of 5 × 5 cm, dried, and then coated to a thickness of 2.8 μm. Thereafter, after drying in an oven at 100° C. for 3 minutes to remove the solvent, the distance from the photomask was set to 300 μm, and the fusion lamp was exposed so that the amount of accumulated light at a wavelength of 365 nm was 40 mJ to prepare a color filter.

The color filter was immersed in KOH aqueous solution having a pH of 14 for 3 minutes, and then taken out, immersed in distilled water for 1 minute and taken out, and cured in an oven at 230° C. for 20 minutes. LV100POL) was observed.

The evaluation criteria of pattern tearing are as follows, and the results of pattern line width and pattern tearing are described in Table 3 below.

<Adhesiveness (pattern tearing) evaluation criteria>

○: No tearing in the pattern,

△: 1 to 3 rips in the pattern,

×: 4 or more torn in the pattern

Experimental example 4. solvent resistance evaluation

Each of the colored photosensitive resin compositions prepared in Examples and Comparative Examples was applied to a glass of 5×5 cm and dried, and then coated to a thickness of 2.5 μm. After removing the solvent by drying in an oven at 100° C. for 3 minutes, the distance from the photomask was set to 300 μm, and the fusion lamp was exposed to a cumulative light amount of 365 nm wavelength of 40 mJ, and cured in an oven at 230° C. for 20 minutes to prepare a color filter. .

The color filter was immersed in NMP solution at room temperature for 30 minutes, washed with ultrapure water and dried for 2 minutes on a hot plate heated to 120° C., and then chromaticity before and after immersion was measured.

The formula used at this time is calculated by the following [Equation 3], which represents the color change in the three-dimensional colorimeter defined by ^{L *} , a ^{* , and b *, and the smaller the color change value, the more reliable the color filter can be manufactured.} do.

[Equation 3]

ΔEab ^* =[(ΔL ^* ) ² +(Δa ^* ) ² +(Δb ^* ) ² ] ^{1 /2}

division ε 365 ε 405 Equation 1 Equation 2 ^* 365nm
transmittance 405nm
transmittance Adhesion evaluation solvent resistance Example 1 22.3 0.4 0.4 0.2 0.15% 0.60% ○ 1.54 Example 2 22.3 0.4 0.4 0.2 0.23% 0.79% ○ 1.11 Example 3 22.3 0.4 0.4 0.2 0.49% 1.33% ○ 0.92 Example 4 22.3 0.4 0.4 0.2 0.29% 0.94% ○ 1.21 Example 5 127.4 25.7 25.7 2.0 0.29% 0.94% ○ 0.98 Example 6 22.3 0.4 0.4 0.2 0.71% 1.72% ○ 0.81 Example 7 127.4 25.7 25.7 2.0 0.71% 1.72% ○ 0.70 Comparative Example 1 22.3 0.4 0.4 0.2 0.07% 0.36% △ 3.71 Comparative Example 2 39.6 0.0 0.0 0.0 0.15% 0.60% × 5.01 Comparative Example 3 39.6 0.0 0.0 0.0 0.29% 0.94% × 4.84 Comparative Example 4 39.6 0.0 0.0 0.0 0.15% 0.60% × 4.88 Comparative Example 5 39.6 0.0 0.0 0.0 0.05% 0.32% × 4.91

Equation 2 ^* means ε 405 × 10 / ε 365.

In the target spectrum of the coating film, the transmittance of 365 nm is 0.1% or more and the transmittance of 405 nm is 0.4% or more, and the colored photosensitive resin composition containing at least one photopolymerization initiator satisfying Equations 1 and 2 according to the present invention is used. It was confirmed that the adhesion and solvent resistance were excellent compared to Comparative Examples 1 to 5, which did not satisfy the transmittance of the coating film or did not satisfy Equations 1 and 2.

Therefore, in the target spectrum of the coating film, the transmittance of 365 nm is 0.1% or more and the transmittance of 405 nm is 0.4% or more, and at least one photopolymerization initiator satisfying Equations 1 and 2 according to the present invention is included. Colored photosensitive resin, characterized in that it contains It can be seen that the composition has excellent sensitivity and solvent resistance, and has excellent adhesion properties by preventing reverse taper phenomenon.

Claims (8)

at least one photopolymerization initiator satisfying the following formulas 1 and 2; and
CI Pigment Yellow 231; as a yellow pigment;
A colored photosensitive resin composition having a transmittance of 0.1% or more at a wavelength of 365 nm after prebake and a transmittance of 0.4% or more at a wavelength of 405 nm:
[Equation 1]
ε 405 > 0.1
[Equation 2]
(ε 405 × 10 / ε 365) > 0.1
(In Equations 1 and 2 above,
ε 365 is the molar extinction coefficient for the wavelength of 365 nm of the photopolymerization initiator,
ε 405 is the molar extinction coefficient for the 405 nm wavelength of the photopolymerization initiator). According to claim 1,
a green pigment comprising CI Pigment Green 59;
CI Pigment Blue 15:6, 15:3, 15:4, and a colorant comprising at least one blue pigment selected from the group consisting of 15:6; the colored photosensitive resin composition further comprising a. delete According to claim 1,
The photopolymerization initiator is a colored photosensitive resin composition that is included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the total solid content of the colored photosensitive resin composition. 3. The method of claim 2,
The colored photosensitive resin composition to be included in an amount of 0.1 to 45 parts by weight based on 100 parts by weight of the total solid content of the colored photosensitive resin composition. According to claim 1,
The colored photosensitive resin composition further comprising at least one selected from the group consisting of alkali-soluble resins, photopolymerizable compounds, solvents and additives. A color filter comprising a cured product of the colored photosensitive resin composition according to any one of claims 1, 2, and 4 to 6. An image display device comprising the color filter according to claim 7 .