KR101311941B1 - Pigment dispersed composition, photosensitive resin composition including same, and color filter using same - Google Patents

Abstract

A pigment comprising a halogenated phthalocyanine-based green pigment represented by Formula 1 below; Pigment derivative containing the tetrabromophthalimide compound represented by following General formula (2); Acrylic binder resins; Dispersing agent; And it provides a pigment dispersion composition comprising a solvent.

[Formula 1]

(2)

(In Formulas 1 and 2, the definition of each substituent is the same as defined in the detailed description of the invention.)

Tetrabromophthalimide, pigment derivative, pigment dispersion, color filter

Description

Pigment dispersion composition, a photosensitive resin composition comprising the same and a color filter manufactured using the same {PIGMENT DISPERSED COMPOSITION, PHOTOSENSITIVE RESIN COMPOSITION INCLUDING SAME, AND COLOR FILTER USING SAME}

The present disclosure relates to a pigment dispersion composition, a photosensitive resin composition comprising the same, and a color filter manufactured using the same.

The color filter is used in a liquid crystal display device, an optical filter of a camera, and the like, and is manufactured by coating a fine region colored with three or more colors on a solid state imaging device or a transparent substrate. Such colored thin films are usually formed by dyeing, printing, electrodeposition, pigment dispersion, inkjet, or the like. Currently, this method is applied to manufacturing LCDs of mobile phones, laptops, monitors, TVs, and the like.

In the dyeing method, an image having a dyeing base material such as natural photosensitive resin such as gelatin, amine-modified polyvinyl alcohol, amine-modified acrylic binder resin and the like is formed on a glass substrate in advance, and then dyed with a dye such as a direct dye. However, in order to form a multi-colored thin film on the same substrate, it is necessary to perform flameproof processing every time the color is changed, so that the process is very complicated and the time is delayed. In addition, the clarity and dispersibility of the commonly used dyes and resins themselves are good, but there are disadvantages in that light resistance, moisture resistance and heat resistance, which are the most important characteristics, are poor.

In the printing method, printing is performed using the ink which disperse | distributed the pigment to thermosetting or photocurable resin, and a colored thin film is formed by hardening with heat or light. According to this method, the material cost can be reduced compared to other methods, but it is difficult to form highly precise and detailed images, and the thin film layer formed is not uniform. Korean Patent Publication No. 1996-0011513 proposes a method of manufacturing a color filter using an inkjet method, and since the colored photosensitive resin composition sprayed from the nozzle is dye-like for printing delicate and accurate pigments, it is similar to the dyeing method. Durability and heat resistance are inferior.

In contrast, Korean Patent Publication No. 1996-0029904 proposes an electrodeposition method using an electroprecipitation method, which can form a precise colored thin film and has a characteristic of excellent heat resistance and light resistance due to the use of a pigment. When the pixel size is precise and the electrode pattern is fine, there is a problem that color unevenness due to electrical resistance appears at both ends or the thickness of the colored thin film becomes thick, which makes it difficult to apply to color filters requiring high precision.

On the other hand, the pigment dispersion method repeats a series of processes of coating a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix, exposing it in the form of a pattern to be formed, and then thermally curing the non-exposed areas with a solvent. It is a method by which a colored thin film is formed. The pigment dispersion method has the advantage of improving heat resistance and durability, which are the most important properties of the color filter, and maintaining the thickness of the film uniformly. In addition, since the fine pattern is excellent in implementation and the manufacturing method is relatively easy, it is commonly adopted. For example, Japanese Patent Laid-Open No. Hei 7-140654, Japanese Patent Laid-Open No. Hei 10-254133 and the like have proposed a method of producing a color resist using pigment dispersion.

The colored photosensitive resin composition used to manufacture the color filter according to the pigment dispersion method is generally composed of a binder resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent and other additives, and the like to form a green color filter. Is mainly composed of a chlorinated copper phthalocyanine pigment (COLOR INDEX) green pigment 7 (hereinafter referred to as "PG7") and a chlorinated brominated phthalocyanine pigment C.I. consisting of a green pigment 36 (hereinafter referred to as "PG36") and a chlorinated zinc bromide phthalocyanine pigment. Green pigment 58 (hereinafter referred to as "PG58") is used. Since PG7 has high coloration power as green but too strong blue color, a large amount of yellow must be mixed in order to be used as a pigment for green pixels according to sRGB, NTSC, and EBU standards, and since the transmittance is low, when green pixels are formed around PG7, It becomes a dark color filter.

On the other hand, PG36 exhibits a spectral transmittance spectrum relatively close to yellow, and has a half-width wide, a low spectral transmittance near the peak top, and also transmits bright lines in the sub-wavelength region, so that the transmittance is considerably high, but the coloring power is low. Therefore, in order to form a green pixel displaying a region of high coloring power (high concentration region) on the color coordinate, the content of the PG36 pigment must be increased. There is a problem that the transmittance of the pixel is lowered.

As a method for securing a high transmittance, there is also a method of shifting the color coordinates in the yellow direction by using a high concentration of yellow pigment, but the total content of the pigment increases because the content of the yellow pigment increases. Therefore, there is a need for a method capable of exhibiting high brightness characteristics and further high contrast ratios without increasing the content of the yellow pigment.

One aspect of the present invention is to provide a pigment dispersion composition which is excellent in dispersion stability and can produce a color filter having high brightness and high contrast ratio.

Another aspect of the present invention is to provide a photosensitive resin composition comprising the pigment dispersion composition.

Another aspect of the present invention is to provide a color filter manufactured using the photosensitive resin composition.

One aspect of the present invention, (A) a pigment comprising a halogenated phthalocyanine-based green pigment represented by the formula (1); (B) a pigment derivative comprising a tetrabromophthalimide compound represented by the following formula (2); (C) acrylic binder resin; (D) dispersants; And (E) provides a pigment dispersion composition comprising a solvent.

[Formula 1]

(In the formula 1,

X ₁ to X ₁₆ are independently selected from the group consisting of hydrogen atom, fluorine atom (F), chlorine atom (Cl), bromine atom (Br) and iodine atom (I), provided that X ₁ to X ₁₆ is Are not all hydrogen atoms,

M is selected from the group consisting of copper (Cu), aluminum (Al), zinc (Zn), iron (Fe), cobalt (Co) and nickel (Ni).)

(2)

(In the formula (2)

X is a hydrogen atom; Substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Substituted or unsubstituted alkyl alcohol group; Substituted or unsubstituted alkyl sulfonic acid group; Substituted or unsubstituted alkenylsulfonic acid group; Substituted or unsubstituted sulfonimide group; A carboxylic acid group; Substituted or unsubstituted alkenyl alcohol group; Substituted or unsubstituted alkylcarboxylic acid group; Substituted or unsubstituted alkenylcarboxylic acid group; A substituted or unsubstituted alkoxyalkylsulfonic acid group; Substituted or unsubstituted alkoxy alkenylsulfonic acid group; Substituted or unsubstituted alkoxyalkynyl sulfonic acid group; Substituted or unsubstituted alkoxyalkylcarboxylic acid group; Substituted or unsubstituted alkoxy alkenylcarboxylic acid group; And a substituted or unsubstituted alkoxyalkynylcarboxylic acid group.)

The pigment (A) may further include a diazo-based yellow pigment.

The diazo-based yellow pigment may be included in an amount of 10 to 60 wt% based on the total content of the (A) pigment.

The acrylic binder resin (C) may have at least one acidic group, and the weight average molecular weight (MW) may be 5,000 to 40,000.

The said pigment dispersion composition is 2-20 weight part of said (B) pigment derivatives, 1-50 weight part of said (C) acrylic binder resins, with respect to 100 weight part of said (A) pigments, and said (D) dispersing agent 10-80 It may include parts by weight, and 10 to 1,000 parts by weight of the solvent (E).

Another aspect of the present invention provides a photosensitive resin composition comprising the pigment dispersion composition according to the aspect of the present invention.

Another aspect of the present invention provides a color filter manufactured using the photosensitive resin composition according to another aspect of the present invention.

The luminance of the color filter may be 56 or more when the Gy coordinate is 0.59, and the contrast ratio may be 5,000 or more when the Gy coordinate is 0.59.

Other details of the embodiments of the present invention are included in the following detailed description.

It is possible to provide a color filter having excellent dispersion stability and high brightness and high contrast ratio.

Hereinafter, aspects of the present invention will be described in more detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless stated otherwise in the present specification, "substituted" means that at least one hydrogen atom of the functional group is a halogen atom (F, Br, Cl, or I), a hydroxyl group, a nitro group, a cyano group, an amino group (-NRR ', R and R 'are independently C1 to C10 alkyl group), amidino group, hydrazine or hydrazone group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted cycloalkyl group, Or substituted or unsubstituted heteroalkyl group, substituted or unsubstituted heteroaryl group, and substituted or unsubstituted heterocycloalkyl group, or substituted with one or more substituents selected from the group consisting of two hydrogen atoms = O, = S, = NR (R is an alkyl group of C1 to C10), = PR (R is an alkyl group of C1 to C10), and = CRR '(R and R' are independently alkyl groups of C1 to C10). Or substituted with one or more substituents Hydrogen atoms are ≡N, ≡P and ≡CR (R is an alkyl group of C1 to C10).

Unless stated otherwise in the specification, "alkyl group" means a C1 to C30 alkyl group, "aryl group" means a C6 to C30 aryl group, "alkyl alcohol group" means a C1 to C30 alkyl alcohol group, " Alkyl sulfonic acid group "means a C1 to C30 alkyl sulfonic acid group," alkenyl sulfonic acid group "means a C1 to C30 alkenyl sulfonic acid group," alkenyl alcohol group "means a C2 to C30 alkenyl alcohol group," alkyl "Carboxylic acid group" means a C1 to C30 alkylcarboxylic acid group, "alkenylcarboxylic acid group" means a C1 to C30 alkenylcarboxylic acid group, "alkoxyalkyl sulfonic acid group" means a C1 to C30 alkoxyalkylsulfonic acid group "Alkoxyalkenylsulfonic acid group" means a C1 to C30 alkoxyalkenylsulfonic acid group, and "alkoxyalkynylsulfonic acid group" means a C3 to C30 alkoxyalkynylsulfonic acid group, and "alkoxyalkylcarboxylic acid group" means C1. To C30 alkoxy By alkyl carboxylic acid group, "alkoxyalkenylcarboxylic acid group" means C1 to C30 alkoxyalkenylcarboxylic acid group, and "alkoxyalkynylcarboxylic acid group" means C6 to C30 alkoxyalkynylcarboxylic acid group. do.

"Combination" as used herein, unless otherwise specified, means mixing or copolymerization.

Pigment dispersion composition according to an aspect of the present invention, (A) a pigment comprising a halogenated phthalocyanine-based green pigment represented by the formula (1); (B) a pigment derivative comprising a tetrabromophthalimide compound represented by the following formula (2); (C) acrylic binder resin; (D) dispersants; And (E) a solvent.

[Formula 1]

(In the formula 1,

X ₁ to X ₁₆ are independently selected from the group consisting of hydrogen atom, fluorine atom (F), chlorine atom (Cl), bromine atom (Br) and iodine atom (I), provided that X ₁ to X ₁₆ is Are not all hydrogen atoms,

M is selected from the group consisting of copper (Cu), aluminum (Al), zinc (Zn), iron (Fe), cobalt (Co) and nickel (Ni).)

(2)

(In the formula (2)

X is a hydrogen atom; Substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Substituted or unsubstituted alkyl alcohol group; Substituted or unsubstituted alkyl sulfonic acid group; Substituted or unsubstituted alkenylsulfonic acid group; Substituted or unsubstituted sulfonimide group; A carboxylic acid group; Substituted or unsubstituted alkenyl alcohol group; Substituted or unsubstituted alkylcarboxylic acid group; Substituted or unsubstituted alkenylcarboxylic acid group; A substituted or unsubstituted alkoxyalkylsulfonic acid group; Substituted or unsubstituted alkoxy alkenylsulfonic acid group; Substituted or unsubstituted alkoxyalkynyl sulfonic acid group; Substituted or unsubstituted alkoxyalkylcarboxylic acid group; Substituted or unsubstituted alkoxy alkenylcarboxylic acid group; And a substituted or unsubstituted alkoxyalkynylcarboxylic acid group.)

Hereinafter, each component is demonstrated in detail.

(A) Pigment

The photosensitive resin composition includes a halogenated phthalocyanine-based green pigment represented by Formula 1 below.

 [Formula 1]

(In the formula 1,

X ₁ to X ₁₆ are independently selected from the group consisting of hydrogen atom, fluorine atom (F), chlorine atom (Cl), bromine atom (Br) and iodine atom (I), provided that X ₁ to X ₁₆ is Not all hydrogen atoms, for example Cl or Br,

M is selected from the group consisting of copper atom (Cu), aluminum atom (Al), zinc atom (Zn), iron atom (Fe), cobalt atom (Co) and nickel atom (Ni), for example, copper atom or It may be a zinc atom.)

The halogenated phthalocyanine-based green pigment may be a halogenated copper phthalocyanine-based green pigment or a halogenated zinc phthalocyanine-based green pigment. Representative examples of the copper halide phthalocyanine-based green pigment include C.I. Green Pigment No. 7, C.I. chlorinated copper phthalocyanine pigment. Green pigment 36 and C.I. Green pigment 37, etc. are mentioned. Representative examples of the halogenated zinc phthalocyanine-based green pigment include a chlorinated zinc bromide phthalocyanine pigment. And green pigment 58. These photosensitive resin compositions may be used alone or in combination thereof, and among these, chlorinated copper phthalocyanine pigments and chlorinated zinc bromide phthalocyanine pigments may be used.

In general, the halogenated phthalocyanine-based green pigment has an average particle diameter of 60 to 100 nm, the shape of the cross section is elliptical, but can be refined to a size in the range of 10 to 70 nm through kneading treatment, and the shape of the cross section is circular. It can be changed to a globular pigment. The pigment dispersion composition prepared by using the refined halogenated phthalocyanine-based green pigment within the particle diameter range may include a spherical halogenated phthalocyanine-based green pigment having an average particle diameter of 10 to 70 nm, so that the transmittance of the pigment dispersion composition may be improved.

The kneading treatment of the halogenated phthalocyanine-based green pigment includes (i) kneading the pigment using a pigment derivative, a water-soluble inorganic salt and a wetting agent, ii) wet grinding the product obtained after kneading, and iii) filtering the product after wet grinding. It can carry out including the process of washing with water.

As the water-soluble inorganic salt added during the kneading treatment, sodium chloride, calcium chloride, or the like may be used, and the wetting agent may be an alkylene glycol monoalkyl ether such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, or the like. Compounds or alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin polyethylene glycol, and the like may be used, and these may be used alone or in combination of two or more thereof. Pigments are salt milled with such water-soluble inorganic salts and wetting agents to have the size of the micronized particles.

The pigment may further include a diazo-based yellow pigment together with the halogenated phthalocyanine-based green pigment.

The diazo-based yellow pigment is C.I. Yellow pigment 138, C.I. Yellow pigment 139, C.I. Yellow pigment 150 etc. can be used.

In addition, if necessary, the diazo-based yellow pigment may also be used as a spherical pigment which has been miniaturized to a size of 50 nm or less through kneading treatment.

The diazo-based yellow pigment may be included in an amount of 10 to 60% by weight, and may be included in an amount of 20 to 50% by weight, based on 100% by weight of the total pigment content. When the content of the diazo-based yellow pigment is in the above range, a desired color may be realized and an appropriate transmittance may be maintained.

(B) pigment derivative

The dye derivative is for improving the dispersion stability by preventing re-agglomeration of the pigment in the photosensitive resin composition, and comprises a tetrabromophthalimide compound represented by the following formula (2).

 (2)

(In the formula (2)

X is a hydrogen atom; Substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Substituted or unsubstituted alkyl alcohol group; Substituted or unsubstituted alkyl sulfonic acid group; Substituted or unsubstituted alkenylsulfonic acid group; Substituted or unsubstituted sulfonimide group; A carboxylic acid group; Substituted or unsubstituted alkenyl alcohol group; Substituted or unsubstituted alkylcarboxylic acid group; Substituted or unsubstituted alkenylcarboxylic acid group; A substituted or unsubstituted alkoxyalkylsulfonic acid group; Substituted or unsubstituted alkoxy alkenylsulfonic acid group; Substituted or unsubstituted alkoxyalkynyl sulfonic acid group; Substituted or unsubstituted alkoxyalkylcarboxylic acid group; Substituted or unsubstituted alkoxy alkenylcarboxylic acid group; And a substituted or unsubstituted alkoxyalkynylcarboxylic acid group.)

Representative products of the pigment derivatives include "SOLSPERSE 5000" by Lubrizol.

The pigment derivative was refined by a kneading treatment together with a halogenated phthalocyanine-based green pigment to improve brightness and contrast ratio without increasing the pigment dosage.

The pigment derivative may be included in an amount of 2 to 20 parts by weight based on 100 parts by weight of the pigment in the pigment dispersion composition, and when the pigment derivative is included in the above range, it does not significantly change the color expression and may maintain an appropriate viscosity, thereby causing the pigment derivative. When applying a pigment dispersion composition comprising a product can ensure excellent optical, chemical quality and reliability.

(C) acrylic binder resin

As the binder resin, an acrylic copolymer resin is used. The acrylic copolymer is styrene, N-benzylphthalicimide, (meth) acrylic acid, alkyl (meth) acrylate, aryl (meth) acrylate, alcohol (meth) acrylate, alkylaryl (meth) acrylate, succinct What copolymerized monomers, such as nick (meth) acrylate, is mentioned, These can be used 1 type or in mixture of 2 or more types.

Specific examples include acrylic acid, methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, ethylhexyl (meth) acrylate, phenyl (meth) acrylate, and benzyl acrylate (meth). ) Acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, o-silyl (meth) acrylate, glycerol (meth) acrylate, alkylaryl (meth) acrylate, succinic (meth) acrylate, etc. The thing which copolymerized the monomer is mentioned.

In addition, the acrylic binder resin has one or more acid groups, and examples of such acid groups include a carboxyl group, a sulfonic acid group or a phosphoric acid group.

It is preferable that the acrylic binder resin has an acid value of 70 to 150 mgKOH / g. The acid value of the acrylic binder resin is determined by the amine value of the dispersant used, but the dispersant usually used has an amine value of 10 to 200 mgKOH / g. The acid value of the acrylic binder resin is to offset the amine value of the dispersant used to increase the stability of the pigment dispersion composition, and to facilitate development of the non-exposed portion when the pigment dispersion composition is color photoresisted. Of course, in order to improve the developability of the unexposed portion, the acid value of the binder resin to be added when preparing the photoresist is primarily important, but also the acid value of the binder resin used when preparing the pigment dispersion composition is of course important. Since the amine value of the dispersant is considerably high, the higher the acid value of the binder resin used for offsetting it, the better, especially when the acid value of the binder resin is 80 to 130 mgKOH / g.

The acrylic binder resin may have a weight average molecular weight of 5,000 to 40,000, and if the weight average molecular weight of the binder resin is in the above range, an excellent balance of dispersibility and viscosity may be obtained.

The acrylic binder resin may be included in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the pigment in the pigment dispersion composition, effective dispersion is made when the acrylic binder resin is included in the above range to improve the dispersion stability and maintain an appropriate viscosity As the optical, physical and chemical qualities are improved in the application of the product, it has an excellent balance of dispersion stability and viscosity.

(D) dispersant

The dispersant is used to uniformly disperse the pigment in a solvent, and may be a polyester compound, a polycarboxylic acid ester compound, an unsaturated polyamide compound, a polycarboxylic acid compound, a polycarboxylic acid alkyl salt compound, or a polyacrylic compound , Polyethyleneimine compounds, polyurethane compounds, and combinations thereof may be used.

Specific examples of the dispersant include DISPERBYK ^® -161, DISPERBYK ^® -163, DISPERBYK ^® -164, DISPERBYK ^® -2000, DISPERBYK ^® -2001, BYK 21116, BYK 130, BYK 109, manufactured by BK Corp .; Efka-4046 and EFKA-4047 from Efka; Lubrizol's SOLSPERSE ^® 24000, SOLSPERSE ^® 32550, SOLSPERSE ^® 32500, and SOLSPERSE ^® 33500.

The dispersant preferably has an amine number of 10 to 200 mgKOH / g, more preferably 40 to 200 mgKOH / g, most preferably 50 to 150 mgKOH / g. When the amine value of the dispersant is 10 to 200 mgKOH / g has the effect of improving dispersibility and developability.

The dispersant may be included in 10 to 80 parts by weight with respect to 100 parts by weight of the pigment in the pigment dispersion composition, may be included in 20 to 60 parts by weight, when the dispersant is included in the above range is effective dispersion is made to improve dispersion stability As the optical, physical and chemical qualities of the product are improved by maintaining an appropriate viscosity, it is desirable in terms of dispersion stability and excellent balance of viscosity.

(E) Solvent

The solvent may be ones which are compatible with the acrylic binder resin and other constituent materials but do not react.

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate; Alkoxy acetate alkyl esters, such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy- Monooximonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyls such as ethyl methyl propionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl 2-hydroxy-3-methylbutanoate; And ethyl ketone esters such as ethyl pyruvate. In addition, there may be mentioned compounds such as N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, But are not limited to, acetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetyl acetone, isophorone, caproic acid, caprylic acid, And high boiling solvents such as benzyl, ethyl benzoate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Considering compatibility and reactivity among these solvents, glycol ethers such as ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Diethylene glycol such as diethylene glycol monomethyl ether; Propylene glycol alkylether acetates such as propylene glycol methylether acetate and propylene glycol propylether acetate can be used.

The solvent may be included in an amount of 10 to 1000 parts by weight with respect to 100 parts by weight of the pigment in the pigment dispersion composition, may be included in 20 to 500 parts by weight of the solvent, if the solvent is in the above range when the viscosity of the pigment dispersion composition is appropriate product application It is advantageous for physical and optical properties.

The photosensitive resin composition which concerns on another aspect of this invention contains the pigment dispersion liquid composition which concerns on one aspect of this invention.

The photosensitive resin composition may include an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a pigment dispersion composition and a solvent according to one aspect of the present invention.

The alkali-soluble resin is a first ethylenically unsaturated monomer And a copolymer of a second ethylenically unsaturated monomer copolymerizable therewith, and a resin including at least one acrylic repeating unit.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing one or more carboxyl groups, and specifically, may be selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and combinations thereof.

The weight ratio of the first ethylenically unsaturated monomer may be 10 to 40% or 20 to 30% with respect to the total amount of the acrylic binder resin. As said 2nd ethylenically unsaturated monomer, an alkenyl aromatic monomer, an unsaturated carboxylic ester compound, an unsaturated carboxylic acid amino alkyl ester compound, a carboxylic acid vinyl ester compound, an unsaturated carboxylic acid glycidyl ester compound, and vinyl cyanide Compound, unsaturated amide compounds, and combinations thereof.

Representative examples of the alkenyl aromatic monomers include styrene, α-methyl styrene, vinyl toluene, vinyl benzyl methyl ether, and the like; Representative examples of the unsaturated carboxylic acid ester compounds include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxy ethyl acrylate, 2-hydride. Hydroxy ethyl methacrylate, 2-hydroxy butyl acrylate, 2-hydroxy butyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate Rate; Representative examples of the unsaturated carboxylic acid amino alkyl ester compounds include 2-amino ethyl acrylate, 2-amino ethyl methacrylate, 2-dimethyl amino ethyl acrylate, 2-dimethyl amino ethyl methacrylate, and the like; Representative examples of the carboxylic acid vinyl ester compounds include vinyl acetate, vinyl benzoate, and the like; Typical examples of the unsaturated carboxylic acid glycidyl ester compound include glycidyl acrylate, glycidyl methacrylate, and the like; Representative examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile and the like; Representative examples of the unsaturated amide compounds include, but are not limited to, acryl amide, methacryl amide, and the like. These unsaturated second ethylenically unsaturated monomers may be used alone or in combination of two or more.

The first ethylenically unsaturated monomer And specific examples of the acrylic binder resin containing a second ethylenically unsaturated monomer include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate Rate / 2-hydroxy ethyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene / 2-hydroxy ethyl methacrylate copolymer, and the like, but are not limited thereto, and these may be used alone or in combination. You may mix and use species or more.

The weight average molecular weight (Mw) of the alkali-soluble resin may be 3,000 to 150,000, may be 5,000 to 50,000. When the weight average molecular weight of alkali-soluble resin is the said range, it is excellent in adhesiveness with a board | substrate, physical and chemical properties are good, and viscosity is appropriate.

The alkali-soluble resin is a factor that has the greatest influence on the resolution of pixels in the photosensitive resin composition. For example, in the case of the methacrylic acid / benzyl methacrylate copolymer, the resolution of the pixel is clearly changed by the acid value and the weight average molecular weight. In this case, the best pixel resolution can be obtained when the content ratio of methacrylic acid / benzyl methacrylate is 25/75 (w / w) with an acid value of 80 to 120 mgKOH / g and a weight average molecular weight of 20,000 to 40,000. .

The said photopolymerizable monomer can mix and use the monomer or oligomer generally used for the conventional photosensitive resin composition.

Examples of the photopolymerizable monomers include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and pentaeryte. Lithitol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethyl All propane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate 1 or 6 or more types are selected or mixed from the rate, 1, 6- hexanediol dimethacrylate, etc. It can be used.

The photopolymerization initiator is a photopolymerization initiator generally used in the photosensitive resin composition, for example, at least one of triazine compounds, acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, and oxime compounds. Any one may be used, but is not necessarily limited thereto.

Specific examples of the triazine compound used as the photoinitiator include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2 -(3 ', 4'-dimethoxy styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxy naphthyl) -4,6-bis (trichloro Methyl) -s-triazine, 2- (p-methoxy phenyl) -4,6-bis (trichloro methyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-biphenyl-4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naph Sat 1-yl) -4,6-bis (trichloro methyl) -s-triazine, 2- (4-methoxy naphtho 1-yl) -4,6-bis (trichloro methyl) -s-tri Azine, 2-4-trichloro methyl (piperonyl) -6-triazine, 2-4-trichloro methyl (4'-methoxy styryl) -6-triazine and the like.

Specific examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone and pt-butyltrichloro acetophenone , pt-butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and the like.

Examples of the benzophenone compounds include benzophenone, benzoyl benzoic acid, benzoyl benzoic acid methyl, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 3,3'-dimethyl-2-methoxy benzophenone, and 4,4 '. -Dichloro benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, and the like.

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2- And Oakstone.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

Examples of the oxime compound include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (O-acetyloxime) -1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 0-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one and the like.

In addition to the compounds listed above, the photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, a biimidazole compound, or the like. In addition, the photopolymerization initiator may be used in combination with a photosensitizer which causes a chemical reaction by transferring energy after absorbing light and becoming excited.

The pigment dispersion composition and the solvent are as described above.

The photosensitive resin composition may include malonic acid in order to prevent stains or spots during coating, generation of residues due to leveling characteristics or undeveloped; 3-amino-1,2-propanediol; Other additives such as a silane coupling agent having a vinyl group or a (meth) acryloxy group may be further included. The amount of these additives to be used can be easily controlled depending on the desired physical properties.

In addition, the photosensitive resin composition may further include an epoxy compound as needed for the improvement of adhesion and other properties. The epoxy compound is selected from the group consisting of epoxy novolac acrylic carboxylate resin, ortho cresol novolac epoxy resin, phenol novolac epoxy resin, tetramethyl bi-phenyl epoxy resin, bisphenol A type epoxy resin, alicyclic epoxy resin 1 or more types can be used. When the epoxy compound is further included, a radical polymerization initiator such as a peroxide initiator or an azobis-based initiator may be further included.

A color filter according to another aspect of the present invention is manufactured using the photosensitive resin composition according to the other aspect of the present invention. Since this may be in accordance with a conventional method, a detailed description thereof will be omitted.

The pigment dispersion composition according to one aspect of the present invention has a transmittance in the range of 75 to 95%. Since the green color filter has a high transmittance in the green region to realize a clear color, when the green color filter is manufactured with a color filter having a pigment dispersion composition having a transmittance of less than 75%, there is a problem in that light of the green region cannot be transmitted smoothly. However, the green color filter of the present invention may have excellent light transmittance.

In addition, the color filter may have a high brightness and high contrast ratio, and as a specific example, the luminance may have a value of 56 or more when the Gy coordinate is 0.59, and the contrast ratio may have a value of 3,000 or more when the Gy coordinate is 0.59.

Hereinafter, the above-described aspects of the present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrative purposes only, and the present invention is not limited to the following examples.

(Synthesis of Pigment Derivatives)

Synthesis Example 1

46.37 g of tetrabromophthalic anhydride represented by the following formula (3) and 15.5 g of n-octylamine represented by the following formula (4) were charged to a reactor containing 500 ml of diethyl ether, and refluxed for 4 hours. After cooling to room temperature, the precipitated product was filtered to synthesize a pigment derivative of the following Formula 5.

(3)

[Formula 4]

[Chemical Formula 5]

Synthesis Example 2

In Synthesis Example 1

A pigment derivative of Formula 7 was synthesized in the same manner as in Synthesis Example 1, except that 11.18 g of phenylamine represented by Formula 6 was used instead of 15.5 g of n-octylamine represented by Formula 4.

[Chemical Formula 6]

[Formula 7]

Synthesis Example 3

In Synthesis Example 1

A pigment derivative of Chemical Formula 9 was synthesized in the same manner as in Synthesis Example 1, except that 9.01 g of hydroxypropylamine represented by Chemical Formula 8 was used instead of 15.5 g of n-octylamine represented by Chemical Formula 4.

[Formula 8]

[Chemical Formula 9]

Synthesis Example 4

In Synthesis Example 1

A pigment derivative of Formula 11 was synthesized in the same manner as in Synthesis Example 1, except that 7.41 g of hydroxypropylamine represented by Formula 10 was used instead of 15.5 g of n-octylamine represented by Formula 4.

[Formula 10]

[Formula 11]

(Production of Spherical Pigments)

Examples 1 to 8 and Comparative Examples 1 to 2

In the kneader, the ingredients according to the respective examples described in Table 1 below were prepared by C.I. A mixture was prepared by adding with 100 g of green pigment 58 and kneading for 8 hours. Each mixture was placed in a mixer with 5 parts of water and stirred for 1 hour, after which the resulting slurry was filtered and washed with water. After washing with water, the obtained pigment was dried in a vacuum oven at 60 DEG C for 1 day, and spherical C.I. Green pigment 58 was prepared.

[Table 1]

Pigment derivative Sodium chloride Polyethylene
Glycol 400 Kneading conditions Kinds Content [g] Content [g] Content [g] Temperature [° C] Example 1 Formula 5 10 800 200 80 Example 2 Formula 5 10 800 200 100 Example 3 Formula 5 10 1,000 200 80 Example 4 Formula 5 15 800 200 80 Example 5 Formula 5 10 800 250 80 Example 6 Formula 7 10 800 200 80 Example 7 Formula 9 10 800 200 80 Example 8 Formula 11 10 800 200 80 Comparative Example 1 Formula 12 10 800 200 80 Comparative Example 2 - - 800 200 80

The polyethylene glycol 400 is a product of Sigma Aldrich.

The pigment derivative of Chemical Formula 12 used in Comparative Example 1 is as follows.

[Chemical Formula 12]

(Physical property evaluation 1: average particle diameter measurement and particle shape observation)

The average particle diameters of the pigments prepared in Examples 1 to 8 and Comparative Examples 1 and 2 were measured by transmission electron microscopy (TEM), respectively, and the respective particle shapes were observed. The results are shown in Table 2 below.

[Table 2]

Average particle diameter [nm] Particle shape Example 1 40 Spherical (elliptical) Example 2 60 Spherical (elliptical) Example 3 60 Sphere + Rod Type Example 4 80 Spherical (elliptical) Example 5 60 Spherical (elliptical) Example 6 80 Spherical (elliptical) Example 7 70 Sphere + Rod Type Example 8 70 Sphere + Rod Type Comparative Example 1 100 Sphere + Rod Type Comparative Example 2 150 Sphere + Rod Type

Referring to Table 2, it was confirmed that the pigments of Examples 1 and 2 that were kneaded were significantly finer than the pigments of Comparative Examples 1 and 2. In addition, it was confirmed that the kneaded pigment had a tendency to deform into a spherical shape, which is advantageous for dispersion and also high light transmission.

1 and 2 are transmission electron microscopy (TEM) images of the pigments prepared in Example 1 and Comparative Example 1, respectively.

1 and 2, the pigment particles prepared in Example 1 was confirmed that the average particle diameter is smaller and uniform than the pigment particles prepared in Comparative Example 1.

(Preparation of photosensitive resin composition)

Example 9

9 g of the pigment of Example 1, C.I. 6 g of yellow pigment 150 (Lanxess), 4 g of dispersant (LPN2001 by BYK), 4 g of polybenzyl methacrylate resin (Sigma Aldrich), 25.5 g of propylene glycol methyl ethyl acetate (PGMEA), and N-methylpyrroli 50 g of NMP were mixed and dispersed using Asada's paint shaker for 46 hours.

45 g of the pigment dispersion, 5 g of acrylic acid-benzyl methacrylate copolymer, 5 g of a photopolymerizable monomer (DPHA (Dipentaerythritol hexaacrylate) of Dongyang Synthetic), 39.5 g of propylene glycol methyl ethyl acetate, triazine photopolymerization 0.5 g of an initiator (TPP manufactured by Nippon Kayaku Co., Ltd.) was mixed and then stirred for 30 minutes to prepare a photosensitive resin composition.

Example 10

A photosensitive resin composition was manufactured in the same manner as in Example 9, except that the pigment of Example 2 was used instead of the pigment of Example 1 in Example 9.

Example 11

A photosensitive resin composition was prepared in the same manner as in Example 9, except that the pigment of Example 3 was used instead of the pigment of Example 1 in Example 9.

Example 12

A photosensitive resin composition was manufactured in the same manner as in Example 9, except that the pigment of Example 5 was used instead of the pigment of Example 1 in Example 9.

Comparative Example 3

In Example 9, C.I. Except for using the green pigment 58, a photosensitive resin composition was prepared in the same manner as in Example 9.

Comparative Example 4

A photosensitive resin composition was manufactured in the same manner as in Example 9, except that the pigment of Comparative Example 2 was used instead of the pigment of Example 1 in Example 9.

(Physical evaluation 2: Viscosity measurement)

The viscosity of each pigment dispersion composition in Examples 9 to 12 and Comparative Examples 3 to 4 was measured using a Brookfield Co., Ltd. DVIII Ultra, and the results are shown in Table 3 below.

(Physical property evaluation 3: color characteristic measurement)

In order to measure luminance, the pigment dispersion compositions of Examples 9 to 12 and Comparative Examples 3 to 4 were spin-coated at respective rotation speeds (300 rpm, 500 rpm, and 700 rpm) on a 10 cm × 10 cm glass, and hot at 100 ° C. After prebaking on the plate was subjected to ultraviolet light exposure at 60 mJ / ㎠ using an exposure machine. Then, after the heat treatment for 30 minutes on a 230 ℃ hot plate, color characteristics were measured using a spectrophotometer MCPD3000 of Otsuka electronic. The color characteristic measurement results are shown in Table 3 below.

[Table 3]

Viscosity [cPs] Gx (Gy = 0.595) Luminance (Y) Contrast ratio Example 9 3.8 0.2946 57.29 6,456 Example 10 4.2 0.2947 56.23 5,574 Example 11 4.1 0.2942 56.15 5,379 Example 12 3.5 0.2919 56.47 5,145 Comparative Example 3 4.3 0.2937 52.32 4,299 Comparative Example 4 4.8 0.2943 52.62 3,521

Referring to Table 3 above, the viscosity of the pigment dispersions of Examples 9 to 12 was measured lower than the viscosity of the pigment dispersions of Comparative Examples 3 and 4. As a result, it was found that the photosensitive resin composition using the pigment prepared by using the pigment derivatives used in Examples 9 to 12 showed good results in terms of stability. In addition, it was confirmed that the photosensitive resin compositions of Examples 9 to 12 showed superior results to the photosensitive resin compositions of Comparative Examples 3 to 4 even in the optical color characteristics measured through the brightness and contrast ratio results.

1 is a transmission electron microscopy (TEM) photograph of the pigment prepared in Example 1. FIG.

2 is a transmission electron micrograph of the pigment prepared in Comparative Example 1.

Claims (8)

(A) Pigment containing a halogenated phthalocyanine green pigment represented by following formula (1); (B) a pigment derivative comprising a tetrabromophthalimide compound represented by the following formula (2); (C) an acrylic binder resin having at least one acidic group and having a weight average molecular weight (MW) of 5,000 to 40,000; (D) dispersants; And (E) Pigment dispersion composition containing a solvent. [Formula 1]

(In the formula 1, X ₁ to X ₁₆ are independently selected from the group consisting of hydrogen atom, fluorine atom (F), chlorine atom (Cl), bromine atom (Br) and iodine atom (I), provided that X ₁ to X ₁₆ is Are not all hydrogen atoms, M is selected from the group consisting of copper (Cu), aluminum (Al), zinc (Zn), iron (Fe), cobalt (Co) and nickel (Ni).) (2)

(In the formula (2) X is a hydrogen atom; Substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Substituted or unsubstituted alkyl alcohol group; Substituted or unsubstituted alkyl sulfonic acid group; Substituted or unsubstituted alkenylsulfonic acid group; Substituted or unsubstituted sulfonimide group; A carboxylic acid group; Substituted or unsubstituted alkenyl alcohol group; Substituted or unsubstituted alkylcarboxylic acid group; Substituted or unsubstituted alkenylcarboxylic acid group; A substituted or unsubstituted alkoxyalkylsulfonic acid group; Substituted or unsubstituted alkoxy alkenylsulfonic acid group; Substituted or unsubstituted alkoxyalkynyl sulfonic acid group; Substituted or unsubstituted alkoxyalkylcarboxylic acid group; Substituted or unsubstituted alkoxy alkenylcarboxylic acid group; And a substituted or unsubstituted alkoxyalkynylcarboxylic acid group.) The method of claim 1, The pigment (A) pigment dispersion composition further comprises a diazo-based yellow pigment. 3. The method of claim 2, The diazo-based yellow pigment is a pigment dispersion composition comprising 10 to 60% by weight when the total content of the (A) pigment is 100% by weight. delete The method of claim 1, The pigment dispersion composition, Based on 100 parts by weight of the above (A) pigment, 2 to 20 parts by weight of the pigment derivative (B), 1 to 50 parts by weight of the (C) acrylic binder resin, 10 to 80 parts by weight of the (D) dispersant, and Pigment dispersion composition comprising 10 to 1,000 parts by weight of the solvent (E).  The photosensitive resin composition containing the pigment dispersion composition of any one of Claims 1-3. The color filter manufactured using the photosensitive resin composition of Claim 6. The method of claim 7, wherein The luminance of the color filter is 56 or more when the Gy coordinate is 0.59, the contrast ratio is 5,000 or more when the Gy coordinate is 0.59.

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