KR101238578B1 - Carbon Black Complex, Black Matrix Composition Comprising The Same, And Color Filter - Google Patents

Abstract

The present invention relates to a method for producing a carbon black dispersion for forming a black matrix having excellent dispersibility and dispersion stability and excellent patternability.

The present invention relates to a method for preparing a carbon black dispersion using a new surface modifier, and more particularly, to dispersing carbon black in a solvent using a surface modifier comprising a polyethoxyalkylphenyl ether ethyl ester including a vinyl group and derivatives thereof. Zero is an invention of a method for preparing a carbon black dispersion by adding a suitable additive, surfactant, and the like to the carbon black dispersion prepared by inducing a graft reaction that chemically binds the surface modifier to the surface of the carbon black.

Black Matrix, Dissipative, Color Filter

Description

Carbon Black Complex, Black Matrix Composition Comprising The Same, And Color Filter

The present invention relates to a carbon black composite, a black matrix composition comprising the same, and a color filter.

Color filters used in display materials, such as liquid crystal display devices and electronic display devices, form black matrices to block light and improve contrast between fine pack cells that are colored in at least two or more colors, and to reduce color purity. use. Conventionally, such a black matrix was formed of a film of metal such as chromium. This technology deposits metals such as chromium on a transparent substrate, etches the chromium layer through a photolithography process, and provides a highly precise, thin, high light-shielding black matrix. However, at the same time, there is a problem that the price is high due to the long production process and low productivity, and the environmental pollution due to the discharge of the waste liquid by the etching treatment or the like. Therefore, a method of forming a black matrix using a photosensitive resin in which a light-shielding pigment having low cost and no environmental pollution is dispersed has been actively studied.

In the resin black matrix, it is necessary to increase the content of the light-shielding pigment or increase the film thickness in order to exhibit the same degree of light shielding properties as the black matrix composed of a film of a metal such as chromium. However, the method of increasing the film thickness deteriorates the flatness of the colored pixels R, G and B.

In the method of increasing the content of the light-shielding pigment, carbon black, which is a light-shielding pigment, is dispersed at a high concentration, so that the viscosity of the resist composition is increased, dispersion stability is deteriorated, and the sensitivity and resolution are deteriorated. No reliability can be obtained.

In addition, a resin black matrix has been proposed as a dispersant having a urethane bond to disperse carbon black. However, this method has a problem in that it is difficult to improve light shielding properties due to the large amount of dispersant used, insufficient dispersion stability, and reaggregation of carbon black particles with time, resulting in deterioration of physical properties of the BM resist composition. .

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a carbon black composite having excellent dispersion stability, and having a good patternability and easily forming a black matrix pattern having a thin film and high light shielding properties by a photolithography method. It is to be able to form.

The present invention for achieving the above object,

The surface modifier of Chemical Formula 1 is adsorbed onto the carbon black and then polymerized with a polymerization initiator to provide a carbon black composite having a surface modified.

≪ Formula 1 >

Wherein R ₁ , R ₃ are each independently H or a C ₁ to C ₁₈ alkyl group, and R ₂ is H or a C ₁ to C ₂₀ linear alkyl group or a cyclo alkyl group. n is an integer from 0 to 30.)

In addition, the carbon black composite particles provide a carbon black composite, characterized in that the average particle diameter of 500nm or less.

In addition, the surface modifier provides a carbon black composite, characterized in that 10 to 40% by weight based on 100 weight of the carbon black.

In addition, there is provided a carbon black composite characterized in that the adsorption and polymerization takes place in the presence of a solvent as a dispersion medium.

The present invention also provides a carbon black composite dispersion comprising the carbon black composite and a solvent.

The present invention also provides a black matrix composition comprising the carbon black composite, a polymer binder, a photopolymerizable monomer, a photoinitiator, and a solvent.

The present invention also provides a color filter manufactured using the black matrix composition.

Hereinafter, the present invention will be described in detail. The following detailed description is for the purpose of describing the exemplary embodiments of the present invention, but the present invention is not intended to limit the scope of the rights defined by the appended claims, even though there is a certain or limiting expression.

Carbon black composite according to an embodiment of the present invention is characterized in that the carbon black surface is modified with the surface modifier of the formula (1) by adsorbing the surface modifier of the formula (1) to the carbon black, and then graft polymerized through a polymerization initiator .

≪ Formula 1 >

Wherein R ₁ , R ₃ are each independently H or a C ₁ to C ₁₈ alkyl group, and R ₂ is H or a C ₁ to C ₂₀ linear alkyl group or a cyclo alkyl group. n is an integer from 0 to 30.)

The present invention adsorbs a polyethoxyalkylphenyl ether ethyl ester including a vinyl group, which is a surface modifier represented by Chemical Formula 1, and a derivative thereof to carbon black, and then polymerizes it through an initiator to induce a graft reaction on the carbon black surface. The surface of the black is modified to achieve excellent dispersion stability.

The surface modifier of Chemical Formula 1 is characterized by having an anchor component having a strong affinity with the carbon black surface and a reactor capable of graft reaction on the carbon black. First, when the surface modifier of Chemical Formula 1 is mixed with carbon black in an acetate solvent, the alkylphenyl moiety is first physically adsorbed to the carbon black, and the vinyl group is grafted to the carbon black surface by the initiator in the adsorbed state. The efficiency of the graft reaction can be expected, and the polyoxyethylene structure and the alkyl ester group portion exhibit a steric hindrance effect, resulting in stability of the dispersion.

The amount of the surface modifier used in the present invention is preferably 10 to 100% by weight, and more preferably 10 to 40% by weight based on 100% by weight of carbon black.

In addition, the surface modifier may be used to obtain a reactive compound containing an acetate group by adding acetic acid to a commercially available reactive emulsifier in order to dissolve well in acetate solvents as a dispersion medium.

The initiator is not particularly limited and may be used a cumene hydroperoxide, diisopropyl benzene hydroperoxide, etc. in combination with commonly used thermal decomposition initiator or redox polymerization initiator ferrous sulfate, dextrose, sodium pyrophosphate and the like. There is a number.

The carbon black is not particularly limited. However, it is recommended to use acidified surface treated carbon black to improve dispersibility and graft reaction efficiency. Examples include Cabot's BLACK PEARS 1300, MONARCH 1000, Degu's FW-200, FW-18, SPECIAL BLACK 4, Columbia Chemical's RAVEN 5250, RAVEN 5000 ULTRA, Mitsubishi's MA100, and MA77.

The present invention is also suitable for a dispersion in which carbon black composites prepared by dispersing carbon black and the surface modifier of Chemical Formula 1 in a solvent and inducing a graft reaction for chemically bonding the surface modifier to the carbon black surface as an initiator. Carbon black composite dispersions may be prepared by adding additives, surfactants, and the like. The amount of carbon black is not limited but is preferably in the range of 5 to 50% by weight of the total dispersion.

The solvent which is a dispersion medium used in the present invention can be any solvent as long as it is an acetate solvent. For example, butyl acetate, ethyl acetate, propylene glycol methyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and the like.

In the present invention, the reaction temperature during the preparation of the carbon black dispersion is not particularly limited, and a range of 25 ° C. to 60 ° C. is suitable. As for reaction time, 30 minutes-3 hours are suitable normally. The reaction method is not particularly limited either. The reaction may be carried out by adding the surface modifier and the initiator in a batch, or by adding the surface modifier and the initiator several times or by continuously adding the reaction.

The average particle diameter of the carbon black composite particles produced by the above method, etc. has a size of less than 500nm, especially 200nm or less.

The present invention also provides a black matrix composition comprising the carbon black composite, a polymer binder, a photopolymerizable monomer, a photoinitiator, and a solvent. The black matrix composition of the present invention can be used without limitation those well known in the art except for the carbon black composite. In addition, as the black pigment, aniline black, perylene black, titanium black, carbon black and the like may be used in combination with the carbon black composite. The carbon black composite is not limited but may be added in an amount of 5-20 parts by weight based on 100 parts by weight of the total black matrix composition.

The photopolymerizable monomer is not limited, but an acrylic photopolymerizable monomer is preferable, and examples thereof include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, and 1,6-hexanediol diacryl. Latene, neopentyl glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol acrylate, pentaerythritol hexaacrylic Latex, bisphenol A diacrylate, trimethylolpropane triacrylate, noblock epoxy epoxy, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanedioldimethacrylate, 1,6-hexanedioldimethacrylate Rate and the like, and one or more thereof can be selected and used. It may be added in the range of 1-20 parts by weight per 100 parts by weight of the total black matrix composition.

The polymer binder may be used without limitation as a binder of the black matrix composition, and examples thereof include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl meta Unsaturated carboxylate compounds such as acrylates; Unsaturated aminoalkyl carboxylate compounds such as aminoethyl acrylate; Unsaturated glycidyl carboxylate compounds such as glycidyl methacrylate; Vinyl carboxylate compounds such as vinyl acetate and vinyl propionate; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile and α-chloroacrylonitrile; 3-methyl-3-acryloxy methyl oxetane, 3-methyl-3-methacryloxy methyl oxetane, 3-ethyl-3-acryloxy methyl oxetane, 3-ethyl-3-methacryloxy methyl oxetane, 3-methyl-3-acryloxy ethyl oxetane, 3-methyl-3-methacryloxy ethyl oxetane, 3-methyl-3-acryloxy ethyl oxetane and 3-methyl-3-methacryloxy ethyl oxetane, etc. Monomers such as unsaturated oxetane carboxylate compounds and polymers selected from two or more and polymerized or copolymerized. On the other hand, a polymer including a monomer unit having a carboxyl group may be included. The polymeric binder is not limited but may be added in the range of 10-40 parts by weight per 100 parts by weight of the total black matrix composition.

The photoinitiator is not limited, and generally used acetophenone-based derivatives, specifically 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2- Methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, benzophenone, 4-chloroacetophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3, 3'-dimethyl-2-methoxybenzophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1- (4-methylthio) phenyl) -2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1one and the like can be used. 0.1 to 10 parts by weight of the photopolymerization initiator may be used per 100 parts by weight of the total black matrix composition.

In the present invention, the solvent may be ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc., these solvents may be used alone or in combination Can be. Preferably, the solvent used in the preparation of the carbon black composite described above may be used.

Since the ratio of the solvent used in the present invention differs depending on the black matrix composition, it cannot be specified in detail, but it is preferable to select the ratio of the solvent so that the black matrix composition has a viscosity that can be applied to the substrate, and usually black 20-80 parts by weight per 100 parts by weight of the matrix composition.

In addition, certain amounts of other additives such as dispersants, surfactants, antioxidants, stabilizers and the like may be added.

The present invention also provides a color filter comprising a black matrix formed by applying and curing the black matrix composition to form a matrix pattern. The construction of the color filter is well known in the art, so a description thereof will be omitted.

Hereinafter will be described in more detail through the synthesis examples and examples.

Synthesis Example 1) Surface Modifier Synthesis

1) First step

SnCl ₂ in 1.5 was dissolved in deionized water dissolved in commercially available reactive emulsifier HITENOL HS-10 (the first industrial product) -polyethoxyalkylphenyletherethylestersodium sulfate-containing vinyl group to obtain the surface modifier used in the present invention. It was added in equivalent ratio and made to react at room temperature for 30 minutes.

2) second stage

Triethylamine, a weak base, was added to the reaction tank in which the reactant polyethoxyalkylphenyl ether ethyl ester ethyl chloride prepared in step 1 was dissolved. Thereafter, acetic acid is added to the reactant polyethoxyalkylphenyletherethyl ester ethyl chloride in a ratio of 1 to 1 equivalent and reacted at 40 ° C. for 4 hours. The vinyl group represented by the following formula (2) is a surface modifier used in the present invention. Polyethoxyalkyl phenyl ether ethyl acetate which was included was obtained.

<Formula 2>

&Lt; Example 1 >

To 100 g of propylene glycol methyl ether acetate, 10 g of the surface modifier prepared in Synthesis Example 1, 20 g of carbon black BLACK PEARS 1300 (Cabot) and 10 g of the polymerization initiator diisopropylbenzene hydroperoxide were added and mixed. After that, the mixture was placed in a chamber of a beads mill and dispersed at rpm 3000 for 30 minutes. After the temperature of the chamber was raised to 40 ° C. using a thermostat, the temperature was maintained for 3 hours and then cooled. It was then passed through a pore size 0.5 μm microcapsule filter to obtain a carbon black dispersion. The average particle size was measured using a particle size analyzer ELS-8000 and is shown in <Table 1>.

Subsequently, in order to evaluate the dispersion stability of the prepared carbon black dispersion, the viscosity was measured after leaving for 1 day at high viscosity (50 ° C.) after dispersion and the viscosity change rate is shown in <Table 1>.

<Example 2>

In preparing the carbon black dispersion, a carbon black dispersion was prepared in the same manner as in Example 1) except that 20 g of the surface modifier prepared in Synthesis Example 1) was used.

<Example 3>

In preparing the carbon black dispersion, a carbon black dispersion was prepared in the same manner as in Example 1) except that 30 g of the surface modifier prepared in Synthesis Example 1) was used.

<Example 4>

8 g of the carbon black dispersion prepared in Example 1, 6 g of the binder polymer epoxy acrylate, 1 g of the photopolymerizable monomer-DPHA (trade name Nippon Kayaku Pharmaceutical Co., Ltd.), 0.5 g of the photopolymerization initiator Monocure 369 (trade name: Ciba-Geigy) 6 g of propylene glycol monomethyl ether acetate was mixed to prepare a resist for forming a black matrix.

Subsequently, the obtained resist is spin-coated on a glass substrate and baked at a temperature of 100 ° C. on a hot plate. Subsequently, an energy of 200 mJ / cm ² was irradiated using a 500 W ultra high pressure silver lamp and through a mask formed of a black matrix pattern. Thereafter, alkali development was carried out, and baking was conducted at an oven temperature of 220 ° C. for 30 minutes to evaluate resist overall physical properties. The results are shown in Table 2 below.

<Example 5>

In preparing the black matrix forming resist, the same procedure as in Example 4) was conducted except that the dispersion prepared in Example 2) was used as the dispersion. Results of the overall evaluation of the resist properties are shown in Table 2.

&Lt; Example 6 >

In preparing the black matrix forming resist, the same procedure as in Example 4) was conducted except that the dispersion prepared in Example 3) was used as the dispersion. Results of the overall evaluation of the resist properties are shown in Table 2.

&Lt; Comparative Example 1 &

To 100 g of propylene glycol methyl ether acetate, 10 g of a commercially available acrylate dispersant and 20 g of carbon black BLACK PEARS 1300 (Cabot) were mixed. After that, the mixture was placed in a chamber of a beads mill and dispersed at rpm 3000 for 30 minutes. It was then passed through a pore size 0.5 μm microcapsule filter to obtain a carbon black dispersion. The average particle size was measured using a particle size analyzer ELS-8000 and is shown in <Table 1>.

Subsequently, in order to evaluate the dispersion stability of the prepared carbon black dispersion, the viscosity was measured after leaving for 1 day at high viscosity (50 ° C) after dispersion and the viscosity change rate is shown in <Table 1>.

Comparative Example 2

8 g of the carbon black dispersion prepared in Comparative Example 1, 6 g of the binder polymer epoxy acrylate, 1 g of the photopolymerizable monomer -DPHA (trade name Nippon Chemical Co., Ltd. 6 g of glycol monomethyl ether acetate was mixed to prepare a resist for forming a black matrix.

Subsequently, the obtained resist is spin-coated on a glass substrate and baked at a temperature of 100 ° C. on a hot plate. Subsequently, an energy of 200 mJ / cm ² was irradiated with a 500 W ultra high pressure silver lamp and through a mask in which a black matrix pattern was formed. Thereafter, alkali development was carried out, and baking was conducted at an oven temperature of 220 ° C. for 30 minutes to evaluate resist properties. The results are shown in Table 2 below.

TABLE 1

Average particle size (nm) Viscosity (cps) Dispersion stability
(Viscosity change after high temperature standing) Example 1 105 nm 5.6 Good (+ 1.5%) Example 2 110 nm 5.8 Good (+ 1.8%) Example 3 190 nm 8.9 Poor (+ 4.5%) Comparative Example 1 120 nm 5.4 Poor (+ 6.6%)

<Table 2>

Developability Pattern Example 4 ○ ○ Example 5 △ ○ Example 6 △ △ Comparative Example 2 △ △

  (In Table 2, ○: good △: normal X: defective)

Carbon black composite according to the present invention is characterized in that the surface modified by a high efficiency graft reaction using a compound having an anchor component having a strong affinity and a reactor capable of graft reaction on carbon black, polyoxyethylene structure and The alkyl ester moiety exhibits excellent compatibility with the solvent, and the graft reaction moiety exhibits steric hindrance, resulting in excellent dispersibility and stability, excellent patternability, and thin film and high light shielding properties by the photolithography method. The black matrix pattern can be easily formed.

Claims (7)

A carbon black composite comprising adsorbing a surface modifier of Chemical Formula 1 to carbon black and then graft polymerizing it through a polymerization initiator to modify the carbon black surface with the surface modifier of Chemical Formula 1. &Lt; Formula 1 >

Wherein R ₁ , R ₃ are each independently H or a C ₁ to C ₁₈ alkyl group, and R ₂ is H or a C ₁ to C ₂₀ linear alkyl group or a cyclo alkyl group. n is an integer from 0 to 30.) The carbon black composite according to claim 1, wherein the carbon black composite particles have an average particle diameter of 500 nm or less. The carbon black composite according to claim 1, wherein the surface modifier is used in an amount of 10 to 40 wt% based on 100 weight of the carbon black. The carbon black composite according to claim 1, wherein adsorption and graft polymerization occur in the presence of a solvent as a dispersion medium. A carbon black composite dispersion comprising the carbon black composite according to any one of claims 1 to 4 and a solvent. The black matrix composition comprising the carbon black composite according to any one of claims 1 to 4, a polymer binder, a photopolymerizable monomer, a photoinitiator, and a solvent. A color filter prepared using the black matrix composition of claim 6.