KR20140011578A

KR20140011578A - Method for preparing of fine pigment and pigment dispersion composition for color filter comprising the same

Info

Publication number: KR20140011578A
Application number: KR1020120077846A
Authority: KR
Inventors: 이수현; 김승호; 민홍기
Original assignee: 주식회사 유엔아이
Priority date: 2012-07-17
Filing date: 2012-07-17
Publication date: 2014-01-29

Abstract

The present invention relates to a method for manufacturing a fine pigment and a pigment dispersion composition for a color filter containing the fine pigment and, more specifically, to a method for manufacturing a fine pigment which prepares a mixed composition by mixing water-soluble inorganic salt, a water-soluble organic solvent, a resin, a sulfonated quinophthalone-based dispersion agent and removes the water-soluble inorganic salt and pigment dispersion composition from the mixed composition, and the pigment dispersion composition for a color filter containing the fine pigment manufactured thereby. The pigment dispersion composition. The pigment dispersion composition according to the present invention exhibits excellent pigment dispersibility and dispersion stability and is able to be usefully applied to the manufacture of a color filter with improved pattern characteristics, photolithography process properties, chemical resistance and color reproduction properties by having high brightness, contrast and transmittance.

Description

Method for preparing of fine pigment and pigment dispersion composition for color filter comprising the same}

The present invention relates to a pigment dispersion composition for a color filter comprising a method for producing a fine pigment and a micropigment, and more particularly, to kneading a pigment, a water-soluble inorganic salt, a water-soluble organic solvent, a resin, and a sulfonated quinophthalone-based dispersant. After obtaining a kneading composition, the present invention relates to a method for producing a fine pigment, characterized in that a water-soluble inorganic salt and a water-soluble organic solvent are removed in water, and a pigment dispersion composition for a color filter comprising the micro pigment thus prepared.

Generally, as a method of pigmentizing coarse crude pigment particles, methods such as solvent salt milling and dry grinding are widely used.

The dry grinding method is a method in which the coarsely prepared pigment particles are pigmented by dry grinding by ball mill, attritor, vibrating mill, etc., and the production efficiency per unit energy is better than that of the solvent salt milling method. However, since the gap of particle diameter is big and the cohesion force between particles is extremely strong, a huge aggregate in which many fine primary particles couple | bonded with very strong force is not obtained. For this reason, various improvement methods are examined about the dry grinding method, but it is difficult to obtain a pigment of high quality.

In the solvent salt milling method, coarse crude pigment particles are mechanically polished by a kneader or the like in the presence of inorganic salts such as sodium chloride or sodium sulfate and highly viscous water-soluble organic solvents such as ethylene glycol, diethylene glycol and polyethylene glycol. By the method of pigmentation, the pigment of predetermined | prescribed degree of refinement | miniaturization can be obtained by processing by kneading | mixing.

As a use use of the pigment with a high degree of refinement | miniaturization, a color filter is mentioned, for example.

Color filters are used in color liquid crystal display devices, and are arranged in parallel or intersecting two or more different fine strips (stripes) of different colors on the surface of transparent substrates such as glass, or fine pixels arranged in a vertical and horizontal constant array. consist of. By using a pigment having a high degree of miniaturization, the color liquid crystal display device can realize high contrast ratio and transparency.

In general, however, it is difficult to disperse pigment particles having a high degree of fineness in a pigment carrier such as a varnish to obtain a stable dispersion. In addition, such a dispersion sometimes becomes highly viscous by aggregation of pigment particles over time, and forms a thixotropic property. Such increase in viscosity and poor fluidity of the dispersion cause various problems in color filter manufacturing work and product value. For example, formation of the filter segment of a color filter is generally performed by apply | coating the coloring composition in which the pigment is disperse | distributed to the carrier containing monomer and resin on transparent substrates, such as glass. At this time, it is not preferable to use a colored composition having high viscosity and poor fluidity because a coating film with a uniform film thickness cannot be obtained due to poor coating properties, poor leveling, or the like. In addition, the color filter formed by using the dispersion in which the pigment particles are aggregated significantly lowers the contrast ratio. Here, the pigment is required to be stable fine particles which do not aggregate and are easy to handle.

In order to develop a color liquid crystal display device for a large screen TV, a monitor, etc., other viewing angle characteristics, such as contrast and transparency, also become an important item, and the technology of wide viewing angle is advanced.

Domestic Patent No. 10-0941733 Domestic Publication No. 10-2009-0037816

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a pigment dispersion composition for a color filter comprising a fine pigment and a method for producing a fine pigment excellent in pigment dispersibility and dispersion stability.

In addition, an object of the present invention is to provide a pigment dispersion composition for a color filter comprising a fine pigment and a method for producing a fine pigment, the optical properties such as contrast, brightness, etc. remarkably improved.

In addition, the present invention has a high brightness, high contrast, and high transmittance color filter comprising a fine pigment manufacturing method and a fine pigment that can be usefully applied to the production of color filters with improved pattern characteristics, development processability, chemical resistance and color reproducibility An object of the present invention is to provide a pigment dispersion liquid composition.

In order to achieve the above object, the present invention comprises the steps of kneading a pigment, a water-soluble inorganic salt, a water-soluble organic solvent, a resin and a sulfonated quinophthalone-based dispersant to prepare a kneading composition; And removing water-soluble inorganic salts and water-soluble organic solvents from the kneading composition.

The kneading composition includes 600 to 1,000 parts by weight of a water-soluble inorganic salt, 250 to 500 parts by weight of a water-soluble organic solvent, 1 to 5 parts by weight of a water-soluble resin, and 1 to 7 parts by weight of a sulfonated quinophthalone-based dispersant based on 100 parts by weight of a pigment. do.

In particular, the sulfonated quinophthalone-based dispersant has a sulfur content of at most 5 mol%, preferably 3 to 5 mol%.

The present invention also provides a pigment dispersion composition comprising an acrylic binder, a fine pigment prepared by the above method, a dispersant, and a solvent.

Specifically, the pigment dispersion composition comprises 0.1 to 40% by weight of the acrylic binder, 1 to 20% by weight of the fine pigment prepared by the above method, 0.1 to 40% by weight of the dispersant and 10 to 80% by weight of the solvent.

It is preferable that the acrylic binder has a number average molecular weight of 10,000 to 50,000 and an acid value of 50 to 150 mg / KOH when the solubility in an alkaline developer is taken into account.

The present invention also provides a color filter photosensitizer composition comprising the pigment dispersion composition.

The present invention also provides a color filter made of a color filter photosensitizer composition.

The pigment dispersion composition according to the present invention is excellent in pigment dispersibility and dispersion stability, and the optical properties such as contrast and brightness are remarkably improved to be useful for the production of color filters having improved pattern characteristics, developing processability, chemical resistance and color reproducibility. Can be.

Hereinafter, the present invention will be described in detail.

The present invention uses the sulfonated quinophthalone-based dispersant in the pigment refining process to produce a fine pigment, and by adding the prepared fine pigment to the pigment dispersion composition to improve the dispersion stability as well as high brightness when applied to the color filter It is possible to manufacture a color filter having high contrast.

The method for preparing a fine pigment of the present invention comprises the steps of kneading a pigment, a water-soluble inorganic salt, a water-soluble organic solvent, a resin and a sulfonated quinophthalone-based dispersant, and adding the kneaded composition in water to prepare a water-soluble inorganic salt and a water-soluble organic solvent. Removing.

Hereinafter, the method for producing the fine pigment of the present invention will be described in detail.

First, a kneading composition is prepared by kneading a pigment, a water-soluble inorganic salt, a water-soluble organic solvent, a resin, and a sulfonated quinophthalone-based dispersant.

The pigment used for the kneading composition can be appropriately selected from various conventionally known inorganic pigments or organic pigments. In particular, it is more preferable to use an organic pigment, and it is preferable to use a pigment having a small particle size.

The average particle size of the pigment is preferably 100 nm or less, more preferably 50 nm or less, and most preferably 30 to 40 nm. If the average particle size is in the above range, the transmittance is high, the color characteristics are good, and it is better to form a high contrast color filter.

The inorganic pigments include metal compounds such as metal oxides and metal complex salts, and specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony and complex oxides of the metals. And the like can be used.

Examples of the organic pigments,

CIPigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: , 81: 2, 81: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: , 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 , 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,

CIPigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36 , 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97 , 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139 , 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179 , 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214,

CIPigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 ,

C.I.Pigment Green 7, 10, 36, 37, 58

Cl substituents of CIPigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Thing 80,

C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42,

C.I. Pigment Brown 25, 28, and

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

These organic pigments can be used alone or in various combinations to improve color purity. Specific examples of the combination are shown below.

For example, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them as a red pigment, a disazo yellow pigment, an isoindolin yellow pigment, Quinophthalone type yellow pigment or perylene type red pigment, anthraquinone type red pigment, diketopyrrolopyrrole type red pigment, etc. can be mixed and used. For example, the anthraquinone pigment may include CIPigment Red 177, and the perylene pigment may include CIPigment Red 155, CIPigment Red 224, and the diketopyrrolopyrrole pigment may be CIPigment Red. 254, and from the viewpoint of color reproducibility, it is preferable to use a mixture of at least one of them and CIPigment Yellow 83, CIPigment Yellow 139 or CIPigment Red 177. Moreover, as for the mass ratio of a red pigment and another pigment, 100: 5-100: 80 are preferable. In 100: 4 or less, it is difficult to suppress the light transmittance of 400 nm-500 nm, and color purity may not be improved. Moreover, the coloring power may fall at 100: 81 or more. Especially as said mass ratio, the range of 100: 10-100: 65 is optimal. In addition, when it is a combination of red pigments, it can adjust to chromaticity.

In addition, as a green pigment, a halogenated phthalocyanine type pigment is used individually by 1 type, or this and a disazo yellow pigment, a quinophthalone type yellow pigment, an azomethine type yellow pigment, and an isododoline type. Yellow pigment etc. can be mixed and used. Examples thereof include CIPigment Green 7, 36, 37, CIPigment Yellow 83, CIPigment Yellow 138, CIPigment Yellow 139, CIPigment Yellow 150, CIPigment Yellow 180, CIPigment Yellow 185, and the like. . As for the mass ratio of a green pigment and a yellow pigment, 100: 5-100: 200 are preferable. When the said mass ratio is less than 100: 5, it may become difficult to suppress the light transmittance of 400-450 nm, and color purity may not be improved. In addition, when the wavelength exceeds 100: 200, the dominant wavelength may be close to the long wavelength, which may cause a large deviation from the NTSC (National Television Standards Committee) target color. As said mass ratio, the range of 100: 20-100: 150 is especially preferable.

As a blue pigment, a phthalocyanine type pigment can be used individually by 1 type, or the mixture of this and a dioxadine type purple pigment can be used. As a particularly preferred example, a mixture of C.I. Pigment Blue 15: 6 and C.I.Pigment Violet 23 may be used.

The water-soluble inorganic salt used in the kneading composition serves as a crushing aid, and when salt milling, the pigment is crushed using the height of the hardness of the inorganic salt to make the primary particles of the pigment fine.

The water-soluble inorganic salt is not particularly limited as long as it is dissolved in water, and for example, sodium chloride, barium chloride, potassium chloride, sodium sulfate, zinc chloride, calcium chloride, magnesium chloride, and the like can be used alone or in combination of two or more thereof. In particular, it is preferable to use sodium chloride or sodium sulfate in terms of cost.

Although the amount of the water-soluble inorganic salt is not particularly limited, it is preferably included in 600 to 1,000 parts by weight with respect to 100 parts by weight of the pigment, when the content is within the above range, it is easy to refine and sizing, the pigment of the kneading composition Due to the high throughput, the productivity is high and industrially advantageous.

The above water-soluble inorganic salts have a particle diameter of 1 to 50 µm in terms of median (median) particle diameter (D50) based on volume, preferably 10 to 30 µm in terms of particle diameter (D50). It is suitable for the miniaturization of the resin, and the processing time for producing the fine pigment is short, which is better in terms of cost.

The water-soluble organic solvent used in the kneading composition is added so that the remaining components contained in the kneading composition are mixed in a uniform phase, and are not particularly limited as long as they are dissolved (mixed) in water and do not substantially dissolve the inorganic salts used. Do not. However, since a temperature rises at the time of salt milling and a solvent becomes easy to evaporate, it is preferable to use the high boiling point solvent of 120 degreeC or more from a viewpoint of safety.

As such a water-soluble organic solvent, 2-methoxyethanol, 2-butoxy ethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene Glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, glycerin, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol , Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, low molecular weight polypropylene glycol, aniline, pyridine, dioxane, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, propylene glycol, propylene glycol mono Methyl ether acetate, ethyl acetate, isopropyl acetate, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. Or more may be used in combination.

The amount of the water-soluble organic solvent is not particularly limited, but may be appropriately adjusted according to the hardness of the kneading composition according to the difference in the amount and oil absorption of the water-soluble inorganic salt and the structure of the pigment, specifically 250 to 100 parts by weight of the pigment It is preferably included in 500 parts by weight. If the amount is less than 250 parts by weight, the pigment and the water-soluble inorganic salt may not be sufficiently wet, which makes it difficult to uniformly kneaded, but rather causes problems such as growth of particles due to heat. When the content exceeds 500 parts by weight, the kneading composition becomes so soft that it is difficult to apply the shearing energy of kneading to the kneading composition.

The resin used in the kneading composition preferably has a polymer backbone having an acryl main chain and at least one functional group selected from hydroxyl group, amide group, carbamoyl group and urea group and having a weight average molecular weight of 1,000 to 100,000. Do. Although it does not restrict | limit especially if it is such resin, It is preferable that the side chain which has a functional group chosen from the group of a hydroxyl group, an amide group, a carbamoyl group, and a urea group is connected to the aromatic group, and most preferably, it is connected to the aromatic hydrocarbon group.

The resin is preferably included 1 to 5 parts by weight with respect to 100 parts by weight of the pigment, if the content is less than 1 part by weight, the adsorption on the surface of the pigment may be undesirably poor results, if more than 5 parts by weight The pigment surface is adsorbed on the surface of the pigment and the excess resin component can interfere with the shear force and inhibit the miniaturization of the pigment.

The sulfonated quinophthalone-based dispersant used in the kneading composition is used for evenly dispersing the components contained in the kneading composition. The sulfonated quinophthalone-based dispersant may lower the viscosity of the kneading composition, increase dispersibility and dispersion stability, and thus may be effectively used in the process of miniaturizing the pigment.

The sulfonated quinophthalone-based dispersant may be represented by the following formula (1).

[Formula 1]

In Formula 1, n is an integer of 1 to 4.

The sulfonated quinophthalone-based dispersant is preferably sulfur (S) content of 5 mol% or less, more preferably 3 to 5 mol%.

The sulfonated quinophthalone-based dispersant may be used in varying amounts depending on the surface area of the micronized pigment to be finally obtained, specifically 1 to 7 parts by weight based on 100 parts by weight of the pigment, more preferably Preferably it is included in 3 to 6 parts by weight. If the content is less than 1 part by weight, the components used in the kneading composition do not function smoothly, and if it exceeds 7 parts by weight, it is difficult to expect an effective action. Deterioration may occur.

The kneading composition may further include additives such as various resins, dispersion aids, plasticizers, and surfactants as necessary.

As described above, the pigment, the water-soluble inorganic salt, the water-soluble organic solvent, the resin and the sulfonated quinophthalone-based dispersant are mechanically kneaded, wherein the mechanically kneaded apparatus is kneader, planetary mixer, trimix (manufactured by Inoue Co., Ltd.). , 2 rolls, 3 rolls, multi-axis rolls, extruders, KRC kneaders (manufactured by Kurimoto Iron Works), or Miracle KCK (manufactured by Asada Iron Works), etc. If it can be given, it can be used regardless of batch type and continuous type.

In addition, the temperature at the time of kneading is not particularly limited, but is preferably made at 20 ~ 100 ℃, preferably 30 ~ 80 ℃. When the temperature at the time of kneading is within the above range, the speed of pulverizing and miniaturizing the pigment particles and the crystal growth rate of the pigment particles can be easily controlled, and a predetermined degree of refinement can be obtained.

The fine pigment after kneading is processed by a conventional method. In other words, the kneaded composition is treated with water or a light aqueous solution, the water-soluble inorganic salt and the water-soluble organic solvent are removed by filtration and washing with water to isolate the fine pigment. Specifically, the fine pigment after kneading is introduced into water, stirred to slurry, and the slurry is filtered and washed to remove the water-soluble inorganic salt and the water-soluble organic solvent, thereby finally obtaining a fine pigment. These processes can of course be repeated several times as needed.

The fine pigments prepared as described above may be used as they are, or may be used in powder form by dry grinding.

The average particle size of the fine pigment is preferably 50 nm or less, more preferably 40 nm or less, and most preferably 20 to 40 nm. When it exceeds 50 nm, transparency and the like may be lowered. When the average particle size is less than 20 nm, pigment dispersion may be difficult, and stability and fluidity may be difficult to maintain.

The fine pigment of the present invention prepared as described above can be used in the pigment dispersion composition. Specifically, the pigment dispersion composition of the present invention comprises an acrylic binder, a fine pigment prepared according to the present invention, a dispersant and a solvent.

In the acrylic binder used in the pigment dispersion composition, the acrylic binder has one carboxyl group in order to have a good performance in the alkali developer in the developing process because the final use is used in the color filter photoresist in the use of the pigment dispersion. It is preferable to use the acrylic binder which consists of the ethylenically unsaturated monomer contained above and the other ethylenically unsaturated monomer copolymerizable with this. For example, the acrylic binder is meta acrylic acid, acrylic acid, maleic anhydride unsaturated polyester, polyester acrylate, polyepoxy acrylate paper, polyurethane acrylate, polyether acrylate, polyol acrylate glycidyl It is preferable to include acrylate, glycidyl methacrylate, and the like.

Specific examples of the acrylic binder comprising an ethylenically unsaturated monomer containing one or more of the carboxyl groups and other ethylenically unsaturated monomers copolymerizable therewith include benzyl acrylate methacrylic acid, methyl methacrylate methacrylate, and benzyl methacrylate methyl methacrylate. Acrylate methacrylic acid, benzyl methacrylate methyl methacrylate acrylic acid, 2-hydroxyethyl methacrylate methyl methacrylate methacrylic acid, 2-hydroxyethyl methacrylate benzyl methacrylate methacrylic acid, styrene 2-hydroxy Hydroxyethyl benzyl methyl methacrylate acrylic acid copolymer and the like.

The acrylic binder has a number average molecular weight of 10,000 to 50,000, it is preferable that the acid value is 50 ~ 150mg / KOH when considering the solubility in the alkaline developer. When the number average molecular weight is out of the above range, the compatibility in the pigment dispersion may decrease, making it difficult to disperse, and may impair the process developability of the photosensitizer in manufacturing the color filter, and the acid value may be out of the range. It may inhibit the stability of the pigment dispersion.

The acrylic binder is preferably included in 0.1 to 40% by weight in the pigment dispersion composition, when the content is less than 0.1% by weight the expression of the effect that can be obtained by using the acrylic binder is not sufficient, exceeding 40% by weight In this case, it is preferable to maintain the above range because problems may occur during thermal curing.

The fine pigment used in the pigment dispersion composition is a pigment refined according to the above-described method, it is preferably included in 1 to 20% by weight in the pigment dispersion composition. If the content is less than 1% by weight, color formation is not easy, and if it exceeds 20% by weight, it is difficult to disperse the manufacturing yield.

In addition, the pigment dispersion composition of the present invention may be used by mixing a conventional pigment used in a conventional pigment dispersion, if necessary, in addition to the fine pigment micronized as described above.

As the conventional pigments that can be mixed with the fine pigments, conventional inorganic pigments or organic pigments described in the preparation of the aforementioned fine pigments may be appropriately selected and used.

The dispersant used in the pigment dispersion composition is used for evenly dispersing the components constituting the pigment dispersion composition together with the acrylic binder, has an solubility in organic solvents commonly used in the art, and is used with an acrylic binder And pigments and the like can be used.

As the commercially available dispersant, dispersants such as polyacrylic, polyester and polyurethane may be used, and commercially available disperbyk-110, 111, 180, 161, 163, 165, 166, 167, 2000, 2001, 2163, LPN -21116, LPN-6919, LPN-21538, LPN-21208 (BYK-chemie) LPN-21324, LPN-21208, PB-821, 822, 880, 881 (AJINOMOTO FINE TECHNO), solsperse 24000 (Lubricol), etc. It can be used individually or in mixture of 2 or more types.

It is preferable that the dispersant is included in the pigment dispersion composition in an amount of 0.1 to 40% by weight, and when the content is less than 0.1% by weight, the dispersion is not sufficient. When the dispersant exceeds 40% by weight, the compatibility of the dispersant in the solvent is increased. This can be degraded, making it difficult to control dispersion stability.

In addition, the solvent used in the pigment dispersion composition is not particularly limited as long as it is a solvent in which the components included in the pigment dispersion composition can be dissolved. Specifically, propylene glycol methyl ether acetate (PGMEA, propylene glycol methyl ether acetate), Propylene glycol monomethyl ether acetate, propylene glycol methyl ether (PGME), ethyl-3-ethoxy propionate (EEP), cyclohexanone (cychohexanone), methyl ethyl ketone (MEK, methyl ethyl ketone), methyl iso butyl ketone (MIBK), methoxy butyl acetate (metoxy butyl acetate) and the like can be used. Such a solvent is more preferably contained in the pigment dispersion composition 10 to 80% by weight in terms of production yield.

The pigment dispersion composition as described above is preferably maintained at a dispersion temperature of 5 to 15 ℃ in order to maintain stability during dispersion.

In another aspect, the present invention provides a photosensitive resin composition comprising a pigment dispersion composition, an acrylic binder resin, an acrylic photopolymerization monomer, a photoinitiator and a solvent as described above. Each component which comprises the said photosensitive resin composition can be used by adjusting suitably in a well-known range.

The pigment dispersion composition is the same as described above.

In addition, the acrylic binder resin and the solvent may be the same as used in the production of the pigment dispersion composition.

It is preferable to use the polyfunctional monomer which has a 2 or more hydroxyl group as said acryl-type photopolymerizable monomer.

Specifically, glycerol (meth) acrylate, pentaerythritol hexa (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate , 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri ( Meta) acrylate, dipentaerythritol (meth) acrylate, bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, novolac epoxy (meth) acrylate, diethylene glycol di (meth) Acrylate, propylene glycol di (meth) acrylate, and the like can be used.

In addition, as the photopolymerization initiator, a photopolymerization initiator commonly used in the photosensitive resin composition may be used, and specifically, an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, and an oxime compound Etc. can be used individually or in mixture of 2 or more types.

Examples of the acetophenone compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylfluorophenone, pt-butyltrichloroacetophenone, and pt- Butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and the like can be used. Examples of the benzophenone compounds include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, and 4,4'-. Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone and the like can be used. Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2- Orcanthon and the like can be used. 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 triazine compound include 2,4,6-trichloro s-triazine, 2-phenyl 4,6-bis (trichloromethyl) -s-triazine, and 2- (3 ', 4'-dimethoxysty Reyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-r Phenyl 4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl s-triazine, 2- (naphtho1-yl) -4,6-bis (trichloro Rhomethyl) -s-triazine, 2- (4-methoxynaphtho1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2-4-trichloro methyl (piperonyl ) -6-triazine, 2-4-trichloro methyl (4'-methoxystyryl) -6-triazine, 2-piperoniro-4,6-bis (trichloromethyl) -1,3, 5-triazine, etc. can be used. Examples of the oxime compounds include 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (o- 6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone.

In addition to the photopolymerization initiator, carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, biimidazole compounds and the like can also be used as the photopolymerization initiator.

The photosensitive resin composition of the present invention comprising a pigment dispersion composition, an acrylic binder resin, an acrylic photopolymerization monomer, a photopolymerization initiator and a solvent as described above is used to prevent staining or spots during coating, leveling properties, or prevention of residues caused by undeveloped. To malonic acid; 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.

The photosensitive resin composition may further include an epoxy compound as needed for the purpose of improving the adhesion and other properties.

As said epoxy compound, single or 2 types of epoxy novolak acrylic carboxylate resin, ortho cresol novolak epoxy resin, phenol novolak epoxy resin, tetramethyl biphenyl epoxy resin, bisphenol-A epoxy resin, alicyclic epoxy resin, etc. It can mix and use the above.

The epoxy compound is preferably contained in 0.01 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition for color filters. When the epoxy compound is included in the above range, the adhesion and other properties can be improved in storage and economically better.

When the epoxy compound is further included as described above, a radical polymerization initiator such as a peroxide initiator or an azobis-based initiator may be further included.

In addition, the present invention provides a color filter prepared from the photosensitive resin composition for the color filter, the color filter may be manufactured according to a conventional method, a detailed description thereof will be omitted.

Hereinafter, the present invention will be described in more detail with reference to examples. These embodiments are for purposes of illustration only and are not intended to limit the scope of protection of the present invention.

Hereinafter, the acrylic resin solution used for the preparation of the fine pigment was prepared and used as follows.

First, 800 parts by weight of propylene glycol monoethyl ether acetate was added to the reaction vessel, and heated to 100 ° C. while injecting nitrogen gas into the vessel. At the same temperature, 80 parts by weight of methacrylic acid, 85 parts by weight of methyl methacrylate, and butyl meta A mixture of 85 parts by weight of acrylate and 10 parts by weight of 2,2'-azobisisobutyronitrile was added dropwise for 1 hour to polymerize. After dripping, after reacting again at 100 degreeC for 3 hours, the thing which melt | dissolved 5 weight part of azobisisobutyronitrile in 50 weight part of propylene glycol monoethyl ether acetate was added, and also reaction was continued at 100 degreeC for 1 hour, An acrylic resin solution having a weight average molecular weight (Mw) of 28,000 was obtained.

Example 1 Preparation of Fine Pigments

Phthalocyanine-based green pigment (CI Number Pigment green 7 [PG7]: 35 parts by weight of Heubach, trade name HEUCO Green 600736, Specific Surface [m2 / g]), 330 parts by weight of sodium chloride as a water-soluble inorganic salt, diethylene as a water-soluble organic solvent 123 parts by weight of glycol, 0.35 part by weight of an acrylic resin solution having a weight average molecular weight (Mw) of 28,000 by resin, and a sulfonated quinophthalone-based dispersant (Daiwa Chemical Co., Ltd., Yellow 138 SR, S content of 3.7 mol%) 1.75 weight The part was put into a trimixer, and the whole water was mechanically kneaded at 19 rpm for a revolution, 57 rpm for a revolution and a processing temperature of 70 ° C. for 8 hours.

The kneaded product thus obtained was introduced into about 5 L of water, stirred for about 1 hour in a high speed mixer, filtered and washed with water to remove sodium chloride and an organic solvent, and dried to obtain a fine pigment having an average particle size of 33 nm. .

Example 2. Fine Pigment Preparation

20 parts by weight of diketopyrrolopyrrole pigment (CIPigment Red 254, manufactured by Chiba Specialty Chemicals, Inc.), 130 parts by weight of sodium chloride as a water-soluble inorganic salt, 90 parts by weight of diethylene glycol as a water-soluble organic solvent, resin 0.4 parts by weight of an acrylic resin solution having a weight average molecular weight (Mw) of 28,000 and 1.0 part by weight of a sulfonated quinophthalone-based dispersant (Daiwa Chemical Co., Ltd., Yellow 138 SR, S content of 3.7 mol%) were used. In the same manner as in Example 1, a fine pigment having an average particle size of 28 nm was obtained.

Example 3. Fine Pigment Preparation

Yellow pigment (CI Number Pigment Yellow 150 [PY150]: product of Lanxess, trade name: E4GN-GT, Specific Surface [m2 / g] 139) 25 parts by weight, 200 parts by weight of sodium chloride as water-soluble inorganic salt, diethylene as water-soluble organic solvent 90 parts by weight of glycol, 0.5 parts by weight of an acrylic resin solution having a weight average molecular weight (Mw) of 28,000, and a sulfonated quinophthalone-based dispersant (Daiwa Chemical Co., Ltd., Yellow 138 SR, S content of 3.7 mol%) 1.0 weight A fine pigment having an average particle size of 30 nm was obtained in the same manner as in Example 1 except that parts were used.

Example 4. Fine Pigment Preparation

Pigment PG7 (manufactured by Heubach, trade name HEUCO Green 600736): PY139 (manufactured by BASF Corporation, trade name 2RP-CF): PY150 pigment (Lanxess company, trade name: E4GN-GT) in a ratio of 70:10:20 40 parts by weight of a mixed pigment, 300 parts by weight of sodium chloride as a water-soluble inorganic salt, 160 parts by weight of diethylene glycol as a water-soluble organic solvent, 0.4 part by weight of an acrylic resin solution having a weight average molecular weight (Mw) of 28,000 as a resin, and sulfonated quinophthalone A fine pigment having an average particle size of 30 nm was obtained in the same manner as in Example 1, except that 2.1 parts by weight of a system dispersant (Daiwa Chemical Co., Ltd., Yellow 138 SR, S content: 3.7 mol%) was used.

Example 5. Pigment Dispersion Composition Preparation

10 wt% of the fine pigment having an average particle size of 33 nm prepared in Example 1, an acrylic binder (benzyl methacrylate, methyl methacrylate and methacrylic acid copolymer of 5: 3: 2, Mw = 15,000, Solid jacket 30%) 6.67% by weight, dispersant (BYK-chemie, LPN-21116, solids 40%) 6.81% by weight and 76.52% by weight propylene glycol monomethyl ether acetate with solvent And vigorously mixed at 2,000 rpm for 1 hour using a high speed resolver.

Dispersing the mixed pigment dispersion composition at 2,000rpm for 1 hour using Dispermat-CV which is a vertical dispersion machine, wherein zirconia beads 2.0 mm are used as the dispersion medium, but the volume ratio of the pigment dispersion composition and the dispersion medium is 1: 1 was filled into the disperser. The temperature of the composition was maintained at 10 to 15 ° C. in order to prevent rapid temperature rise of the pigment dispersion composition during dispersion and to allow the dispersion to proceed smoothly.

After removing the beads from the primary dispersion in which the primary dispersion was completed, the 0.1 mm zirconia beads were filled so that the volume ratio of the primary dispersion to the beads was 1: 1 and the secondary dispersion was performed at 2,000 rpm for 3 hours. Proceeded. The dispersion temperature was maintained at 10 to 15 ℃ even during the secondary dispersion, and after the dispersion was completed, the secondary dispersion was stabilized while stirring at a low speed (300 rpm) for 12 hours at room temperature (20 to 25 ℃) and a 1 μm membrane filter Filtration using to prepare a pigment dispersion composition.

Example 6. Pigment Dispersion Composition Preparation

Except for using a fine pigment having an average particle size of 28nm prepared in Example 2 was carried out in the same manner as in Example 5.

Example 7. Pigment Dispersion Composition Preparation

Except for using a fine pigment having an average particle size of 30nm prepared in Example 3 was carried out in the same manner as in Example 5.

Example 8. Pigment Dispersion Composition Preparation

Except for using a fine pigment having an average particle size of 30nm prepared in Example 4 was carried out in the same manner as in Example 5.

Example 9. Preparation of photosensitive resin composition for color filters

Using the pigment dispersion composition prepared in Example 5 to prepare a photosensitive resin composition for a color filter by the following steps using a formula.

First, 1.0% by weight of a triazine photopolymerization initiator (TPP) was dissolved in 32.5% by weight of propylene glycol methyl ethyl acetate, followed by stirring at room temperature for 30 minutes. To this mixture, 6.9% by weight of acrylic acid benzyl methacrylate copolymer binder and 4.6% by weight of photopolymerizable monomer (Dongyang Synthetic Co., Ltd., DPHA) were added and stirred at room temperature for 30 minutes. 55.0% by weight of the pigment dispersion composition prepared in Example 5 was added to the mixture thus obtained, followed by stirring at room temperature for 1 hour, and then filtered once to prepare a photosensitive resin composition for color filters.

Example 10. Preparation of photosensitive resin composition for color filters

The same procedure as in Example 10 was carried out except that the pigment dispersion composition prepared in Example 6 was used.

Example 11. Preparation of the photosensitive resin composition for color filters

Except for using the pigment dispersion composition prepared in Example 7 was carried out in the same manner as in Example 10.

Example 12. Preparation of photosensitive resin composition for color filters

Except for using the pigment dispersion composition prepared in Example 8 was carried out in the same manner as in Example 10.

Comparative Example 1. Preparation of Fine Pigments

Phthalocyanine-based green pigment (CI Number Pigment green 7 [PG7]: 35 parts by weight of Heubach, trade name HEUCO Green 600736, Specific Surface [m2 / g]), 210 parts by weight of sodium chloride as a water-soluble inorganic salt, diethylene as a water-soluble organic solvent 70 parts by weight of glycol, 0.4 parts by weight of an acrylic resin solution having a weight average molecular weight (Mw) of 28,000, and 1.0 part by weight of a dispersant (BYK-chemie, Disperbyk-2001) were added to a trimix, and the rotation speed was set to 19 rpm by revolution. And mechanically kneaded for 8 hours at 57 rpm and 40 ° C by rotation.

The kneaded product thus obtained was introduced into about 5 L of water, stirred for about 1 hour in a high speed mixer, filtered and washed with water to remove sodium chloride and an organic solvent, and dried to obtain a fine pigment having an average particle size of 45 nm. .

Comparative Example 2. Preparation of Pigment Dispersion Composition

The same procedure as in Example 5 was carried out except that the fine pigment having an average particle size of 45 nm prepared in Comparative Example 1 was used.

Comparative Example 3. Preparation of Photosensitive Resin Composition for Color Filter

Except that the pigment dispersion composition prepared in Comparative Example 2 was used in the same manner as in Example 10.

Experimental Example 1. Contrast Measurement

The pigment dispersion compositions prepared in Examples 5 to 9 and Comparative Example 2 were respectively mixed with the same amount of acrylic resin and sufficiently stirred to obtain a resin mixture. It was sprayed with a spin coater and dried in an oven at 100 ° C. for 3 minutes to form a coating film. Contrast was measured by using a contrast test meter (CT-1 / tsubosaka) on each film formed. And luminance values were measured using a spectrophotometer (TFCA-700 / Lamda vision). The results are shown in Table 1 below.

division Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Contrast 6789 3780 6850 5321 4120

As shown in Table 1, the pigment dispersion composition of Examples 5 to 8 comprising a micropigment prepared using a sulfonated quinophthalone-based dispersant according to the present invention has superior contrast characteristics compared to Comparative Example 1. Could confirm.

Experimental Example 2. Luminance Measurement

The pigment dispersion composition prepared in Examples 6 to 10 and Comparative Example 2 was spin-coated at each rotational speed (300 rpm, 500 rpm, 700 rpm) on a 10 cm × 10 cm glass for luminance measurement, and then free on a hot plate at 100 ° C. After baking, ultraviolet light was exposed to 100 mJ / cm 2 using an exposure machine, heat-treated at 220 ° C. for 20 minutes, and then color characteristics were measured using a spectrophotometer (TFCA-700 / Lamda vision). The results are shown in Table 2 below.

division Example 5 Example 6 Example 7 Example 8 Comparative Example 1 x 0.202 0.6 0.503 0.259 0.201 y 0.356 0.318 0.49 0.523 0.356 Y 56.0 23.8 70.2 49.5 55.2

As shown in Table 2, the pigment dispersion composition of Examples 5 to 8 including the micropigment prepared using the sulfonated quinophthalone-based dispersant according to the present invention has excellent luminance as compared to Comparative Example 1. I could confirm it.

Although the present invention has been described in terms of the preferred embodiments mentioned above, it is possible to make various modifications and variations without departing from the spirit and scope of the invention. It is also to be understood that the appended claims are intended to cover such modifications and changes as fall within the scope of the invention.

Claims

Preparing a kneading composition by kneading a pigment, a water-soluble inorganic salt, a water-soluble organic solvent, a resin, and a sulfonated quinophthalone-based dispersant; And
Removing the water-soluble inorganic salt and the water-soluble organic solvent from the kneading composition;
Method for producing a fine pigment, characterized in that it comprises a.

The method of claim 1,
The kneading composition includes 600 to 1,000 parts by weight of a water-soluble inorganic salt, 250 to 500 parts by weight of a water-soluble organic solvent, 1 to 5 parts by weight of a water-soluble resin, and 1 to 7 parts by weight of a sulfonated quinophthalone-based dispersant based on 100 parts by weight of a pigment. Method for producing a fine pigment, characterized in that.

The method of claim 1,
The sulfonated quinophthalone-based dispersant is a method for producing a fine pigment, characterized in that the sulfur content is up to 5 mol%.

The method of claim 1,
The pigment is a method for producing a fine pigment, characterized in that the inorganic pigment or organic pigment having an average particle size of up to 100nm.

The method of claim 1,
The water-soluble inorganic salt is a method of producing a fine pigment, characterized in that any one or more selected from sodium chloride, barium chloride, potassium chloride, sodium sulfate, zinc chloride, calcium chloride and magnesium chloride.

The method of claim 1,
The water-soluble organic solvent is 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, glycerin, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, di Propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, low molecular weight polypropylene glycol, aniline, pyridine, dioxane, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, propylene glycol, propylene glycol monomethyl ether Any one selected from acetate, ethyl acetate, isopropyl acetate, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone The manufacturing method of the fine pigment characterized by the above.

The method of claim 1,
The resin has an acryl main chain, and has at least one functional group selected from hydroxyl, amide, carbamoyl and urea groups in the side chain, and has a weight average molecular weight of 1,000 to 100,000.

The method of claim 1,
The average particle size of the fine pigment is a method for producing a fine pigment, characterized in that up to 50nm.

A pigment dispersion composition comprising an acrylic binder, a fine pigment, a dispersant and a solvent prepared by the method of claim 1.

The method of claim 10,
The pigment dispersion composition is characterized in that it comprises 0.1 to 40% by weight acrylic binder, 1 to 20% by weight fine pigment prepared by the method of claim 1, 0.1 to 40% by weight dispersant and 10 to 80% by weight solvent. Pigment dispersion composition.

The method of claim 10,
The acrylic binder has a number average molecular weight of 10,000 to 50,000, the acid value is 50 ~ 150mg / KOH when the solubility in alkali developer in mind.

The color filter photosensitive resin composition containing the pigment dispersion liquid composition of Claim 10.

A color filter manufactured from the color filter photosensitive resin composition according to claim 13.