KR101620843B1 - pigment additives, their preparation and compositions containing the same - Google Patents

Abstract

The present invention relates to a novel pigment additive, a process for producing the same, and a pigment dispersion composition containing the same, wherein the pigment dispersion composition of the present invention contains the pigment additive of the present invention and has excellent optical properties, dispersibility and dispersion stability.

Description

TECHNICAL FIELD The present invention relates to a novel pigment additive, a process for producing the same, and a pigment dispersion composition containing the pigment additive,

The present invention relates to a novel pigment additive, a process for producing the same, and a pigment dispersion composition containing the same, and more particularly, to a pigment additive having an azo group on both diphenylenes, a process for producing the same, and a pigment dispersion composition containing the same .

The color filter used in the production of liquid crystal color display and image pickup device is made by applying a pigment dispersion composition for a color filter in which three colors of red (R), green (G), and blue (B) To form a colored film, and the colored film is exposed and developed by using a photomask to form a desired colored film by patterning the colored film.

 Properties required for a pigment dispersion composition for a color filter are required to have excellent optical properties such as high luminance, coloring power and high contrast ratio, dispersibility, and storage stability. In order to prepare a pigment dispersion composition for satisfying such characteristics, fine pigment particles of 100 nm or less must be dispersed with a uniform distribution.

 As a conventional technique for obtaining a fine pigment suitable for a pigment dispersion composition for a color filter, there is a salt milling method in which pigment particles are finely dispersed using salt, and a fine pigment having a desired particle size and distribution is obtained by using this method To improve optical properties such as high luminance, tinting strength and high contrast ratio.

However, if the pigment becomes finer, the coagulation power of the pigment particle itself becomes strong, and the dispersibility and dispersion stability of the pigment become poor, which is problematic. To solve this problem, a technique using a dispersing agent or the like is known, but it is still insufficient to obtain the properties required in the above applications.

 Therefore, it is required to develop an additive for a pigment dispersion composition that not only satisfies optical properties such as high luminance, tinting strength and high contrast ratio but also satisfies high dispersibility and dispersion stability.

Japanese Unexamined Patent Publication 2001-220520 Japanese Unexamined Patent Publication 2001-264528

The present invention provides a pigment additive capable of enhancing optical properties, dispersibility, and dispersion stability of a pigment dispersion composition and a method for producing the same.

The present invention also provides a pigment dispersion composition comprising the pigment additive of the present invention.

The present invention also provides a color resist composition comprising the pigment dispersion composition of the present invention and a color filter manufactured using the same.

The present invention provides a novel pigment additive for producing a pigment dispersion composition having high brightness and high contrast ratio and excellent dispersibility and dispersion stability.

The pigment additive of the present invention is represented by the following general formula (1).

[Chemical Formula 1]

[In the above formula (1)

,

,

또는

이며, A is

,

,

or

Lt;

R ₁ is hydrogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C1-C30) alkoxy, (C6-C30) aryl, (C6-C30) ar ( (C1-C30) alkyl, (C3-C30) heteroaryl, (C6-C30) aryloxy, (C6-C30) arylamino, di (C6-C30) arylamino, (C1-C30) alkylcarbonyl, carboxylic acid group, sulfonyl, halogen, amino, cyano or nitro,

o is an integer from 1 to 3,

p is an integer of 1 to 2;

M is Na, H, K, or Li;

B is selected from the group consisting of hydrogen, amino, (C 1 -C 30) alkyl, (C 1 -C 30) alkoxy, (C 6 -C 30) aryl, mono (C 1 -C 30) alkylamino, ) Arylamino or di (C6-C30) arylamino;

Wherein R ₁ is selected from the group consisting of alkyl, cycloalkyl, heterocycloalkyl, alkoxy, aryl, aralkyl, heteroaryl, aryloxy, alkyloxy, monoalkylamino, dialkylamino, monoarylamino, diarylamino and alkylcarbonyl and B (C1-C30) alkyl, (C6-C30) alkyl, alkoxy, aryl, monoalkylamino, dialkylamino, monoarylamino, and diarylamino groups are optionally substituted with one or more substituents selected from the group consisting of halogen, carboxylic acid group, sulfonyl, cyano, nitro, C30) aryl, (C3-C30) heteroaryl, and the like.

The pigment additive of the present invention has azo groups on both sides of biphenylene substituted with a sulfonic acid group or sulfonate group as a diazo compound and can have excellent brightness and contrast ratio and has sulfonic acid group or sulfonate group substituted in biphenylene group, To improve dispersibility and dispersion stability of the pigment dispersion composition.

In addition, it is possible to control various physical properties such as solubility and dispersibility as well as optical properties of the pigment dispersion composition by converting various substituents on both azo groups, specifically, A and B in the above formula (1) into various substituents.

In a preferred embodiment of the present invention, R ₁ in the formula ( ₁₎ is independently selected from the group consisting of (C ₁ -C 30) alkyl, (C 6 -C 30) (C6-C30) aryl, (C6-C30) aryl (C1-C30) alkyl, mono Arylamino, (C1-C30) alkylcarbonyl, carboxylic acid group, sulfonyl, halogen, cyano, amino or nitro;

Alkyl of said R _1, aryl, aralkyl, monoalkylamino, dialkylamino, mono-arylamino and diarylamino ahminoeun halogen, carboxylic acid group, a sulfonyl, cyano, nitro, hydroxy, (C1-C30) alkyl, (C6-C30) aryl, (C3-C30) heteroaryl, and the like.

More preferably, Formula 1 according to an embodiment of the present invention may be represented by Formula 2 or Formula 3 below.

(2)

(3)

[In the above formulas (2) and (3)

R ₁₁ to R ₁₂ and R ₁₅ are independently of each other hydrogen, (C 1 -C 30) alkyl, (C 6 -C 30) aryl or (C 6 -C 30) aryl (C 1 -C 30) alkyl;

R ₁₃ and R ₁₄ are, independently of each other, hydrogen, (C 1 -C 30) alkyl or a carboxylic acid group;

The alkyl, aryl and aralkyl of R ₁₁ to R ₁₂ and R ₁₅ and the alkyl of R ₁₃ and R ₁₄ are independently selected from the group consisting of halogen, carboxylic acid group, sulfonyl, cyano, nitro, hydroxy, (C 1 -C 30) C6-C30) aryl, (C3-C30) heteroaryl, and the like.

The pigment additive of the present invention represented by the above general formula (2) or (3) has a nitrogen atom or an amino group contained in the ring and can increase the solubility and dispersibility as well as the optical properties of the pigment dispersion composition containing the nitrogen atom or amino group.

Specifically, the pigment additive according to one embodiment of the present invention may be selected from the following compounds, but is not limited thereto.

The substituents including the "alkyl", "alkoxy" and other "alkyl" moieties described in the present invention described in the present invention include both linear and branched forms.

The term " aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and may be a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, A ring system, and a form in which a plurality of aryls are connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like.

"Heteroaryl" in the present invention includes 1 to 4 heteroatoms selected from B, N, O, S, P (= O), Si and P as aromatic ring skeletal atoms and the remaining aromatic ring skeletal atoms are carbon Means a 5 to 6 membered monocyclic heteroaryl and a polycyclic heteroaryl condensed with at least one benzene ring and may be partially saturated. The heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected to a single bond.

&Quot; Cycloalkyl ", alone or as part of another group described in the present invention, refers to a fully saturated and partially unsaturated hydrocarbon ring of 3 to 9 carbon atoms, inclusive of the fused aryl or heteroaryl do.

"Heterocycloalkyl" in the present invention means a fully saturated and partially unsaturated hydrocarbon ring containing oxygen, sulfur or nitrogen as a heteroatom in the ring, the number of heteroatoms being 1-4, preferably 1 -2. Cycloalkyl in heterocycloalkyl is preferably monocycloalkyl or bicycloalkyl, including those in which an aromatic cyclic aryl or heteroaryl is fused and also includes a double bond or a triple bond.

The present invention also provides a process for preparing the pigment additive of the present invention.

The method for preparing a pigment additive according to the present invention comprises the steps of: reacting a compound represented by the formula (4) with sodium nitrite in the presence of an acid to form a diazonium salt represented by the following formula (4); And

Reacting a diazonium salt of the following formula (4) with a compound of the following formula (5) to prepare a pigment additive represented by the formula (1).

[Chemical Formula 4]

[Chemical Formula 5]

[In the formulas (4) to (5)

,

,

또는

이며, A is

,

,

or

Lt;

R ₁ is hydrogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C1-C30) alkoxy, (C6-C30) aryl, (C6-C30) ar ( (C1-C30) alkyl, (C3-C30) heteroaryl, (C6-C30) aryloxy, (C6-C30) arylamino, di (C6-C30) arylamino, (C1-C30) alkylcarbonyl, carboxylic acid group, sulfonyl, halogen, amino, cyano or nitro,

o is an integer from 1 to 3,

p is an integer of 1 to 2;

M is Na, H, K, or Li;

B is selected from the group consisting of hydrogen, amino, (C 1 -C 30) alkyl, (C 1 -C 30) alkoxy, (C 6 -C 30) aryl, mono (C 1 -C 30) alkylamino, ) Arylamino or di (C6-C30) arylamino;

Wherein R ₁ is selected from the group consisting of alkyl, cycloalkyl, heterocycloalkyl, alkoxy, aryl, aralkyl, heteroaryl, aryloxy, alkyloxy, monoalkylamino, dialkylamino, monoarylamino, diarylamino and alkylcarbonyl and B (C1-C30) alkyl, (C6-C30) alkyl, alkoxy, aryl, monoalkylamino, dialkylamino, monoarylamino, and diarylamino groups are optionally substituted with one or more substituents selected from the group consisting of halogen, carboxylic acid group, sulfonyl, cyano, nitro, C30) aryl, (C3-C30) heteroaryl, and the like.

The acid according to an embodiment of the present invention may be hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, or a mixed acid thereof, and may be hydrochloric acid in view of reaction efficiency.

It is needless to say that the above-mentioned chemical formulas (4) and (5) according to one embodiment of the present invention can be synthesized as a reaction used in the field of organic synthesis or can be purchased commercially.

The solvent used in the production method of the present invention may be an organic solvent, water or a mixture thereof. Any organic solvent may be used, but ethyl acetate (EA), dichloromethane (DCM), dichloroethane (DCE) , toluene (toluene), acetonitrile (MeCN), nitro methane (Nitromethan), tetrahydrofuran (THF), N, N - dimethylformamide (DMF) and N, N - dimethylacetamide (DMA) Is preferably used.

Although the reaction temperature of the present invention can be used at a temperature used in conventional organic synthesis, it can be varied depending on the amount of the reaction material and the starting material, and it is confirmed through the TLC or the like that the starting material is completely consumed, . When the reaction is completed, it can be separated and purified by a method commonly used in organic synthesis. For example, after the extraction process, the solvent may be distilled off under reduced pressure, and the target product may be separated and purified through a conventional method such as column chromatography.

The present invention also provides a pigment dispersion composition comprising the novel pigment additive of the present invention.

The pigment dispersion composition of the present invention is excellent in optical properties such as brightness and contrast ratio, as well as excellent dispersibility and stability, including the pigment additive of the present invention.

The pigment dispersion composition according to an embodiment of the present invention may include the pigment additive and the organic pigment of the present invention, and the blending ratio of 0.1 to 30 parts by weight is preferable for 100 parts by weight of the organic pigment, 20 parts by mass is preferable. If the compounding ratio of the pigment additive is too small, it is difficult to obtain a desired effect sufficiently, and if the compounding ratio is too large, the effect proportional thereto can not be obtained and the physical properties of the pigment dispersing composition and the coloring composition using the pigment are deteriorated Which causes the original color to largely change.

The organic pigments contained in the pigment dispersion composition of the present invention are not particularly limited, and examples thereof include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene / perinone pigments, isoindolinone pigments pigments, isoindoline pigments, dioxazine pigments, quinophthalone pigments, diketopyrrolopyrole pigments, anthraquinone pigments, anthraquinone pigments, , Thioindigo pigments, and metal complex pigments. [0035] The term " pigments "

The pigment dispersion composition of the present invention may be used alone or in combination of red, green, yellow, and purple pigments.

C.I. Pigment Red 7, 14, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 146, 177, 184, 185, 187, 200, 210, 246, 254, 255, 264, 270, and 272 may be used. In the case of the green pigment, CI Pigment Green 7, 10, 36, 37 and the like can be used. In the case of the blue pigment, C.I. Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 80 and the like. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 169, 170, 171, 172, 173, 193, 194, 199, 213 and 214 can be used. In the case of the purple pigment, CI Pigment Violet 23, 34, 35, 37 or the like may be used, and these may be used singly or in combination of two or more kinds.

 Particularly, in the case of the red pigment dispersion composition, the organic pigment is preferably selected from the group consisting of C.I. Pigment Red 122, C.I. Pigment Red 177, C.I. Pigment Red 254 and C.I. Pigment Violet < SEP > 19 < SEP >

 The organic pigments described above are surface-modified with the pigment additive, which means that the pigment additive binds on the surface of an atomized pigment which is pulverized through milling and dispersion processes such as milling, It becomes possible to improve the properties. That is, the pigment additive forms a coating layer on the surface of the organic pigment, which means a continuous or discontinuous coating layer. The dispersion stability, storage stability and color characteristics of the organic pigment can be improved through the pigment additive forming the surface layer.

It is preferable that the residue of the pigment additive and the organic pigment use the same series, but they do not necessarily have to be the same, and it is not always necessary to combine those having the same hue, and it is also possible to use a material exhibiting a different hue . That is, it is also possible to modify the surface of the red pigment with a yellow pigment additive to improve color characteristics, and it is also possible to improve the color purity by using organic pigments and pigment additives having the same color.

The pigment dispersion composition of the present invention may contain a dispersant in addition to the pigment additive of the present invention. The dispersant is not limited to such a dispersant, but it is preferable to use a high molecular weight dispersant.

The high molecular weight dispersant may preferably have a weight average molecular weight in the range of 1,000 to 100,000, and more preferably 10,000 to 30,000 in the high molecular weight dispersant. Examples of such a high molecular weight dispersant include commercially available products such as EFKA4046 (trade name, manufactured by EFKA), PB-821 (manufactured by Ajinomoto Fine Techno), DISPERBIK 160, 161, 162, 163, 164 and 182 , DISPARLON DA-234, 325, 375, 725 (trade name) of Auxia Limited, SOLSPERSE 22000, 24000, 28000 (trade name) , But are not limited thereto.

 The high molecular weight dispersant is not limited, but may be used in an amount of 1 to 30 parts by weight based on 100 parts by weight of the organic pigment. If the content of the dispersant is less than 1 part by weight, a sufficient dispersing effect can not be obtained. If the amount is more than 30 parts by weight, economical efficiency is lowered.

The pigment dispersion composition may further contain a resin. Examples of the thermoplastic resin include petroleum resin, casein, shellac, rosin-modified maleic resin, rosin-modified phenolic resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, chlorinated rubber, oxidized rubber, A vinyl chloride resin, a vinyl chloride-vinyl acetate copolymer, an acrylic resin, a methacrylic resin, a polyurethane resin, a silicone resin, a fluorine resin, a drying oil, a synthetic drying oil, a polyester resin, an unsaturated polyester resin, an amino resin, , A styrene-modified maleic resin, a polyamide resin, a polyimide resin, a benzoguanamine resin, a melamine resin, a urea resin polypropylene chloride, a butyral resin and a vinylidene chloride resin.

 Further, a photosensitive resin may be used as the resin. As the photosensitive resin, for example, a resin having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group by reaction between a (meth) acrylic compound having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group or cinnamic acid, A resin obtained by introducing a photo-crosslinkable group such as a (meth) acryloyl group or a styryl group into a linear polymer; And (meth) acrylic compounds having a hydroxy group such as a hydroxyalkyl (meth) acrylate with a linear polymer containing an acid anhydride such as styrene-maleic anhydride copolymer or? -Olefin-maleic anhydride copolymer, A resin obtained by esterification can be used. Such a resin can be used in an amount of 1 to 30 parts by weight based on 100 parts by weight of the organic pigment.

The organic solvent used in the pigment dispersion composition of the present invention is not particularly limited as long as it can disperse the organic pigment and the like, and is preferably a solvent selected from esters, ketones, ethers, alcohols and hydrocarbons having 3 to 12 carbon atoms . The ester, ketone, ether or alcohol may have a ring structure. Compounds having two or more functional groups (-O-, -CO- and -COO-) such as esters, ketones and ethers can also be used as solvents and other functional groups such as alcoholic hydroxyl groups can be present at the same time. In the case of a solvent having two or more functional groups, a large number of carbon atoms may be present within a defined range for the compound having the functional group.

 Examples of the ester having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate or pentyl acetate. Examples of the ketone having 3 to 12 carbon atoms include acetone, methyl isobutyl ketone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and methylcyclohexanone. Examples of the ether having 3 to 12 carbon atoms include propylene glycol monomethyl ether acetate, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, Anisole and phenetole are examples. Examples of the organic solvent having two or more functional groups include 2-ethoxyhexyl acetate, 2-methoxyethanol and 2-butoxyethanol. The alcohols usable in combination with the chlorinated organic solvent may be linear, branched or cyclic, of which saturated aliphatic hydrocarbons are preferred. The hydroxy group of the alcohol may be monovalent, divalent or trivalent. Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. Examples of the fluorinated alcohols include 2-fluoroethanol, 2,2,2-trifluoroethanol and 2,2,3,3-tetrafluoro-1-propanol. The hydrocarbons may be linear, branched or cyclic, and aromatic hydrocarbons or aliphatic hydrocarbons may be used. Aliphatic hydrocarbons can be used both saturated and unsaturated. Examples of such hydrocarbons include cyclohexane, hexane, benzene, ethylbenzene, toluene and xylene.

 The organic solvent may be used in an amount such that the organic pigment particles can be dispersed in the pigment dispersion composition. The organic solvent may be used in an amount of 100 to 1,000 parts by weight based on 100 parts by weight of the organic pigment. If the content of the organic solvent is less than 100 parts by weight, sufficient pigment dispersion can not be obtained, viscosity becomes high and workability is lowered, and when the amount is more than 1,000 parts by weight, the pigment concentration is too low, have.

The pigment dispersion composition of the present invention may contain conventional auxiliary agents or additives such as surfactants, fillers, standardizers, antifoaming agents, anti-dust agents, enhancing agents, antistatic agents, preservatives, drying retarders, wetting agents, antioxidants, In an amount of 0.01 to 10% by weight, especially 0.5 to 5% by weight, based on the total weight of the pigment dispersion composition.

On the other hand, in order to prepare the pigment dispersion composition, it is preferable that the organic pigment has a primary particle diameter of 100 nm or less, or an organic pigment having a primary particle diameter of 100 nm or less by the atomization treatment, And from the viewpoint of improvement of sharpness. Examples of the atomization treatment method of the organic pigment include a salt-milling method in which milling is carried out in the presence of a common salt (see, for example, JP-A-2001-220520 and JP-A-2001-264528 ), But the present invention is not limited thereto.

 The pigment dispersion composition according to one embodiment of the present invention can be produced by mixing the organic pigment and the pigment additive respectively by a conventionally known method (for example, Japanese Patent Application Laid-Open Nos. 2001-271004 and 2004-91497) have. For example, a method of mixing the organic pigment and the pigment additive powder, a method of mixing suspensions between the organic pigment and the pigment additive dispersed in water or a dissolvable organic solvent, And a method of adding the pigment additive to the process of the present invention. However, the production method is not particularly limited. Examples of the optional step in the organic pigment production process include, but are not limited to, salt milling. The state when the pigment additive is added may be in the form of powders, pastes or suspensions, but is not limited thereto.

 For example, the pigment dispersion composition of the present invention can be prepared by a wet dispersion stabilization process in which an organic pigment powder is wetted while mixing the components with an appropriate amount of the above components, and the organic pigment in the thus- And have an average particle size of 20 to 150 nm. In order to maximize the physical impact force in consideration of the efficiency of pigment dispersion, beads having a diameter of 0.05 to 2.0 mm may be used. Such beads may be glass, stainless steel, zirconium or the like.

 Examples of the dispersing machine used in the stirring step include a bead mill, a roll mill, an attritor, a super mill, a dissolver, a homomixer, a sand mill, a 3-roll mill, a disc mill, a paint shaker and a scandel. Bead mill is the most used.

 The present invention also provides a color resist composition comprising the pigment dispersion composition of the present invention.

The present invention also provides a color filter manufactured using the color resist composition of the present invention.

In detail, the pigment dispersion composition of the present invention can be used as a coating material, a printing ink, or the like, and can be applied as a color resist composition which can be mixed with a photosensitive film forming material and form an image by light irradiation. When a pixel is formed by a known method and structure using a color resist composition including the pigment dispersion composition of the present invention, a color filter having excellent characteristics is obtained. The color resist composition is obtained by mixing the pigment-dispersed composition of the present invention and the photosensitive film-forming material in a highly dispersed state. The photosensitive film-forming material is not particularly limited. In general, a photosensitive resin varnish such as a photosensitive polyacrylate resin, a photosensitive acrylic resin, a photosensitive polyamide resin, a photosensitive polyimide resin or a photosensitive unsaturated polyester resin, or a monomer or oligomer is further added as such a resin reaction diluent A varnish, a photoinitiator (if necessary, together with a sensitizer), and a solvent. By using the pigment dispersion composition of the present invention, it is possible to obtain a color resist composition and a color filter for color filter pixel formation which are excellent in dispersibility, dispersion stability, transparency and clarity.

 Examples of the monomer or oligomer include (meth) acrylic acid ester, (meth) acrylic acid, (meth) acrylamide, vinyl acetate, styrene, (meth) acrylonitrile, , But are not limited thereto. Examples of the photoinitiator include, but are not limited to, acetophenone, benzoin, benzophenone, thioxanthone, triazine, carbazole, and imidazole. Examples of the sensitizer include acylphosphine oxide, methylphen ylglyoxylate, quinone-based, anthraquinone-based, isophthaloyl-isophthaloquinone, phenone-based, ester-based, benzyl-based, benzophenone-based, and the like. Examples of the solvent include (poly) alkylene glycol monoalkyl ether, (poly) alkylene glycol monoalkyl ether acetate, ether, ketone, fatty acid alkyl ester, other esters, aromatic hydrocarbons and amides. But are not limited thereto.

The pigment additive of the present invention has high brightness and contrast ratio and thus improves the optical properties of the pigment dispersion composition containing it.

The pigment additive of the present invention is contained in a pigment dispersion composition to inhibit the aggregation of fine organic pigments, thereby enhancing dispersion stability of the pigment dispersion composition as well as dispersion stability.

As described above, the pigment dispersion composition of the present invention includes the novel pigment additive of the present invention and has very high dispersibility and dispersion stability as well as optical properties.

The color resist composition of the present invention also includes a pigment dispersion composition of the present invention having high dispersibility and high dispersion stability, so that a color filter of good quality can be produced.

Hereinafter, concrete examples of the pigment additive, a synthesis method and the like will be described through specific examples. The following description is only an example of the present invention, and thus the present invention is not limited to the structure or the description.

[Example 1] Production of Pigment Additive A

Synthesis of intermediate (2,6-bis (mesitylamino) -4-methylpyridine-3-carbonitrile)

(16.04 mmol) of 2,6-dichloro-4-methylnicotinon itrile and 1530 mg of zinc oxide were added to 9.0 ml (64.16 mmol) of 2,4,6-trimethyaniline and 0.8 ml of NMP, It has warmed up. And the mixture was heated and stirred at 180 캜 for 4 hours while removing water produced during the reaction. Thereafter, the solution was cooled to 80 DEG C, and the reaction solution was added dropwise to 1000 ml of water over 30 minutes, cooled to room temperature, and then filtered. The obtained crystals were washed and dried to obtain 4.2 g (yield: 68%) of the aimed compound.

Preparation of pigment additive A

2,2'-Benzidinedisulfonic acid 1g (2.9 mmol), 1ml의 진한 염산, 및 3ml의 물의 혼합물을 5℃인 내부 온도에서 교반시킨 후 여기에 0.4g (5.8 mmol)의 Sodium nitrite를 분획하여 5분에 걸쳐 첨가하였다, 첨가 후 30분 동안 교반을 계속하여 디아조늄 염을 형성하였다.

After stirring a mixture of 1 g (2.9 mmol) of 2,2'-benzidinedisulfonic acid, 1 ml of concentrated hydrochloric acid, and 3 ml of water at an internal temperature of 5 ° C., 0.4 g (5.8 mmol) of sodium nitrite was added thereto, Stirring was continued for 30 minutes after addition to form the diazonium salt.

 Separately, 2.1 g (5.5 mmol) of 2,6-bis (mesitylamino) -4-methylnicotinonitrile was added to a three-necked flask and 5.9 g (72.59 mmol) of sodium acetate, 5 ml of DMF and 5 ml of EA were added. The mixture was stirred and cooled to an internal temperature of 5 < 0 > C. The diazonium salt was added thereto over 10 minutes, and stirring was continued for an additional 1 hour. 50 ml of a saturated aqueous sodium chloride solution was added to the reaction mixture. The precipitate thus formed was collected by filtration by suction to obtain 2.5g (yield 75%) of pigment additive A.

ESI-MS: MW 1179.33, m / z 1178.40

[Example 2] Production of Pigment Additive B

Preparation of intermediate

(16.04 mmol) of 2,6-dichloro-4-methylnicotinonitrile and 1530 mg of zinc oxide were added to 13.2 ml (80.2 mmol) of 2,6-diethylaniline and 0.8 ml of NMP, and the temperature was raised to 180 ° C in an oil bath. The resulting mixture was heated and stirred at 180 캜 for 4 hours while removing water produced during the reaction. Thereafter, the reaction mixture was cooled to 80 deg. C, 1000 ml of water was added dropwise to the reaction mixture over 30 minutes, cooled to room temperature and filtered. The obtained crystals were washed and dried to obtain 4.0 g (yield: 60%) of the aimed compound.

Preparation of pigment additive B

 A mixture of 1 g (2.9 mmol) of 2,2'-benzidinedisulfonic acid, 1 ml of concentrated hydrochloric acid and 3 ml of water was stirred at an internal temperature of 5 ° C and 0.4 g (5.8 mmol) of sodium nitrite was added and added over 5 minutes The stirring was continued for 30 minutes after the addition to form a diazonium salt.

Separately, 2.2 g (5.5 mmol) of 2,6-bis ((2,6-diethylphenyl) amino) -4-methylnicotinonitrile was added to a three-necked flask and 5.9 g (72.59 mmol) of sodium acetate, 5 ml of DMF and 5 ml of EA . The mixture was stirred and cooled to an internal temperature of 5 < 0 > C. The diazonium salt was added to the reaction mixture over 10 minutes and stirring was continued for an additional 1 hour. 50 ml of a saturated aqueous sodium chloride solution was added to the reaction mixture and the precipitate formed was collected by filtration by suction to obtain 2.4 g (69% yield) of pigment additive B.

ESI-MS: MW 1235.43, m / z 1234.46

[Example 3] Production of Pigment Additive C

Preparation of intermediate

(16.04 mmol) of 2,6-dichloro-4-methyl nicotinonitrile and 1530 mg of zinc oxide were added to 11.4 ml (80.2 mmol) of 2-ethylhexan-1-amine and 0.8 ml of NMP, It has warmed up. And the mixture was stirred at 180 캜 for 4 hours while removing water produced during the reaction. Thereafter, the reaction mixture was cooled to 80 deg. C, and 1000 ml of water was added dropwise to the reaction mixture over 30 minutes, cooled to room temperature, and then filtered. The obtained crystals were washed and dried to obtain 4.1 g (yield: 62%) of the aimed compound.

Preparation of pigment additive C

2,2'-Benzidinedisulfonic acid 1g (2.9 mmol), 1ml의 진한 염산, 및 3ml의 물의 혼합물을 5℃의 내부 온도에서 교반하고, 0.4g (5.8 mmol)의 Sodium nitrite를 분획하여 5분에 걸쳐 첨가하였다, 첨가 후 30분 동안 교반을 계속하여 디아조늄 염을 형성하였다.

A mixture of 1 g (2.9 mmol) of 2,2'-benzidinedisulfonic acid, 1 ml of concentrated hydrochloric acid and 3 ml of water was stirred at an internal temperature of 5 ° C and 0.4 g (5.8 mmol) of sodium nitrite was added and added over 5 minutes The stirring was continued for 30 minutes after the addition to form a diazonium salt.

 Separately, 2.0 g (5.5 mmol) of 2,6-bis (hexylamino) -4-methylnicotinonitrile was placed in a three-necked flask, 5.9 g (72.59 mmol) of sodium acetate, 5 ml of DMF and 5 ml of EA were added, And cooled to an internal temperature. The diazonium salt prepared above was added thereto over 10 minutes, and stirring was further continued for 1 hour. 50 ml of a saturated aqueous sodium chloride solution was added to the reaction mixture, and the formed precipitate was collected by filtration by suction to obtain 2.4 g (yield 72%).

ESI-MS: MW 1155.47, m / z 1154.59

[Example 4] Synthesis of pigment additive D

2,2'-Benzidinedisulfonic acid 1g (2.9 mmol), 1ml의 진한 염산, 및 3ml의 물의 혼합물을 5℃의 내부 온도에서 교반하고, 0.4g (5.8 mmol)의 Sodium nitrite를 분획하여 5분에 걸쳐 첨가하였다, 첨가 후 30분 동안 교반을 계속 하여 디아조늄 염을 형성하였다.

A mixture of 1 g (2.9 mmol) of 2,2'-benzidinedisulfonic acid, 1 ml of concentrated hydrochloric acid and 3 ml of water was stirred at an internal temperature of 5 ° C and 0.4 g (5.8 mmol) of sodium nitrite was added and added over 5 minutes The stirring was continued for 30 minutes after the addition to form a diazonium salt.

 Separately, 1.4 g (5.5 mmol) of 4- (3-methyl-5-oxo-4,5-dihydro-1H- pyrazol-1-yl) benzenesulfonic acid was placed in a three- 5 ml of DMF and 5 ml of EA were added and stirred and cooled to an internal temperature of 5 캜. The diazonium salt prepared above was added thereto over 10 minutes, and stirring was further continued for 1 hour. 50 ml of a saturated sodium chloride aqueous solution was added to the reaction mixture, and the precipitate formed was collected by filtration by suction to obtain 1.7 g (67% yield) of pigment additive D.

ESI-MS: MW 918.82, m / z 918.01

[Example 5] Synthesis of pigment additive E

2,2'-Benzidinedisulfonic acid 1g (2.9 mmol), 1ml의 진한 염산, 및 3ml의 물의 혼합물을 5℃의 내부 온도에서 교반하고, 0.4g (5.8 mmol)의 Sodium nitrite를 분획하여 5분에 걸쳐 첨가하였다, 첨가 후 30분 동안 교반을 계속 하여 디아조늄 염을 형성하였다.

A mixture of 1 g (2.9 mmol) of 2,2'-benzidinedisulfonic acid, 1 ml of concentrated hydrochloric acid and 3 ml of water was stirred at an internal temperature of 5 ° C and 0.4 g (5.8 mmol) of sodium nitrite was added and added over 5 minutes The stirring was continued for 30 minutes after the addition to form a diazonium salt.

 Separately, 1.4 g (5.5 mmol) of 5-oxo-1- (4-sulfophenyl) -4,5-dihydro-1H-pyrazole-3-carboxylic acid was placed in a three-necked flask and 5.9 g (72.59 mmol) Of DMF and 5 ml of EA were added and stirred and cooled to an internal temperature of 5 < 0 > C. The diazonium salt prepared above was added over 10 minutes and stirring was continued for a further 1 hour. 50 ml of saturated sodium chloride aqueous solution was added to the reaction mixture, and the precipitate formed was collected by filtration by suction to obtain 1.9 g (70% yield) of pigment additive E.

ESI-MS: MW 978.78, m / z 977.96

[Example 6] Production of pigment additive F

A mixture of 1 g (2.9 mmol) of 2,2'-benzidinedisulfonic acid, 1 ml of concentrated hydrochloric acid and 3 ml of water was stirred at an internal temperature of 5 ° C and 0.4 g (5.8 mmol) of sodium nitrite was added and added over 5 minutes The stirring was continued for 30 minutes after the addition to form a diazonium salt.

 Separately, 0.9 g (5.5 mmol) of 3-methyl-1-phenyl-1H-pyrazol-5 (4H) -one was placed in a three-necked flask and 5.9 g (72.59 mmol) of sodium acetate, 5 ml of DMF and 5 ml of EA Respectively. The mixture was stirred and cooled to an internal temperature of 5 < 0 > C. The diazonium salt prepared above was added thereto over 10 minutes, and stirring was further continued for 1 hour. 50 ml of a saturated aqueous sodium chloride solution was added to the reaction mixture, and the precipitate formed was collected by filtration by suction to obtain 1.4 g of pigment additive F (67% yield).

ESI-MS: MW 758.69, m / z 758.109

[Examples 7 to 12 and Comparative Example 1] Preparation of pigment dispersion composition

 The pigment and the pigment additive were mixed at the composition ratios shown in Table 1 below, and 100 g of 0.5 mm zirconia was added and dispersed in a paint shaker for 5 hours to obtain a pigment dispersion composition.

The evaluation of each composition was carried out as described below using the patterns formed from the pigment dispersion compositions of Examples 6 to 12 and Comparative Example 1 thus prepared.

The results of the evaluation are shown in Table 2 below.

Items not specifically described in the following evaluation method or standard are in accordance with the evaluation standard or ordinary method commonly used in this technical field.

(1) Contrast

The pigment-dispersed compositions of Examples 6 to 12 and Comparative Example 1 were spin-coated on a glass substrate of 60 mm X 60 mm size having a plate thickness of 0.5 mm so that x = 0.650 after curing (C light source) 100 seconds dry after ultra-high pressure mercury lamp used, the accumulated light quantity 60mJ / cm ² ultraviolet ray was carried out exposing the coated glass substrate 230 ℃ after heating 90 minutes the luminance meter CT-1 (sseubo saccharose) and the polarizing plates on each dry coating film The contrast value was calculated as the ratio of the luminance in the case of parallelism to the luminance in the case of orthogonalization.

(2) Brightness

 As a luminance meter, RY was measured at x = 0.650 (C light source) using a color luminance meter MCPD 3000 (Otsuka). The x and y coordinates of each component of RGB on the display are represented by a point, where x is the size of the red component in the chromaticity diagram and RY is the brightness of the red component (y is the size of the green component, GY is the size of the green component Brightness, z is the size of the blue component, and BY is the brightness of the blue component).

As shown in Table 2, the pigment dispersion composition according to the present invention has low viscosity as compared with the comparative example and shows little dispersion of viscosity with time, showing excellent dispersion stability. .

Claims (11)

A pigment additive represented by the following formula (1):
[Chemical Formula 1]

[In the above formula (1)
A is

or

Lt;
R ₁ is hydrogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C1-C30) alkoxy, (C6-C30) aryl, (C6-C30) ar ( (C1-C30) alkyl, (C3-C30) heteroaryl, (C6-C30) aryloxy, (C6-C30) arylamino, di (C6-C30) arylamino, (C1-C30) alkylcarbonyl, carboxylic acid group, sulfonyl, halogen, amino, cyano or nitro,
o is an integer from 1 to 3,
p is an integer of 1 to 2;
M is Na, H, K, or Li;
B is selected from the group consisting of hydrogen, amino, (C 1 -C 30) alkyl, (C 1 -C 30) alkoxy, (C 6 -C 30) aryl, mono (C 1 -C 30) alkylamino, ) Arylamino or di (C6-C30) arylamino;
Wherein R ₁ is selected from the group consisting of alkyl, cycloalkyl, heterocycloalkyl, alkoxy, aryl, aralkyl, heteroaryl, aryloxy, alkyloxy, monoalkylamino, dialkylamino, monoarylamino, diarylamino and alkylcarbonyl and B (C1-C30) alkyl, (C6-C30) alkyl, alkoxy, aryl, monoalkylamino, dialkylamino, monoarylamino, and diarylamino groups are optionally substituted with one or more substituents selected from the group consisting of halogen, carboxylic acid group, sulfonyl, cyano, nitro, C30) aryl, (C3-C30) heteroaryl, and the like. The method according to claim 1,
Wherein R ₁ is independently selected from the group consisting of (C ₁ -C 30) alkyl, (C 6 -C 30) aryl, (C 6 -C 30) aryl (C 1 -C 30) alkyl, C30) alkylamino, mono (C6-C30) arylamino, di (C6-C30) arylamino, (C1-C30) alkylcarbonyl, carboxylic acid group, sulfonyl, halogen, cyano, amino or nitro;
Wherein said alkyl, aryl, aralkyl, monoalkylamino, dialkylamino, monoarylamino and diarylamino of said R ₁ are independently selected from the group consisting of halogen, carboxylic acid group, sulfonyl, cyano, nitro, hydroxy, (C 1 -C 30) , (C6-C30) aryl, and (C3-C30) heteroaryl. The method according to claim 1,
Wherein the formula (1) is represented by the following formula (2).
(2)

[In the formula (2)
R ₁₁ to R ₁₂ are independently of each other hydrogen, (C 1 -C 30) alkyl, (C 6 -C 30) aryl or (C 6 -C 30) aryl (C 1 -C 30) alkyl;
R ₁₃ is independently from each other hydrogen, (C 1 -C 30) alkyl or a carboxylic acid group;
The alkyl, aryl and aralkyl of R ₁₁ to R ₁₂ and the alkyl of R ₁₃ are independently selected from the group consisting of halogen, carboxylic acid group, sulfonyl, cyano, nitro, hydroxy, (C 1 -C 30) alkyl, (C 6 -C 30) (C3-C30) heteroaryl. ≪ / RTI > The method according to claim 1,
Wherein the formula (1) is selected from the following compounds.

(4) with sodium nitrite in the presence of an acid to form a diazonium salt of the following formula
Reacting a diazonium salt of the following formula (4) with a compound of the following formula (5) to prepare a pigment additive represented by the following formula (1).
[Chemical Formula 1]

[Chemical Formula 4]

[Chemical Formula 5]

[In the formulas (1) and (4) to (5)
A is

or

Lt;
R ₁ is hydrogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C1-C30) alkoxy, (C6-C30) aryl, (C6-C30) ar ( (C1-C30) alkyl, (C3-C30) heteroaryl, (C6-C30) aryloxy, (C6-C30) arylamino, di (C6-C30) arylamino, (C1-C30) alkylcarbonyl, carboxylic acid group, sulfonyl, halogen, amino, cyano or nitro,
o is an integer from 1 to 3,
p is an integer of 1 to 2;
M is Na, H, K, or Li;
B is selected from the group consisting of hydrogen, amino, (C 1 -C 30) alkyl, (C 1 -C 30) alkoxy, (C 6 -C 30) aryl, mono (C 1 -C 30) alkylamino, ) Arylamino or di (C6-C30) arylamino;
Wherein R ₁ is selected from the group consisting of alkyl, cycloalkyl, heterocycloalkyl, alkoxy, aryl, aralkyl, heteroaryl, aryloxy, alkyloxy, monoalkylamino, dialkylamino, monoarylamino, diarylamino and alkylcarbonyl and B (C1-C30) alkyl, (C6-C30) alkyl, alkoxy, aryl, monoalkylamino, dialkylamino, monoarylamino, and diarylamino groups are optionally substituted with one or more substituents selected from the group consisting of halogen, carboxylic acid group, sulfonyl, cyano, nitro, C30) aryl, (C3-C30) heteroaryl, and the like. 6. The method of claim 5,
Wherein the acid is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and mixed acid thereof. An organic pigment and at least one pigment additive selected from the group consisting of the pigments of any one of claims 1 to 4. 8. The method of claim 7,
Wherein the organic pigment is at least one selected from anthraquinone-based, dianthraquinone-based, diketopyrrolopyrrole-based, and quinophthalone-based pigments. 8. The method of claim 7,
Wherein the pigment additive is contained in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the organic pigment. A color resist composition comprising the pigment dispersion composition of claim 7. A color filter produced using the color regent sheet composition of claim 10.