JPH11189732A - Dispersant for pigment, pigment dispersion and pigment dispersion for color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new dispersant capable of obtaining colarants good in fluidity and storage stability and useful for the production of coating materials, printing inks, pigment printing agents, colorants for synthetic resins and, especially, color filters. SOLUTION: This dispersant is represented by the formula [X is H or an acylamino; Y is anthraquinonylamino, phenylamino or the like; Z is phenylamino, a 2-30C aliphatic or alicyclic amine reaction residue or the like; G is a reaction residue of a 2-30C aliphatic or alicyclic hydrocarbon or the like; (n) is 0-3]. This dispersant is obtained e.g. by the following process: in an inert solvent such as o-dichlorobenzene, 1 mol 1-aminoanthraquinone, 1 mol aniline or phenol and 1 mol cyanuric chloride are reacted at 130-160 deg.C for 2-6 h and thereafter at 150-170 deg.C for 3-4 h on adding 1 mol polyamine having at least two amino groups (e.g. N,N-dimethylaminomethylamine, N,N-diethylaminomethylamine).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pigment dispersant and a pigment dispersion, and more particularly, to a pigment dispersion having excellent fluidity and storage stability and particularly suitable for producing a color filter (abbreviated as CF). .

[0002]

2. Description of the Related Art Conventionally, CF used for manufacturing a liquid crystal color display, an image pickup device and the like is prepared by dispersing three color pigments of red (R), green (G) and blue (B) in a photosensitive resin liquid. The pigment dispersion for CF is applied to the substrate for CF by spin coating to form a colored film, and then, through a photomask, the colored film is exposed to light and developed to pattern the colored film to form desired pixels. Created mainly by the way.

[0003] The main pigments used in the production of CF are:
Green is phthalocyanine green, for example, C.I. I. Pigment Green (hereinafter referred to as "PG") 36 and red are anthraquinone red, for example, C.I. I. Pigment Red (hereinafter referred to as PR) 177 is generally used. However, there is a difference between the hue of these pigments and the color characteristics required for a liquid crystal display, and a small amount of a yellow pigment is used together as a complementary color for each color.

As the film-forming resin in the pigment dispersion for CF, an acrylic resin having a high acid value, which can be developed with an aqueous alkali solution after the film is formed, is mainly used. However, in the conventional pigment dispersion containing the pigment and the high acid value acrylic resin, aggregation of the pigment occurs, the viscosity of the pigment dispersion tends to increase over time, and the storage stability of the pigment dispersion is poor. Often. When CF is prepared by a method using a pigment dispersion with the above-described difficulties,
The pigment dispersion to be used is applied to the CF substrate by a spin coating method, but when the viscosity of the pigment dispersion is high or the pigment particles in the liquid are aggregated and the pigment dispersion exhibits thixotropic viscosity. This is because the coating liquid rises in the center of the substrate, and when a large-screen CF is produced, unevenness or a density difference occurs in the hue of the colored film between the center and the periphery of the substrate.

[0005] Therefore, despite the fact that the pigment content of the CF pigment dispersion is usually in the range of 5 to 10% by weight, the dispersion state is such that the pigment particles do not agglomerate and the pigment dispersion is as low as 5 to 20 centipoise. It must have excellent viscosity and storage stability. To solve these problems, Japanese Unexamined Patent Publication No.
In JP-A-237403 and JP-A-60-247603, aggregation of a pigment is prevented by adding a derivative of a phthalocyanine blue-based pigment to a green pigment and a derivative of an anthrone-based pigment to a red pigment as a dispersing agent for the pigment. It is disclosed that a suitable pigment dispersion can be obtained.

[0006]

SUMMARY OF THE INVENTION However, C
Phthalocyanine green, which is mainly used as the green color of F, is obtained by adding a phthalocyanine blue-based pigment derivative as a dispersant to the dispersion, thereby greatly reducing the viscosity of the obtained pigment dispersion and having excellent storage stability. Although the above-mentioned pigment dispersion is obtained, the above-mentioned derivative of the phthalocyanine blue-based pigment is usually blue, so that the maximum absorption wavelength of the green pixel of CF shifts to the short wavelength side, the bluish transmitted light becomes strong, and the liquid crystal becomes liquid. The CF for a display has a disadvantage that the color quality is deteriorated. Further, the dispersion effect of the above-mentioned phthalocyanine blue-based pigment derivative is hardly recognized for the yellow pigment used as a complementary color of green.

The present inventors have solved the above-mentioned drawbacks of the conventional pigment derivative as a dispersant, and have developed a pigment derivative (dispersant) capable of improving the color quality and lowering the viscosity of a CF pigment dispersion. As a result of intensive research, it has been found that a specific anthraquinonylaminotriazine-based compound acts as an excellent dispersant in common with phthalocyanine green, which is the main pigment of green, and yellow pigment, which is a complementary color pigment, and has a low viscosity of the pigment dispersion. And the obtained pigment dispersion also prevents thickening gelation during storage and improves the transparency which is most important as CF. Furthermore, surprisingly, the main pigment of red, anthraquinone red (PR.177) and pyrrolopyrrole-based pigments (PR.254, PO.71) were found to exhibit a remarkable dispersing effect, and the present invention was completed.

[0008]

That is, the present invention provides a pigment dispersant represented by the following general formula (1), a pigment dispersion liquid for CF using the dispersant, and production of CF. The method and the resulting CF.

Wherein X in the above formula is a hydrogen atom or an acylamino group, Y is an anthraquinonylamino group having a hydrogen atom or an acylamino group at the 5-position, a phenylamino group or a phenoxy group, and Z is Anthraquinonylamino group having a hydrogen atom or an acylamino group at the position
A reactive residue of an aliphatic, alicyclic or heteroalicyclic amine having 2 to 30 carbon atoms having a phenylamino group, a phenoxy group or at least one amino group, and G represents at least one amino group each. A reactive residue of at least one compound selected from aliphatic, alicyclic or heteroalicyclic hydrocarbons having 2 to 30 carbon atoms, n is an integer of 0 to 3, and n is 0 In some cases, Z is a reactive residue of an aliphatic, alicyclic or heteroalicyclic polyamine having at least two amino groups and having 2 to 30 carbon atoms.

The pigment dispersant of the present invention is useful as a conventionally known dispersant for various pigments, and disperses various pigments used in various paints, various printing inks, various pigment printing agents, colorants of synthetic resins, and the like. Useful as an agent. A particularly useful use is as a dispersant in a pigment dispersion for CF.
Hereinafter, the present invention will be described by taking a pigment dispersion liquid for CF as a typical example.

The CF pigment dispersion of the present invention is obtained by using an anthraquinonylaminotriazine compound represented by the general formula (1) as a pigment dispersant.
It is possible to prevent aggregation of the pigment particles in the pigment dispersion. Therefore, the structural viscosity of the pigment dispersion is reduced, and a low viscosity is developed. As a result, thickening gelation of the pigment dispersion is suppressed, and storage stability also increases.

The dispersant represented by the general formula (1) of the present invention is yellow, orange yellow or brown, and when added to a green pigment dispersion using phthalocyanine green as a main pigment of the pigment dispersion, When the maximum absorption wavelength of the green pigment is shifted to a longer wavelength side and used for a CF of a liquid crystal display or the like, a pixel having a desired color quality can be formed.

When added to a red pigment dispersion using anthraquinone red (PR.177) as the main pigment, the dispersant has an anthraquinone structure and thus strongly adsorbs on the surface of the anthraquinone red pigment. The alkylamino group introduced into the dispersant has a strong affinity with the free carboxyl group of the film-forming resin dissolved in the pigment dispersion, imparting amphiphilicity to the pigment, It is considered that aggregation of the pigment is prevented by the effect of obstacles or the like.

[0014]

Next, the present invention will be described in more detail with reference to preferred embodiments. In the pigment dispersant of the present invention, when n is 0 in the general formula (1), and when n is 1 to
If it is 3, it is roughly classified. When n is 0, the pigment dispersant of the present invention is represented by the following general formula (A).

[0015] (However, X, Y and Z in the above formula are as defined above.)

For example, the pigment dispersant of the present invention can be prepared, for example, by adding 1 mol of 1-aminoanthraquinone, 1 mol of aniline or phenol, and 1 mol of cyanuric chloride to an inactive compound such as o-dichlorobenzene. 130 ° C in solvent
At 160 ° C. for 2 to 6 hours, further add 1 mol of a polyamine having at least two amino groups,
At a reaction condition of 3 to 4 hours.

The polyamine having at least two amino groups used in the above method includes, for example, N,
N-dimethylaminomethylamine, N, N-diethylaminomethylamine, N, N-dipropylaminomethylamine, N, N-dibutylaminomethylamine, N, N-
Dimethylaminoethylamine, N, N-diethylaminoethylamine, N, N-dipropylaminoethylamine, N, N-dibutylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminopropylamine, N, N-diamine Propylaminopropylamine, N, N-dimethylaminobutylamine, N, N-
Diethylaminobutylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminobutylamine, N, N-dimethylaminolaurylamine, N, N-
Diethylaminolaurylamine, N, N-dibutylaminolaurylamine, N, N-dimethylaminostearylamine, N, N-diethylaminostearylamine,
N, N-diethanolaminoethylamine, N, N-diethanolaminopropylamine, N-aminopropylmorpholine, N-aminopropyl-4-pipecholine, N
-Aminopropylpiperidine, N, N-diethylaminoethoxypropylamine, N, N, N ", N" -tetraethyldiethylenetriamine and the like. Preferred among these polyamines are those represented by the following structural formula.

[0018] However, R ₁ and R ₂ are a substituted or unsubstituted alkyl group or a cycloalkyl group, or R ₁ and R ₂ together with an adjacent nitrogen atom optionally include a heterocycle containing a nitrogen, oxygen or sulfur atom. It may be formed. m is an integer of 2 to 30.

Specific examples of the dispersant (A) of the present invention obtained according to the above method include, for example, 2,4-bis [anthraquinonyl (-1 ′)-amino] -6- (N, N-dimethyl) Amino) ethylamino-s-triazine, 2,4
-Bis [anthraquinonyl (-1 ′)-amino] -6-
(N, N-diethylamino) propylamino-s-triazine, 2,4-bis [anthraquinonyl (-1 ′)-
Amino-6- (N, N-dibutylamino) -s-triazine, 2,4-bis [5′-benzamide-anthraquinonyl (-1 ′)-amino] -6- (N, N-dimethylamino) ethylamino -S-triazine, 2,4-bis [anthraquinonyl (-1 ′)-amino] -6- (N,
N-dihydroxyethylamino) propylamino-s-
Triazine, 2,4-bis [5′-benzamide-anthraquinonyl (-1 ′)-amino] -6- (N, N-diethylamino) propylamino-s-triazine,
4-bis [anthraquinonyl (-1 ′)-amino] -6
-(N, N-dimethylaminoethoxy) propylamino-s-triazine, 2,4-bis [5'-benzamide-anthraquinonyl (-1 ')-amino] -6-butylamino-s-triazine, 2- [ Anthraquinonyl (-
1 ′)-Amino] -4-phenoxy-6- (N, N-diethylamino) propylamino-s-triazine, 2-
Mono [anthraquinonyl (-1 ′)-amino] -4-phenylamino-6- (N, N-diethylamino) propylamino-s-triazine, 2-mono [5′-benzamide-anthraquinonyl (-1 ′)-amino 4-phenylamino-6- (N, N-diethylamino) propylamino-s-triazine, 2,4-bis [anthraquinonyl (-1 ')-amino] -6- (N-morpholinyl) ethylamino-s -Triazine, 2,4-bis [anthraquinonyl (-1 ′)-amino] -6- (N-piperidyl) propylamino-s-triazine, 2,4-bis [anthraquinonyl (-1 ′)-amino] -6 −
[(N, N-diethylamino) phenyl (-1 ″,
4 ")-amino] -s-triazine and the like.

The pigment dispersant of the present invention wherein n is 1 to 3 in the general formula (1) is represented by the following general formula (B). Here, X, Y, Z, G and n in the above formula are as defined above.

In the present invention, as the anthraquinonylaminotriazine-based compound (yellow pigment) as a raw material of the dispersant (B), in addition to the dispersant (A), for example,
2,4,6-tris [anthraquinonyl (-1 ′)-amino] -s-triazine, 2,4,6-tris [5′-
Benzamide-anthraquinonyl (-1 ')-amino]
-S-triazine, 2,4-bis [anthraquinonyl (-1 ')-amino] -6-phenylamino-s-triazine, 2,4-bis [5'-benzamide-anthraquinonyl (-1')-amino] -6-phenylamino-
s-Triazine, 2,4-bis [anthraquinonyl (-
1 ')-amino] -6-phenoxy-s-triazine,
2,4-bis [5'-benzamido-anthraquinonyl (-1 ')-amino] -6-phenoxy-s-triazine, 2,4-bis [anthraquinonyl (-1')-amino] -6-phenyl-s -Triazine, 2,4-bis [5'-benzamide-anthraquinonyl (-1 ')-
Amino] -6-phenyl-s-triazine, 2-mono [anthraquinonyl (-1 ')-amino] -4,6-bis (phenylamino) -s-triazine, 2-mono [5'-benzamide-anthraquinonyl ( -1 ')-
Amino] -4,6-bis (phenylamino) -s-triazine, 2,4-bis [anthraquinonyl (-1 ′)-
Amino] -6- (N, N-dimethylamino) ethylamino-s-triazine, 2,4-bis [anthraquinonyl (-1 ′)-amino] -6- (N, N-diethylamino) propylamino-s- Triazine and the like.

The above-mentioned anthraquinonylaminotriazine compounds are described, for example, in JP-B-46-33232, JP-B-46-33233, and JP-B-46-3.
It is manufactured by the manufacturing method disclosed in Japanese Patent No. 4518 or a method equivalent thereto. The reaction at the time of production is, for example, the reaction of 1 to 3 mol of 1-aminoanthraquinone and 1 mol of cyanuric chloride in a solvent such as phenol at 110 ° C. for 5 minutes.
The reaction is further carried out at 150 ° C. for 2 to 3 hours, and after addition of 0 to 2 mol of other primary amines and phenols, the resulting reaction mixture is heated at 150 ° C. for 2 to 3 hours. This is done by heating.

An example of the synthesis of the dispersant (B) will be described. An anthraquinonylaminotriazine compound used as the raw material is dissolved in concentrated sulfuric acid, fuming sulfuric acid or polyphosphoric acid, and paraformaldehyde and monochloroacetic acid amide are dissolved. To obtain a compound represented by the following formula (a). Monochloroacetic acid amides usable in this reaction include, for example, monochloroacetic acid amide, N-methyl-monochloroacetic acid amide, N-ethyl-monochloroacetic acid amide, 3-chloropropionic acid amide, N-methyl-3-acid
Chloropropionamide, N-ethyl-3-chloropropionamide and the like can be mentioned.

As another method, the anthraquinonylaminotriazine-based compound as a raw material is added to concentrated sulfuric acid or a mixture of fuming sulfuric acid and chlorosulfonic acid, and paraformaldehyde is further added to cause a chloromethylation reaction. The compound represented by b) is obtained. Alternatively, a compound represented by the following formula (b) can be obtained by reacting a compound represented by the following formula (a) with phosphorus oxychloride in the presence of dimethylformamide or the like.

[0025]

[0026] However, X, Y, Z and n in the above formulas (a) and (b) are as defined above, R ₃ is a hydrogen atom or a lower alkyl group, and k is an integer of 1 or 2. .

Then, the compound represented by the formula (a) or (b) is reacted with water or an inert solvent in an aliphatic, alicyclic or heterocyclic group having 2 to 30 carbon atoms having at least one amino group. By reacting with at least one amino compound selected from alicyclic hydrocarbons, the dispersant of the present invention represented by the formula (c) or (d) is synthesized.

[0028]

[0029] However, X, Y, Z, R ₁ , R ₂ , R ₃ , k, n in the above formula
Is as defined above, m is an integer of 2 to 30,
l (ell) is an integer of 0 or 1.

In order to obtain the dispersant represented by the formula (c) or (d) of the present invention, the compound of the above formula (a) or (b) is added to the amino compound having a primary or secondary amino group. The compound is reacted. The reaction of the compounds of formula (a) or (b) with these amino compounds is carried out by reacting the compound of formula (a) or (b) in water or an inert solvent at 50-150 ° C. in the presence of excess amino compound. For several hours. As the amino compound used in the reaction, an aliphatic compound having 2 to 30 carbon atoms,
Known primary or secondary monoamines selected from alicyclic or heteroalicyclic hydrocarbons can also be used, but preferred amines are the polyamines used in the production of the dispersant (A).

Preferred groups as the substituent G in the dispersant (B) of the present invention are the following groups. However, R ₁ , R ₂ and m are as defined above.

When a pigment dispersion is prepared using the pigment dispersant of the present invention, the pigment dispersant of the present invention is
0.5 to 50 parts by weight, preferably 1 to 50 parts by weight,
Used in a proportion of 30 parts by weight. If the amount is less than 0.5 part by weight, the effect of the pigment dispersant of the present invention is hardly recognized. On the other hand, if the amount is more than 50 parts by weight, the effect corresponding to the amount used is not obtained.

As a method for producing the pigment dispersion of the present invention, a pigment and a dispersant are added to an organic solvent solution or aqueous solution containing an appropriate film-forming resin, premixed, and then mixed and dispersed. . For example, a pigment and a dispersant to be used are uniformly mixed and pulverized with a dispersing machine such as a tumbler, Henschel mixer, hammer mill, pin mill, kneader, attritor, ball mill, and the like, and added and mixed in a liquid containing a film-forming resin. Method: A pigment is uniformly suspended in water or an organic solvent, a solution containing a dispersant is added and mixed, and a solution in which the dispersant is adsorbed on the pigment particle surface is added to a liquid containing a film-forming resin. A method of mixing, a method of dissolving a pigment and a dispersing agent in sulfuric acid or the like, then precipitating the sulfuric acid solution in water, separating both as a solid solution, and adding and mixing this into a liquid containing a film-forming resin. .

In the present invention, as a liquid containing a film-forming resin for dispersing a pigment into a pigment dispersion, a liquid containing a film-forming resin used in a conventionally known pigment dispersion for CF is used. Further, an organic solvent, water, and a mixture of an organic solvent and water are used as a liquid medium. If necessary, conventionally known additives, for example, additives such as a dispersing aid, a leveling agent, and a cohering agent can be added to the pigment dispersion.

The weight ratio of the pigment to the resin in the liquid containing the film-forming resin is preferably in the range of 5 to 500 parts by weight based on 100 parts by weight of the film-forming resin.
As the liquid containing a film-forming resin, a liquid containing a photosensitive film-forming resin or a liquid containing a non-photosensitive film-forming resin is used. Examples of the liquid containing a photosensitive film-forming resin include, for example, a liquid containing a photosensitive film-forming resin used in an ultraviolet curable ink, an electron beam-curable ink, and the like. As the liquid containing a non-photosensitive film-forming resin, For example, varnish used for printing ink such as letterpress ink, planographic ink, intaglio gravure ink, stencil screen ink, varnish used for room temperature drying and baking paint, varnish used for electrodeposition coating, development of electronic printing and electrostatic printing And a varnish used for a thermal transfer ribbon.

Examples of the photosensitive film forming resin include a photosensitive cyclized rubber resin, a photosensitive phenol resin, a photosensitive polyacrylate resin, a photosensitive polyamide resin, a photosensitive polyimide resin, and an unsaturated polyester resin. Examples thereof include resins, polyester acrylate resins, polyepoxy acrylate resins, polyurethane acrylate resins, polyether acrylate resins, and polyol acrylate resins, and various monomers can be added as a reactive diluent. Among the above-mentioned photosensitive film-forming resins, preferred resins are acrylate-based alkali developable resins each having a free carboxyl group in the molecule.

Further, a photopolymerization initiator such as benzoin ether or benzophenone is added to a pigment dispersion containing a photosensitive resin, and the mixture is bricked by a conventionally known method to obtain a photocurable photosensitive pigment dispersion. Can be. Further, a thermosetting pigment dispersion can be obtained by using a thermal polymerization initiator instead of the photopolymerization initiator.

When a CF pattern is formed using the above-mentioned photosensitive pigment dispersion, the photosensitive pigment dispersion is applied to a transparent CF substrate such as a glass substrate by a spin coater, a low-speed rotation coater, a roll coater, or a knife. Perform full-surface coating using a coater, etc., or perform full-surface printing by one of various printing methods or partial printing of a slightly larger size than the pattern, and adhere the photomask to the film obtained after preliminary drying. Then, exposure is performed using an ultra-high pressure mercury lamp to print the pattern. Next, development and washing are performed, and post-baking is performed as necessary, so that CF
Can be formed.

Examples of non-photosensitive film-forming resins include cellulose acetate resins, nitrocellulose resins,
Styrene (co) polymer, polyvinyl butyral resin, amino alkyd resin, rosin modified phenol resin, polymerized linseed oil, petroleum resin, polyester resin, amino resin modified polyester resin, polyurethane resin, acrylic polyol urethane Resin, soluble polyamide resin, soluble polyimide resin, soluble polyamideimide resin, soluble polyesterimide resin, casein, hydroxyethylcellulose, water-soluble salt of styrene-maleic acid ester copolymer, (meth) acrylic acid ester Water-soluble salts of (co) polymers, water-soluble aminoalkyd resins, water-soluble aminopolyester resins,
Water-soluble polyamide-based resins and the like can be mentioned.

In the case of forming a CF pattern using the above non-photosensitive pigment dispersion, the above-mentioned non-photosensitive pigment dispersion, for example, the above-mentioned various types of inks using the CF printing ink on a similar CF substrate. A method of printing a colored pattern directly on a substrate by one of the printing methods described above, a method of forming a colored pattern on a substrate by electrodeposition coating using an aqueous electrodeposition coating composition for CF, an electronic printing method, An electroprinting method, a method in which a colored pattern is once formed on a transferable base material by one of the above methods, and the like, and then transferred to a CF substrate. Next, baking is performed as necessary, polishing for smoothing the surface is performed, and top coating for protecting the surface is performed according to a conventional method. Further, a black matrix is formed according to a conventional method, and the C
F can be obtained.

[0041]

Now, the present invention will be described in further detail with reference to Synthesis Examples, Examples and Comparative Examples. It should be noted that “part” or “%” in the text is based on weight. Example for Dispersant A Synthesis Example A1 To 1000 parts of o-dichlorobenzene, 71 parts of 1-aminoanthraquinone and 30 parts of cyanuric chloride were added, and 170 ° C.
And stir for 5 hours. After cooling, 50 parts of N, N-dimethylaminopropylamine is further added, and the mixture is stirred at 170 ° C. for 3 hours. After filtration, washing with alcohol and drying, 86 parts of the following dispersant A1 were obtained.

[0042]

Synthesis Example A2 In the same manner as in Synthesis Example A1, 1-aminoanthraquinone, aniline and N, N-dimethylaminopropylamine were successively reacted with cyanuric chloride to obtain a dispersant A2 of the following formula.

[0044]

Synthesis Example A3 In the same manner as in Synthesis Example A1, cyanuric chloride was reacted with 5-benzamide-1-aminoanthraquinone and N, N-diethylaminopropylamine to obtain a dispersant A3 of the following formula.

[0046]

Synthesis Example A4 In the same manner as in Synthesis Example A1, cyanuric chloride was successively reacted with 5-benzamide-1-aminoanthraquinone, aniline and N, N-diethylaminopropylamine to obtain a dispersant A4 of the following formula. Was.

[0048]

Synthesis Example A5 The same operation as in Synthesis Example A1 was repeated except that N-aminopropylmorpholine was used instead of N, N-dimethylaminopropylamine in Synthesis Example A1, and a dispersant A of the following formula was prepared.
5 was obtained.

[0050]

Synthesis Example A6 The same operation as in Synthesis Example A1 was repeated except that laurylaminopropylamine was used instead of N, N-dimethylaminopropylamine in Synthesis Example A1, and a dispersant A of the following formula was prepared.
6 was obtained.

[0052]

Synthesis Example A7 The same procedure as in Synthesis Example A1 was repeated except that N-aminopropyl-4-pipecholine was used in place of N, N-dimethylaminopropylamine of Synthesis Example A1, and a dispersant A7 of the following formula was prepared. I got

[0054]

Synthesis Example A8 The same operation as in Synthesis Example A1 was repeated except that N, N-diethanolaminopropylamine was used instead of N, N-dimethylaminopropylamine in Synthesis Example A1, and a dispersant of the following formula was obtained. A8 was obtained.

[0056]

Example A1 Acrylic resin (methacrylic acid / butyl acrylate / styrene / hydroxyethyl acrylate = 25/50 /
Polymerized at a molar ratio of 15/10. Molecular weight 12,0
00 and a solid content of 30%), a brominated phthalocyanine green (PG.36), the dispersant A1 and a solvent (propylene glycol monomethyl ether acetate) (hereinafter abbreviated as PGMAc) are blended as shown in Table 1 below. ,
After premixing, the mixture was dispersed by a horizontal bead mill to obtain a green base color.

Examples A2 to 3 In the same manner as in Example A1 except that each of the dispersants A2 to 3 was used in place of the dispersant A1, two kinds of green A base color was obtained.

Examples A4 to A7 Anthraquinonyl red (PR.177) was used in place of the brominated phthalocyanine green used in Example A1, and the dispersants A4 to A7 were used as dispersants. Except for the above, four kinds of red base colors were obtained in the same manner as in Example A1. The composition is shown in Table 1.

Examples A8 to 10 In place of the brominated phthalocyanine green used in Example A1, a yellow pigment isoindoline (P.Y.139) was used, and the dispersants A8, A1, and A2 were used as dispersants, respectively. A yellow base color was obtained in the same manner as in Example A1, except that the above procedure was repeated. The composition is shown in Table 1.

Comparative Example A1 A green base color was prepared in the formulation shown in Table 1 below in the same manner as in Example A1 except that a dispersant (abbreviated as BD), which is a derivative of a commercially available blue pigment, was used. Obtained.

Comparative Example A2 A red base color was prepared in the same manner as in Example A4 except that a dispersant (abbreviated as YD), which is a derivative of a commercially available yellow pigment, was used. Obtained.

Comparative Example A3 A yellow base color was obtained in the same manner as in Example A8 except that the above-mentioned dispersant (abbreviated as YD) was used.

Table 1 Examples A1 to 10 and Comparative Examples A1
Composition table of 3 (numerical values represent "parts")

Example A11 The base colors of Examples A1 to A10 and Comparative Examples A1 to A3 were applied to a glass substrate with a spinner, dried, and the maximum transmittance and the maximum absorption wavelength of the coating film were measured. The base color was stored at room temperature for one month, and the change in viscosity was measured.
Table 2 shows the results. For each of the maximum transmissions of red and yellow, the values shown in the table are 6 for that color.
It is 1/2 of the transmittance at 50 nm.

Table 2 Examples A1 to 10 and Comparative Examples A1
Light transmission characteristics and storage stability of 3

The green base color obtained in each of Examples A1 to A3 has a longer maximum absorption wavelength and a lower viscosity than the green base color of Comparative Example A1, and has a low viscosity. Is also small. Compared to the red base color of Comparative Example A2 and the yellow base color of Comparative Example A3, the red base color and yellow base color of Examples A4 to A7 and Examples A8 to 10 had little difference in hue. And one month later, the viscosity is significantly lower.

Example A12 In order to obtain a CF of RGB, photosensitive pigment dispersions of R, G and B were obtained according to the formulation shown in Table 3 below. Regarding the blue base color, instead of cyanine green of Comparative Example A1, cyanine blue P.I. B. 15: 6 and prepared using a commercially available derivative of copper phthalocyanine blue as the dispersant.

Table 3 Formulation of R, G and B photosensitive pigment dispersions (numerical values represent "parts")

The glass substrate treated with the silane coupling agent was set on a spin coater, and the above-described photosensitive pigment dispersion for CF of R was spin-coated at 300 rpm for 5 seconds, and then at 1,200 rpm for 5 seconds. did.
Next, prebaking was performed at 80 ° C. for 10 minutes, a photomask having a mosaic pattern was brought into close contact, and exposure was performed using a super-high pressure mercury lamp at a light amount of 100 mJ / cm ² .
Next, development and washing were performed with a dedicated developer and a dedicated rinse to form a red mosaic pattern on the glass substrate.

Subsequently, a green mosaic pattern and a blue mosaic pattern are formed by applying and baking according to the above-described method using the above-mentioned photosensitive pigment dispersion liquid for G and B CF, and forming RGB CF and mosaic patterns. I got The CF obtained above has excellent spectral curve characteristics, excellent fastness such as light resistance and heat resistance, and also excellent properties of light transmission, and is excellent as CF for liquid crystal color displays. Properties.

Examples for Dispersant B Synthesis Example B1 140 parts of 2,4,6-tris [anthraquinonyl (-1 ')-amino] -s-triazine were added to 98
The mixture was dissolved in concentrated sulfuric acid, and 147 parts of paraformaldehyde and 96 parts of 2-chloroacetic acid amide were added, and the mixture was reacted at 80 ° C for 5 hours. After the reaction, the reaction mixture was poured into a large amount of ice water, and the generated solid was filtered and washed with water. As a result of drying a part of the paste thus obtained and performing elemental analysis, it was found that 2.0 substituents were introduced per molecule. Next, the obtained paste is poured into 20 times water,
68 parts of N, N-dimethylaminopropylamine was added and reacted at 70 ° C. for 3 hours. The resulting solid was filtered, washed with water and dried to obtain a dispersant B1 of the following formula. The obtained dispersant was dissolved in acetic acid.

[0073]

Synthesis Example B2 2,4-bis [anthraquinonyl (-1 ′)-amino]
Except that -6-phenylamino-s-triazine was used, the same reaction as in Synthesis Example B1 was performed to obtain a dispersant B2 of the following formula. This was dissolved in acetic acid.

[0075]

Synthesis Example B3 A reaction similar to that of Synthesis Example B1 was carried out except that 2,4,6-tris [5'-benzamide-anthraquinonyl (-1 ')-amino] -s-triazine was used. Was obtained. This was dissolved in acetic acid.

[0077]

Synthesis Example B4 A reaction similar to that of Synthesis Example B1 was carried out except that 2,4-bis [5′-benzamide-anthraquinonyl (-1 ′)-amino] -6-phenylamino-s-triazine was used.
A dispersant B4 represented by the following formula was obtained. This was dissolved in acetic acid.

[0079]

Synthesis Example B5 2,4-bis [anthraquinonyl (-1 ′)-amino]
80 parts of 6-chloro-s-triazine were dissolved in 1600 parts of o-dichlorobenzene,
Twice mole of N, N-dimethylaminopropylamine was added and reacted at 170 ° C. for 6 hours. After cooling, the resulting solid was filtered, washed with alcohol, and dried.

The obtained yellow powder (100 parts) was diluted 15 times to 98
% Parasulfuric acid, and 40 parts of paraformaldehyde and 93 parts of monochloroacetic acid amide were added and reacted at 80 ° C. for 6 hours. After the reaction, the mixture was poured into a large amount of ice water, and the generated solid was filtered and washed with water. As a result of drying a part of the paste thus obtained and performing elemental analysis, it was found that 2.0 substituents were introduced per molecule. Next, the obtained paste was poured into 20 times the volume of ice water, 100 parts of N, N-dimethylaminopropylamine was added, and the mixture was reacted at 70 ° C. for 4 hours. The resulting solid was filtered, washed with water, and dried. Of dispersant B5 was obtained. The obtained dispersant was dissolved in acetic acid.

[0082]

Synthesis Example B6 The same operation as in Synthesis Example B5 was repeated except that 2,4-bis [5-benzamide-anthraquinonyl (-1 ′)-amino] -6-chloro-s-triazine was used, and the following formula was used. Of dispersant B6 was obtained. The obtained dispersant was dissolved in acetic acid.

[0084]

Synthesis Example B7 80 parts of 2,4,6-tris [anthraquinonyl (-1 ')-amino] -s-triazine was added to a mixture of 150 parts of 98% sulfuric acid and 200 parts of chlorosulfonic acid at 20 ° C. or lower. Then, 45 parts of paraformaldehyde was added at 30 ° C. or lower, and the mixture was stirred for 1 hour. Further heating was performed at 80 ° C. for 6 hours. After the reaction, the mixture was poured into a large amount of ice water, and the generated solid was filtered and washed with water. As a result of drying a part of the paste thus obtained and performing an elemental analysis, it was found that the number of substituents per molecule was 2.0. Next, the obtained paste was put into 20 times water, 80 parts of N, N-dimethylaminopropylamine was added, and the mixture was reacted at 70 ° C. for 4 hours. The resulting solid was filtered, washed with water, and dried. Was obtained as dispersant B7. The obtained dispersant was dissolved in acetic acid.

[0086]

Synthesis Example B8 2,4-bis [anthraquinonyl (-1 ′)-amino]
Except that -6-phenylamino-s-triazine was used, the same reaction as in Synthesis Example B7 was performed to obtain a dispersant B8 of the following formula. This was dissolved in acetic acid.

[0088]

Example B1 Acrylic resin (methacrylic acid / butyl acrylate / styrene / hydroxyethyl acrylate = 25/50 /
Polymerized at a molar ratio of 15/10. Molecular weight 12,0
00 and a solid content of 30%), a brominated phthalocyanine green (PG.36), the dispersant B1 and PGMAc were mixed as shown in Table 4 below, and after premixing, dispersed by a horizontal bead mill to obtain a green color. A base color was obtained.

Examples B2-8 Example B2 except that the dispersants B2 to B8 were used.
In the same manner as in Example 1, a green base color was obtained with the composition shown in Table 4 below.

Example B9 A red base color was obtained in the same manner as in Example B1, except that anthraquinonyl red (PR 177) was used in place of the brominated phthalocyanine green used in Example B1. I got The composition is shown in Table 4.

Example B10 A yellow base color was obtained in the same manner as in Example B1, except that the yellow pigment isoindoline (PY139) was used in place of the brominated phthalocyanine green used in Example B1. I got The composition is shown in Table 4.

Comparative Example B1 The procedure of Example B1 was repeated, except that BD was used.
A green base color was obtained with the composition shown in Table 4 below.

Comparative Example B2 Same as Example B7 except that YD was used.
A green base color was obtained with the composition shown in Table 4 above.

Comparative Example B3 The procedure of Example B1 was repeated except that YD was used.
A green base color was obtained with the composition shown in Table 4 above.

Table 4 Examples B1 to 10 and Comparative Examples B1
Table 3

Example B11 The base colors of Examples B1 to B10 and Comparative Examples B1 to B3 were applied to a glass substrate with a spinner, dried, and the maximum transmittance and the maximum absorption wavelength of the coating film were measured. The base color was stored at room temperature for one month, and the change in viscosity was measured.
Table 5 shows the results. For each of the maximum transmissions of red and yellow, the values shown in the table are 6 for that color.
It is 1/2 of the transmittance at 50 nm.

Table 5 Examples B1 to 10 and Comparative Examples B1
Light transmission characteristics and storage stability of 3

The green base color obtained in each of Examples B1 to B8 has a longer maximum absorption wavelength and a lower viscosity than the green base color of Comparative Example B1, and has a low viscosity. Is also small. Comparative Example B9 and Example B1
The red base color and the yellow base color of 0 had little difference in hue, but the viscosity was significantly low both initially and after one month.

Example B12 In order to obtain an RGB color filter, R, G and B photosensitive pigment dispersions were prepared according to the formulations shown in Table 6 below. Regarding the blue base color, cyanine blue P. was used instead of cyanine green of Comparative Example B1. B. 15: 6, and by using commercially available derivatives of copper phthalocyanine blue.

Table 6 Formulation of R, G and B photosensitive pigment dispersions

The glass substrate treated with the silane coupling agent was set on a spin coater, and the above-described photosensitive pigment dispersion for a color filter of R was first spun at 300 rpm for 5 seconds, and then at 1,200 rpm for 5 seconds. Coated. Then pre-bake at 80 ° C for 10 minutes,
A photomask having a mosaic pattern was brought into close contact, and exposure was performed using a super-high pressure mercury lamp at a light amount of 100 mJ / cm ² . Next, development and washing were performed with a dedicated developer and a dedicated rinse to form a red mosaic pattern on the glass substrate.

Subsequently, a green mosaic pattern and a blue mosaic pattern are formed by applying and baking according to the above-mentioned method using the above-mentioned photosensitive pigment dispersions for the color filters of G and B to form an RGB color pattern. A filter was obtained. The color filter obtained above has excellent spectral curve characteristics, excellent fastness such as light resistance and heat resistance, and also has excellent properties of light transmission. As excellent properties.

Examples of Other Applications Example C1 10 parts of dispersant A1 are dissolved in 100 parts of an aqueous solution containing 5 parts of glacial acetic acid, and this solution is slurried with a yellow pigment (PY-110) (pigment content: 100 parts). And stirred for 60 minutes. Next, the pH of the system is adjusted to 8.5 by gradually adding a 10% aqueous solution of sodium hydroxide. After further stirring for 30 minutes, the resulting solid was filtered, washed, dried and pulverized at 90 ° C. to obtain 108 parts of a surface-treated yellow pigment powder.

When the pigment composition thus obtained was dispersed in a commercially available melamine / alkyd paint by a ball mill (pigment content: 15%), it had a low viscosity and a fluidity almost similar to Newtonian flow. Indicated. Further, this yellow paint was mixed with a commercially available white paint of melamine / alkyd to prepare a pale yellow paint, and stored for one week. As a result, the color was uniform without color separation. As a comparative example, when a yellow pigment (PY-110) not surface-treated with the dispersant A1 was used and dispersed in the same composition, the mixture had a high viscosity, and in a mixed paint with a white paint, the yellow pigment caused aggregation. Separation and sedimentation had occurred.

Example C2 Eight parts of dispersant A1 was dissolved in 100 parts of an aqueous solution containing 5 parts of glacial acetic acid, and this solution was added to a yellow pigment (PY-154) slurry (pigment content: 100 parts). Stir for a minute.
Next, a 10% aqueous solution of sodium hydroxide is gradually added to adjust the pH of the system to 8.5. After stirring for another 30 minutes,
The resulting solid was filtered, washed, dried and pulverized at 90 ° C. to obtain 105 parts of a surface-treated yellow pigment powder.

The pigment composition thus obtained was dispersed in a commercially available acrylic lacquer using a bead mill.
A yellow paint having a pigment content of 13% was prepared. The viscosity of this paint was adjusted with a thinner for lacquer, and spray coating was performed on an iron plate to obtain a yellow paint plate having a dry film thickness of 32 μm. This was excellent in sharpness and showed high gloss. Dispersant A2 for comparison
A yellow pigment (PY-154) not subjected to surface treatment was dispersed in the same composition, and after adjusting the viscosity, spray coating was performed to prepare a yellow coated plate. In this case, the surface of the coating film was not smooth and had low gloss.

Example C3 When a green pigment (PG-7) was dispersed in a commercially available melamine / alkyd paint, a dispersant A3 was added in an amount of 8% based on the green pigment, and a green paint having a total pigment content of 15% was added. It was created. This paint is different from the paint without the dispersant A3.
Although the hue was slightly yellow, the viscosity was low when the flowability was measured, indicating a flow behavior close to Newtonian flow.
Further, when a pale green paint was prepared by mixing with a commercially available melamine / alkyd white paint and stored at 50 ° C. for one week, the one containing the dispersant A3 was a uniform pale green paint.
In the paint made without adding the dispersant A3, the green pigment and the white pigment were aggregated, and a nearly transparent liquid medium appeared as an upper layer on the paint.

In the above description, the pigment dispersant of the present invention has been described with reference to the production example of CF and the production example of paint. However, the present invention is not limited to the production of CF and paint. For example, the pigment dispersant of the present invention is useful as a conventionally known dispersant for various pigments, and various pigments used in various paints, various printing inks, various pigment printing agents, synthetic resin colorants, etc. It is useful as a dispersant.

[0110]

According to the present invention, a pigment dispersion can be stably produced by adding the dispersant of the present invention as a dispersant for a pigment dispersion for forming R and G colors of CF. When used as a pigment dispersion for CF, the resulting colored film has excellent spectral curve characteristics, and is clear, clear, highly transparent, and has light resistance and heat resistance. Excellent in various fastnesses such as solvent resistance, chemical resistance, water resistance, etc.
F can be obtained.

──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. ⁶ Identification code FI G03F 7/004 505 G03F 7/004 505 (72) Inventor Mitsuo Yamazaki 1-9-4 Horinouchi, Adachi-ku, Tokyo Dainichi Seika Industrial Co., Ltd. (72) Inventor Tetsuo Fukuda 1-9-4 Horinouchi, Adachi-ku, Tokyo Dainichi Seika Industrial Technology Research Center (72) Inventor Shiro Yamamiya 1-9-4, Horinouchi, Adachi-ku, Tokyo Large (72) Inventor Yoshio Abe 1-9-4 Horinouchi, Adachi-ku, Tokyo Daini-Seika Industry Co., Ltd. Technical Research Center (72) Michie Nakamura 1 Horinouchi, Adachi-ku, Tokyo -9-4 Dainichi Seika Industry Co., Ltd. Technology Research Center

Claims (11)

[Claims] 1. A pigment dispersant represented by the following general formula (1). (However, X in the above formula is a hydrogen atom or an acylamino group, Y is an anthraquinonylamino group having a hydrogen atom or an acylamino group at the 5-position, a phenylamino group or a phenoxy group, and Z is a 5-position. Reaction residue of aliphatic, alicyclic or heteroalicyclic amine having 2 to 30 carbon atoms having an anthraquinonylamino group having a hydrogen atom or an acylamino group, a phenylamino group, a phenoxy group or at least one amino group Wherein G is at least one selected from aliphatic, alicyclic and heteroalicyclic hydrocarbons having 2 to 30 carbon atoms each having at least one amino group.
N is an integer of 0 to 3; and when n is 0, Z is an aliphatic or alicyclic group having 2 to 30 carbon atoms and having at least 2 amino groups. Or a reactive residue of a heteroalicyclic polyamine. ) 2. When n is 0 and Z is (However, R ₁ and R ₂ are a substituted or unsubstituted alkyl group or a cycloalkyl group, or R ₁ and R ₂ are, together with an adjacent nitrogen atom, optionally a heterocycle containing a nitrogen, oxygen or sulfur atom, The pigment dispersant according to claim 1, wherein m is an integer of 2 to 30. 3. n is an integer of 1 to 3, and G is (However, R ₁ and R ₂ are a substituted or unsubstituted alkyl group or a cycloalkyl group, or R ₁ and R ₂ are, together with an adjacent nitrogen atom, optionally a heterocycle containing a nitrogen, oxygen or sulfur atom, The pigment dispersant according to claim 1, wherein m is an integer of 2 to 30. 4. The dispersant according to claim 1, wherein in the pigment dispersion comprising a pigment, a dispersant, a film-forming resin, and a liquid medium, the pigment is a green pigment, a red pigment, or a yellow pigment, and the dispersant is the dispersant according to claim 1. A pigment dispersion, characterized in that: 5. The pigment dispersion according to claim 4, comprising 0.5 to 50 parts by weight of the pigment dispersant with respect to 100 parts by weight of the pigment. 6. The green pigment is C.I. I. Pigment Green 36, and the red pigment is C.I. I. Pigment Red 17
The pigment dispersion according to claim 4, which is 7. 7. The pigment dispersion according to claim 4, wherein the film-forming resin contains a photosensitive resin. 8. The pigment dispersion according to claim 7, wherein the photosensitive resin contains an acrylic resin having a free carboxyl group in a molecule. 9. The pigment dispersion according to claim 4, for producing a color filter. 10. A method for producing a color filter including a step of forming a colored pattern on a substrate for a color filter, wherein the colored pattern is formed by using the pigment dispersion according to claim 4. Manufacturing method. 11. A color filter formed by the method according to claim 9.