TWI472581B - Triarylmethane and rosy red pigment compositions, and the use of such pigment dispersions - Google Patents

Description

Triarylmethane and rose red pigment compositions and pigment dispersions using the same

The present invention relates to a triarylmethane-based and rosin-based pigment composition, and more particularly, the present invention relates to a triarylmethane-based and rosin-based pigment composition excellent in light resistance and heat resistance, and a pigment dispersion using the same body.

In the past, triarylmethane-based dyes and pigments have been used for coloring agents, inkjet inks, color filters, and the like (Patent Documents 1 to 4).

However, triarylmethane dyes and pigments have disadvantages of poor heat resistance and light resistance when compared with anthraquinone pigments and the like. Therefore, attempts have been made to eliminate this disadvantage. For example, an attempt has been made to develop a color filter using a polymer containing a triphenylmethane dye (Patent Document 5). Further, attempts have been made to use a salt of a triarylmethane and an organic acid (Patent Document 6).

Patent Document 1: Japanese Laid-Open Patent Publication No. 61-006659

Patent Document 2: Japanese Laid-Open Patent Publication No. 61-036758

Patent Document 3: International Publication No. 2002/100959

Patent Document 4: Japanese Laid-Open Patent Publication No. Hei 11-223720

Patent Document 5: Japanese Laid-Open Patent Publication No. 2000-162429

Patent Document 6: Japanese Laid-Open Patent Publication No. 2006-306933

However, in actuality, the triarylmethane-based pigment obtained above is insufficient in light resistance and heat resistance, and the production steps are complicated, and it has not been put into practical use.

Therefore, the object of the present invention is to provide an excellent light resistance and heat resistance. The triarylmethane-based pigment composition and the pigment dispersion using the same, and a rose-red pigment composition excellent in light resistance and heat resistance, and a pigment dispersion using the same.

The present invention has been completed according to the following findings: a lake pigment having a triarylmethane structure and a lake pigment having a rose-red structure are treated with a sulfonic acid or a carboxylic acid having an aryl group, whereby the pigment can be greatly enhanced Light resistance and heat resistance.

That is, the pigment composition of the present invention is characterized in that an untreated pigment selected from a lake pigment having a triarylmethane structure represented by the formula 1 and/or a rose-red structure represented by the formula 3 is selected from the group consisting of The organic acid of the group consisting of a substituted or unsubstituted arylsulfonic acid and a substituted or unsubstituted aryl carboxylic acid is subjected to treatment.

Here, in the formula 1, R ¹ , R ² , R ³ and R ⁴ are each independently -H, -CH ₃ , C ₂ H ₅ , -Ph(phenyl), -PhCH ₃ , -CH ₂ Ph(SO) _{3 .} 1/2Ba), or -CH ₂ Ph(SO ₃ .1/3Al), substituted or unsubstituted phenyl or naphthyl group represented by R system 2

In the formula 2, R ⁵ is -H, -NHCH ₃ , -N(CH ₃ ) ₂ , -N(C ₂ H ₅ ) ₂ , -NHPh, or -NHPh(CH ₃ )(SO ₃ H) or a salt thereof , R ⁶ is -H, -Cl, or -SO ₃ H or a salt thereof, and R ⁷ is -NHC ₂ H ₅ ,

In the formula 3, R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently -H or an alkyl group, R ¹² is a -H, an alkyl group, or a substituted or unsubstituted phenyl group.

The pigment dispersion of the present invention is a pigment dispersion obtained by performing a dispersion treatment by using the above pigment composition.

Further, the pigment dispersion of the present invention can also be obtained by the following method: an untreated pigment selected from a lake pigment having a triarylmethane structure represented by the formula 1 and/or a rose-red structure represented by the formula 3. The dispersion treatment is carried out in the presence of an organic acid selected from the group consisting of substituted or unsubstituted arylsulfonic acids and substituted or unsubstituted arylcarboxylic acids.

The triarylmethane-based and rosin-based pigment composition of the present invention is treated with an arylsulfonic acid or an arylcarboxylic acid, thereby causing some state change of the surface of the pigment particles, and using the same to prepare a pigment dispersion, By using, for example, a color filter using the dispersion, a coating film excellent in light resistance and heat resistance can be obtained.

The triarylmethane-based pigment used in the present invention is a lake pigment having an ion of a chemical structure represented by the above formula 1, and specifically, CI Pigment Blue 1, CI Pigment Blue 1: 2, CI Pigment Blue 9, CI Pigment Blue 14, CI Pigment Blue 24, CI Pigment Violet 3, CI Pigment Violet 3: 1, CI Pigment Violet 3:3, CI Pigment Violet 27, CI Pigment Violet 39, C.1. Pigment Blue 78, CI pigment green 1, CI pigment green 2, CI pigment green 4, CI pigment blue 56, CI pigment blue 56: 1, CI pigment blue 61, CI pigment blue 61: 1, CI pigment blue 62 and other lake pigments.

Further, the rose-red pigment used in the present invention is a lake pigment having an ion of a chemical structure represented by the above formula 3, and specific examples thereof include Pigment Violet 1, Pigment Violet 1:1, Pigment Violet 2 , pigment purple 2: 2, pigment purple 81, pigment red 81: 1, pigment red 81: 2, pigment red 81: 3, pigment red 81: 4, pigment red 169, pigment red 173 and other lake pigments.

The lake former in the triarylmethane pigment and/or the rose red pigment may, for example, be phosphotungstic acid, phosphomolybdic acid, phosphotungstic acid, copper ferrocyanide, lanthanum molybdate or aluminum.

In the present invention, the organic acid for treating the triarylmethane-based pigment and/or the rose-red pigment is a substituted or unsubstituted arylsulfonic acid and/or a substituted or unsubstituted arylcarboxylic acid. Here, the substituted or unsubstituted arylsulfonic acid refers to a sulfonic acid having an aryl group having a substituent or having no substituent, and the substituted or unsubstituted arylcarboxylic acid means having a substitution. A carboxylic acid having an aryl group or a substituent having no substituent. The substituted or unsubstituted arylsulfonic acid may, for example, be an alkylbenzenesulfonic acid such as benzenesulfonic acid, naphthalenesulfonic acid, methylbenzenesulfonic acid or dimethylbenzenesulfonic acid, an alkylnaphthalenesulfonic acid or a dialkyl group. Further, naphthalenesulfonic acid or the like may be used as a heterocyclic ring such as pyridinesulfonic acid. Further, in either case, an amine group or a hydroxyl group may be substituted, and a salt such as sodium, calcium or potassium may be used. Specific examples of such an acid include sodium 2-naphthalenesulfonate, 2-naphthalenesulfonic acid hydrate, and 3-(2H-benzotriazol-2-yl)-5-dibutyl. Sodium -4-hydroxybenzenesulfonate, sodium p-styrene sulfonate, 3-methyl-1-(4-sulfophenyl)-5-pyrazolium and the like. Further, the substituted or unsubstituted aryl carboxylic acid may be benzoic acid (benzoic acid), phthalic acid, 1,2,4-benzenetricarboxylic acid, naphthoic acid (naphthalenecarboxylic acid), Naphthalene dicarboxylic acid (naphthalenedicarboxylic acid) of naphthalene-2,3-dicarboxylic acid, or methyl benzoic acid, dimethyl benzoic acid, salicylic acid (hydroxybenzoic acid), decanoic acid a substituted (2-(carboxycarbonyl)benzoic acid), hydroxynaphthalenecarboxylic acid or the like, or a salt of such sodium, calcium, potassium or the like.

The "treatment" of the arylsulfonic acid and/or the arylcarboxylic acid in the present invention includes the treatment of applying the acid to the surface of the untreated pigment, and generally refers to the above untreated pigment. After the solution of the arylsulfonic acid and/or the arylcarboxylic acid is added and stirred at a specific temperature for a specific period of time, the pigment is filtered and separated. In this case, a solution of a sulfonic acid and/or a carboxylic acid is preferably an acid such as acetic acid, citric acid, formic acid or oxalic acid. By adding such an acid, the cationic portion of the surface of the pigment can be activated, the adsorption of the sulfonic acid can be promoted, and the dispersibility of the pigment can be improved. The preferred concentration when acetic acid is added is 0.5% by mass or more, and the range in which the pigment does not dissolve. Further, the temperature of the above treatment is preferably in the range of 60 to 100 °C.

The dispersion of the present invention is obtained by dispersing a pigment composition obtained by treating a triarylmethane-based pigment and/or a rose-red pigment with an arylsulfonic acid and/or an arylcarboxylic acid in a solvent. The method of dispersing can be exemplified by a method using a paint conditioner (Paint Conditioner), a sand mixer, APEX MILL, and DISPERMAT.

Further, in the present invention, the treatment with an arylsulfonic acid and/or an arylcarboxylic acid may be carried out simultaneously with the dispersion of the triarylmethane-based pigment and/or the rose-red pigment. The amount of the arylsulfonic acid and/or the arylcarboxylic acid to be added at this time is 1 to 20 parts by mass, preferably 5 to 20 parts by mass, per 100 parts by mass of the untreated pigment. The specific dispersion method is the same as the dispersion method of the above pigment composition.

When preparing the pigment composition and the pigment dispersion of the present invention, a surfactant may be added. By adding a surfactant, the surfactant adsorbs on the surface of the pigment to enhance the dispersibility of the pigment. The surfactant which can be used in the present invention may, for example, be a sulfonic acid-based substance such as a naphthalenesulfonic acid formaldehyde condensate or a lignosulfonic acid.

The solvent which can be used in the pigment dispersion of the present invention is not particularly limited as long as it is a solvent which is generally used, but as long as the light resistance of the pigment is generally better than that of the dye, the pigment is not made into heat resistance and light resistance. The dissolver is better.

[Examples]

Hereinafter, the present invention will be described based on specific examples, but the present invention is not limited to the following description. In addition, the "parts" and "%" in the present specification indicate "mass parts" and "% by mass", unless otherwise specified.

(Example 1)

As shown in Table 1, 10 parts of untreated CI Pigment Blue 1 and 1 part of sodium 2-naphthalenesulfonate were put into 250 parts of 2.5% aqueous acetic acid solution, stirred well with a disperser, and then heated to 80 ° C, and stirred 2 hour. The obtained slurry was filtered, washed with water and dried at 80 ° C overnight to obtain 9.9 parts of the desired pigment composition.

5 parts of the pigment composition, 36.7 parts of propylene glycol monomethylether acetate, 8.3 parts of a polymer dispersant (BYK170, manufactured by BYK-Chemie Japan Co., Ltd.), and zirconia beads of Φ 0.5 mm After being placed in a paint bottle together and dispersed for one hour with a paint conditioner, 0.2 part of an acrylic resin (SPC-2000, Showa Polymer Co., Ltd.) was added to obtain a blue pigment dispersion.

(Examples 2 to 11)

The blue pigment dispersions of Examples 2 to 11 were obtained in the same manner as in Example 1 using the respective components shown in Table 1. Further, in Examples 9 and 10, the surfactant was introduced into an aqueous acetic acid solution together with C.I. Pigment Blue 1 and 1 part of sodium 2-naphthalenesulfonate.

(Comparative Examples 1 to 2)

Directly using the untreated pigment shown in Table 1, 36.7 parts of propylene glycol monomethyl ether acetate and 8.3 parts of a polymer dispersant (BYK170, manufactured by BYK-Chemie Japan Co., Ltd.) were placed together with Φ 0.5 mm zirconia beads. After the paint bottle was dispersed by the paint conditioner for one hour, 0.2 part of an acrylic resin (SPC-2000, Showa Polymer Co., Ltd.) was added to obtain a blue pigment dispersion.

(Evaluation)

[Production of glass coated plate for test]

The pigment dispersion was applied to a square glass plate having a side length of 10 cm using a spin coater to prepare a glass plate for test.

[Evaluation of heat resistance]

The glass coated plate was allowed to stand in an air bath heated to 200 ° C for one hour. The color difference (ΔEab) of the glass coated plate before and after the air bath was measured was measured using a colorimeter (CM3700D, manufactured by Konica Minolta). The coated plates of the dispersions of Comparative Examples 1 and 2 were simultaneously placed in an air bath as standard data, and the color difference was defined as a reference (1.00), and the ratio of the color difference of each of the glass coated plates was shown in Table 1.

[Evaluation of light resistance]

It was exposed to a 180 W xenon light for 24 hours using a light resistance tester (XL75 low temperature Cycle Xenon Weather Meter, Suga tester). The color difference (ΔEab) of the glass coated plate before and after the exposure was measured using a colorimeter (CM3700D, manufactured by Konica Minolta). The coated plates of the dispersions of Comparative Examples 1 and 2 were simultaneously placed in an air bath as standard materials, and the color difference was defined as a reference (1.00), and the ratio of the color difference of each of the glass coated plates was shown in Table 1.

[Evaluation results]

It is understood that the ratio of the color difference (ΔEab) of the test glass coated sheets produced using the dispersions of Examples 1 to 11 is less than 1 in the heat resistance and light resistance test items, and the comparative examples in which the organic acid treatment is not performed. It is excellent in heat resistance and light resistance compared to a coated plate.

(Examples 12 to 13)

As shown in Table 2, 4.65 parts of untreated CI Pigment Blue 1, 0.35 parts of sodium 2-naphthalenesulfonate, 36.7 parts of propylene glycol monomethyl ether acetate, and 8.3 parts of polymer dispersant (BYK170, BYK-Chemie‧ Japan) Φ 0.5 mm zirconia beads were placed in a paint bottle, and after dispersing for one hour with a paint regulator, 0.2 part of an acrylic resin (SPC-2000, Showa Polymer Co., Ltd.) was added to obtain a blue pigment dispersion.

(Comparative Examples 3 to 4)

As shown in Table 2, an untreated pigment was used, and a blue pigment dispersion was obtained in the same manner as in Examples 12 to 13 except that the organic acid was not used.

(Comparative Example 5)

5.0 g of Basic Blue 7 was stirred and dissolved in 250 g of water to prepare an aqueous solution of Basic Blue 7. Separately, 2.5 g of sodium naphthalenesulfonate was dissolved in 200 g of water at 80 ° C to prepare an aqueous solution of naphthalenesulfonic acid. The aqueous solution of the naphthalenesulfonic acid was gradually added to the aqueous solution of the basic blue 7 under stirring at 50 ° C, and the mixture was further stirred for 2 hours, and the precipitate was filtered, dried, and pulverized to obtain a pigment composition.

(Evaluation)

A test glass coated plate was produced in the same manner as above, and heat resistance and light resistance tests were carried out in the same manner as above. The results are shown in Table 2.

[Evaluation results]

It is understood that the ratio of the color difference (ΔEab) of the test glass coated sheets produced by using the dispersions of Examples 12 to 13 is less than 1 in the heat resistance and light resistance test items, and the comparative examples in which the organic acid treatment is not performed. It is excellent in heat resistance and light resistance compared to a coated plate.

[Industrial availability]

When the triarylmethane-based and rosin-based pigment composition of the present invention and the pigment dispersion using the same are used, since a coating film excellent in heat resistance and light resistance can be obtained, it can be used for a liquid crystal display device or a color filter. In addition to fields such as color filters such as organic EL displays, it can also be used in the field of toners and inkjet inks.

Claims (11)

A pigment composition characterized in that an untreated pigment selected from a lake pigment having a triarylmethane structure represented by the formula 1 and/or a rose-red structure represented by the formula 3 is selected from the group consisting of substituted or unsubstituted The organic acid of the group consisting of the substituted arylsulfonic acid and the substituted or unsubstituted aryl carboxylic acid is treated, Here, in the formula 1, R ¹ , R ² , R ³ and R ⁴ are each independently -H, -CH ₃ , C ₂ H ₅ , -Ph, -PhCH ₃ , -CH ₂ Ph(SO ₃ .1/ 2Ba), or -CH ₂ Ph(SO ₃ .1/3Al), substituted or unsubstituted phenyl or naphthyl group represented by R; In the formula 2, R ⁵ is -H, -NHCH ₃ , -N(CH ₃ ) ₂ , -N(C ₂ H ₅ ) ₂ , -NHPh, or -NHPh(CH ₃ )(SO ₃ H) or a salt thereof, R ⁶ is -H, -Cl, or -SO ₃ H or a salt thereof, R ⁷ is -NHC ₂ H ₅ ; In the formula 3, R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently -H or an alkyl group, R ¹² is a -H, an alkyl group, or a substituted or unsubstituted phenyl group. The pigment composition of claim 1, wherein the untreated pigment is C.I. Pigment Blue 1. The pigment composition of claim 1, wherein the untreated pigment is C.I. Pigment Violet 1. The pigment composition according to any one of claims 1 to 3, wherein the organic acid is a compound selected from the group consisting of: . The pigment composition according to any one of claims 1 to 3, further comprising a surfactant. A pigment dispersion using the pigment composition of any one of claims 1 to 5. A pigment dispersion characterized in that an untreated pigment selected from a lake pigment having a triarylmethane structure represented by Formula 1 and/or a Rose Ben structure represented by Formula 3 is selected from substituted or unsubstituted Dispersing treatment in the presence of a substituted organic acid of the group consisting of a substituted aryl sulfonic acid and a substituted or unsubstituted aryl carboxylic acid, Here, in the formula 1, R ¹ , R ² , R ³ and R ⁴ are each independently -H, -CH ₃ , C ₂ H ₅ , -Ph, -PhCH ₃ , -CH ₂ Ph(SO ₃ .1/ 2Ba), or -CH ₂ Ph(SO ₃ .1/3Al), substituted or unsubstituted phenyl or naphthyl group represented by R; In the formula 2, R ⁵ is -H, -NHCH ₃ , -N(CH ₃ ) ₂ , -N(C ₂ H ₅ ) ₂ , -NHPh, or -NHPh(CH ₃ )(SO ₃ H) or a salt thereof, R ⁶ is -H, -Cl, or -SO ₃ H or a salt thereof, R ⁷ is -NHC ₂ H ₅ ; In the formula 3, R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently -H or an alkyl group, R ¹² is a -H, an alkyl group, or a substituted or unsubstituted phenyl group. The pigment dispersion of claim 7, wherein the untreated pigment is C.I. Pigment Blue 1. The pigment dispersion of claim 7, wherein the untreated pigment is C.I. Pigment Violet 1. The pigment dispersion according to any one of claims 7 to 9, wherein the organic acid is a compound selected from the group consisting of the compound 4, The pigment dispersion according to any one of claims 7 to 9, which is further subjected to a dispersion treatment in the presence of a surfactant in addition to the organic acid.