TW201107422A - Pigment composition of triarylmethane and rhodamine and pigment dispersion using the same - Google Patents

Abstract

The invention provides a color lake pigment with excellent light resistance and heat resistance and having the triarylmethane structure and/or rhodamine structure, and also provides a pigment dispersion using the same. A pigment composition, characterized by processing the unprocessed pigment selected from the color lake pigments having the triarylmethane structure and/or rhodamine structure with an organic acid selected from the group consisting of substituted or unsubstituted aryl sulfonic acids and substituted or unsubstituted aryl carboxylic acids.

Description

[Technical Field] The present invention relates to a triaryl decane-based and rosin-based pigment composition, and more particularly, the present invention relates to a triaryl fluorene which is excellent in light resistance and heat resistance. • Rhodium and rose red pigment compositions and the use of such pigment dispersions. [Prior Art] In the past, triarylmethane-based dyes and pigments have been used as coloring agents, inkjet inks, color filters, and the like (Patent Documents 1 to 4). However, triaryl decane-based 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 trisyl group and an organic acid (Patent Document 6). [Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei. No. Hei. Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2006-306933. The triaryl sulphur-based pigments are not sufficient; the photo-forming and heat-resistance are not sufficient, and the steps of the biosynthesis are complicated, and have not been put into practical use. Therefore, the object of the present invention is to provide a light-blocking and heat-resistant excellent 201107422 diarylmethane-based pigment composition and a pigment dispersion using the same, and to provide a rose excellent in light resistance and heat resistance. The red pigment composition and the pigment dispersion using the same. The present invention has been completed according to the following findings: a lake pigment having a bismuth-based sinter structure and a lake pigment having a rose-red structure, treated with a sulfonic acid or a carboxylic acid having an aryl group, This greatly enhances the pigment: resistance and heat resistance. That is, the pigment composition of the present invention is characterized in that an untreated pigment selected from the lake pigment having the triarylsulfane structure shown in Formula 1 and/or the Roser red structure shown in Formula 3 is selected. The organic acid of the group consisting of a freely substituted or unsubstituted arylsulfonic acid and a substituted or unsubstituted aryl carboxylic acid is subjected to treatment. [Chemical 1]

R Here, in the formula 1, R1, R2, and R3 ' R4 are each independently _ Η ' - CH3, C2H5, -Ph(phenyl), -PhCH3' -CH2Ph(S〇3. 1/2Ba), or CH2Ph(S〇3 · 1/2A1), substituted or unsubstituted phenyl or naphthyl group represented by R system 2, 4 201107422 [Chemical 2]

In the formula 2, R5 is _H, -NHCH3, - n(Ch3)2, _n(C2H5)2, -NHPh, or -NHPh(CH3)(S03H) or a salt thereof, R6 is -n, -Cl, or A S03H or its salt, R7 is -NHC2H5, [Chemical 3]

^^/COORl2 3, ..., ^ 以 丨丨 丨丨 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 颜料 颜料 颜料 颜料 颜料 颜料 颜料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: The untreated pigment of the ternary pigment of the 201107422 rose-red structure shown in the structure of the triaryl group and/or the <3>, is selected from substituted or unsubstituted aryl acid and substituted or unsubstituted The dispersion treatment is carried out in the presence of an organic acid of a group consisting of substituted aromatic acids. The triarylsulfonate and rosin pigment composition of the present invention is treated with an aryl or acid aryl acid to thereby cause some state change of the surface of the pigment particles, and the pigment is used to prepare the pigment. In the η, y shape, the dispersion 1 is used as, for example, a color former, and a coating film excellent in light resistance and heat resistance can be obtained. [Embodiment] The triarylmethyl ketone system used in the present invention is a color chamber & c I « , /, and s, which have the chemical structure of the chemical formula 1 described above. Blue 24,. Pigment Violet 3, CJ Pigment Violet 3: i ci J Shake Rabbit 3. 3, cl Pigment Violet 27, c I Pigment 呰CI ^ M ^ 1.1. 枓 枓 '39, 〇:.]. Pigment Blue 78, CI Pigment Blue broad pigment green 2.丄Pigment Green 4,. · Pigment blue 56, yan ^ ray blue 56: 1, c 丄 pigment blue 61, CJ. pigment M6i: i, ci Yan 枓 blue 62 and other lake pigments. The rose-red pigment used in the crystallization month shown is a color-activated pigment having the ion of the above-mentioned formula 3 pigment violet. Specifically, 81, pigment: pigment violet 1: ^ Pigment Violet 2 Pigment violet 2: 2, pigment violet if red red 81: 1, pigment red Μ: 2, pigment red 81: 3, pigment red / red 169, pigment red 173 and other lake pigments. Diarylmethane-based pigments and commensurate examples of secondary pigments, pigments in industrial pigments, New Zealand. , cut, sorrel, sulphuric acid, copper ferrocyanide, acid, 6 201107422 In the present invention, the organic acid used to treat the triarylmethane pigment and/or the rose red pigment is substituted or not Substituted aryl acid and/or substituted or unsubstituted aryl carboxylic acid. Here, the substituted or unsubstituted aryl acid refers to a sulfonic acid having a substituent or an aryl group having no substituent, and the substituted or unsubstituted aryl carboxylic acid means having a substitution. A carboxylic acid having an aryl group or a substituent having no substituent. The substituted or unsubstituted aryl stone is only known, and examples thereof include alkylbenzenesulfonic acid, alkylnaphthalenesulfonic acid, and dialkylbenzene such as benzoic acid, naphthic acid, methylbenzene acid, and dimethylbenzenesulfonic acid. Further, a naphthalenesulfonic acid or the like may be used, and a heterocyclic ring such as pyridinesulfonic acid may be used. Further, in any of them, 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 acids include sodium 2-naphthalenesulfonate represented by Chemical Formula 4, 2-naphthalenesulfonic acid hydrate, and 3-(2H-benzotriazol-2-yl)-5 primary Butyl-4 sodium hydroxybenzene sulfonate, sodium p-styrene sulfonate, 3-methyl- _ sulfonyl sulfonate _5 〇 〇 ° ° ° ° ° ° ° ° '' Carboxylic acid, which may be benzoic acid (cracked acid), o-dibenzoic acid, 1,2,4-benzenetricarboxylic acid, naphthoic acid (naphthoic acid), naphthalene-2,3 as shown in Figure 4. Naphthalene dicarboxylic acid (naphthalenedicarboxylic acid) of dicarboxylic acid, and may also be methyl benzoic acid, dimercapto benzoic acid, salicylic acid (hydroxybenzoic acid), decanoic acid (2-(carboxycarbonyl) benzoin A salt such as an acid, a hydroxynaphthalenecarboxylic acid or the like, or a salt of such a sodium, calcium or potassium. 201107422 【化4】

Naph-SNa *s〇3Na

Naph-SH Naph-2C00H

COOH COOH T a 595

s〇iNa

St-SNa 3py ^O-s 〇

The "virtual" of the A^^-based decanoic acid and/or aryl carboxylic acid of the present invention includes the treatment of the crucible, and typically, the surface of the untreated pigment is The above untreated pigment is charged with an arylsulfonate/amp;/or aryl carboxylic acid, and after being stirred at a specific temperature for a specific period of time, the pigment is passed through and separated. Preferably, the solution of the sulfonic acid and/or the carboxylic acid is added with acetic acid, hydrazine, carboxylic acid, oxalic acid or the like. By adding such an acid, the cationic portion of the surface of the pigment can be activated to promote the adsorption of the acid to enhance the dispersibility of the pigment. The preferred concentration when acetic acid is added is a range in which the pigment is not dissolved. Further, the temperature of the above treatment is preferably in the range of 60 to 10 °C. The dispersion of the present invention is obtained by dispersing a triarylmethane-based pigment and/or a rosin-based pigment as a pigment composition treated with an aryl acid and/or an aryl carboxylic 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 arylsulfonic acid and/or the arylsulfonic acid and/or the aryl carboxylic acid may be simultaneously treated with the dispersion of the triarylmethane pigment and/or the rose 8 201107422 red pigment. The amount of the aryl carboxylic acid to be added is, for example, 1 to 20 parts by mass, preferably 5 to 20 parts by weight, based on 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 will adsorb to the surface of the pigment to enhance the pigmentation (4). The surfactant which can be used in the present invention may, for example, be a naphthalenesulfonic acid formaldehyde condensate or a sulfonic acid-based material such as lignosulfonic acid. 0 The solvent used in the pigment dispersion of the present invention may be used, and there is no particular light resistance compared with the dye. Good, better for heat. The solvent which can be used is generally limited to the nature of the pigment, and does not dissolve the pigment in terms of optical properties. [Examples] Hereinafter, the present invention will be described in accordance with specific examples, but The invention is not limited to the following description. In addition, in this specification, f-knives and %" respectively indicate r mass parts "what is the case", except for the case where it is specified, respectively. (Example 1) As shown in Table W, 'H' is not processed. ι················································································································ After drying overnight at 80 ° C, 9.9 parts of the pigmented pigment composition was obtained. 201107422 5 parts of the pigment composition, 36.7 parts of propylene glycol monomethylether acetate ' 8.3 parts of polymer 糸 dispersing agent (BYK1 70, BYK - manufactured by Chemie Japan), and 〇5mm The zirconia beads were placed in a lacquer bottle together and dispersed for one hour with a paint regulator, and 0.2 part of an acrylic resin (SPC-2000, Showa Polymer Co., Ltd.) was added to obtain a blue pigment dispersion. (Examples 2 to 1 1) Using the respective components shown in Table 1, the blue pigment dispersions of Examples 2 to 1 were applied in the same manner as in Example 。. Further, in the implementation of 9 and 1 ,, the surfactant was introduced into an aqueous acetic acid solution together with C.L pigment blue quinone and sodium 2-naphthalene sulfonate. (Comparative Examples 1 to 2) The untreated pigments shown in Table 1 were used as they were, and 36 7 parts of propylene glycol mono-acetate and 8.3 parts of a polymer dispersant (BYK17®, BYK-chemie) were used.

It is placed in a lacquer bottle together with φ 〇 5mm yttrium oxide beads. After the coating is dispersed for one hour, 〇 2 parts of acrylic resin (spc 20〇〇 'Showa Polymer Co., Ltd.) is added to obtain blue Color pigment dispersion 10 201107422 [I ΐ 垅 Light resistance standard (1.00) 0.66 0.72 0.80 0.66 0.76 0.65 0.79 0.59 0.73 0.62 Reference (1.00) 0.37 7.73 f; For heat j inch inch (Noomvor*-inch O^oc^^o ^t^n^n^foo^ovo ^ooocJoocJooo Benchmark (1.00) 0.90 5.61 Processing Temperature 80°C 80°C 80°C 80°C 80°C 80°C 80°C 80°C 80°C 80°CIO ^P 1 ο 〇00 Addition amount oo rn ro V0 Ridge rp *Learning oo SS w ω QQ Treatment of aqueous solution 250 parts 250 parts 250 parts 250 parts 250 parts 250 parts 250 parts 250 parts 250 parts 250 parts umbrella 1 ο 〇 ^ in (N inch 2.5% 1.0% 2.5% 2.5% 2.5% 2.5% 2.5% 2.5% 2.5% 2.5% 1佘1 oi Fried acetic acid citric acid acetic acid acetic acid acetic acid acetic acid acetic acid acetic acid acetic acid acetic acid 1 organic acid addition amount 1.0 part 1 _ 0.5 0.5 parts 2.0 parts 1.0 parts 1.0 parts 1.0 parts 2.0 parts 1.0 parts 2.0 parts, ^ Φ 1 ο V-) " CN ' compound UW cd C3 Λ C&qu Ot;\ Λ 扣 z ZZ ^ ^ Z U1 zzz Naph-SNa Naph-SNa 埏 量 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 PB1 PB1 PB1 PB1 PB1 PB1 PB1 PB1 PB1 "g Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 2 Example 11 Comparative Example 5

(3) uisBCQnr'CQe (inch=. (铋e<<^-te^^T-lJir) (荽伞柴·过&- 翘蝥濉)HN lowwQr ^^穿丨5 — (^械努—S丨一丨毛®-丨£h>^<j£ Signing Yuan Yuan 0蚪脔=SNS-1S (铋s3ilo>.lI.2u3ds Jqlo6SMAnNIl)冢键^-f澍-inch-fh赛Μ-ς- (砩-CN-^w --H3) -ε=ιο6ιη-Η #^^^^M — etl^=HOOu(N-M&N (%0z,) ^^^^^^—cs=bns-j3&n

铋5T3 = lAd l 3sd=sdF 201107422 (Evaluation) [Preparation of glass coated plate for test] A pigment dispersion was applied to a square glass plate having a side length of 10 cm using a spin coater (Spin Coater) to prepare a test glass. Coated. [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 (Δ Eab) 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 incorporated into Table 1. [Evaluation of Light Resistance] A light resistance tester (XL75 type low temperature Cycle Xenon Weather Meter, Suga tester) was used to expose to a 180 W xenon lamp for 24 hours. The color difference (Δ Eab) of the glass coated plate before and after the exposure was measured using a colorimeter (CM3700D '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 determined as a reference (1.〇〇), and the ratio of the color difference of each of the glass coated plates was incorporated into the table. 1 indicates. [Evaluation Results] It can be seen that the ratio of the color difference (Δ Eab) of the test glass coated sheets prepared using the dispersions of Examples 1 to 11 was less than 1 ' in the test items of the heat and the light and the organic acid. The heat treatment and light resistance of the comparative examples of the comparative examples were excellent. 12 201107422 (Examples 12 to 13) As shown in Table 2, 4.65 parts of diced persimmon + - c chopped CI. Pigment blue 1, 0.35 parts of 2 - naphthoic acid, 36.7 parts of propylene with Narumol Monoterpene ether acetate, 8.3 parts of polymer dispersant (BYK170, BYK-τ Al,

Lhemie · japan system), φ 〇 5mm oxidized wrong beads were placed in a paint bottle, dispersed for one hour with a paint regulator, and 2 parts of acrylic resin (SPC-2000, Showa Polymer Co., Ltd.) was added to obtain blue pigment dispersion. body. (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 25 μg of water to prepare an aqueous solution of Basic Blue 7. Separately, 2.5 g of naphthoic acid was dissolved in 2 g of water to prepare a naphthalenesulfonic acid aqueous solution. The aqueous solution of naphthalenesulfonic acid was gradually added to the aqueous solution of 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. [Table 2] / Organic acid evaluation result Name addition amount Compound 2 Addition amount Heat resistance Light resistance Comparative Example 3 Example 12 PB1 PB1 4.65 parts 4.65 parts Naph-S 0.35 parts basis (].00) 0.65 basis (1.00) 0.68 Comparative Example 4 Example 13 PV1 PV1 Main 1 Λ ω rr 4.65 parts 4.65 parts Naph-S 0.35 parts basis (1.00) 0.90 basis (1.00) 0.37 Ή), *2)... same as Table 1 13 201107422 (Evaluation) A test glass plate was produced in the same manner, and the heat resistance and light resistance test were carried out in the same manner as above. The results are shown in Table 2. Incorporation of [Evaluation Results] It is understood that the ratio of the color difference (Δ Eab) of the test glass coated sheets produced using the dispersions of Examples 12 to 13 is less than 1' and not in the heat resistance and light resistance test items. The heat resistance and light resistance were superior to those of the comparative examples of the organic acid treatment. [Industrial Applicability] When the use of the composition of the Sanfang 4A Institute and the Meishen Red pigment of the present invention is cold and the use of such a pigment dispersion is obtained, since a coating film excellent in heat resistance and light resistance is obtained, In addition to being used in the fields of liquid crystal display m color filters, color filters such as EL displays, etc., it can also be utilized in the field of toner inkjet inks. [Simple diagram description] None [Main component symbol description] None 14

Claims (1)

201107422 VII. Patent application scope: i A pigment composition characterized in that: an untreated color of a lake pigment selected from the group consisting of a triaryl decane structure represented by Formula 1 and/or a rose block structure represented by Formula 3. a pigment which is treated with an organic acid selected from the group consisting of substituted or unsubstituted aryl sulfonic acids and substituted or unsubstituted aryl carboxylic acids; R Here, in the formula 1, R1, R2, R3, and R4 are each independently -H, -CH3, C2H5, -Ph, - PhCH3, -CH2Ph (S03.), or -CH2Ph(S〇3.1) /2A1)' substituted or unsubstituted phenyl or naphthyl group represented by R system 2; 15 201107422 2 In the R2 system, a ring, a NHCH3, a N(CH3)2, -N(c2H)-NHPh, or -NHPh(CH3)(S03H) or a salt thereof, R6 system~H, c or a S03H or its salt, R7 is a NHC2H5; [Chemical 3] 8 >^^/C00Rl2 10 'Rll 3, R8, R9, r10 p 12 are each independently -II ι> R is -H, alkyl n is H, or alkyl, 9 ,. Unsubstituted! I 2 · If the scope of the patent application is replaced by the base. The chemical pigment is c.i·pigment blue enamel. The pigment composition of the item, wherein the material is not in the third place, as in the patent application scope, the pigment is c丄 pigment purpura. a pigment composition, wherein the portion is not included in the scope of the patent application, wherein the organic acid is a pigment composition selected from the group consisting of 3, and the compound of the compound: 16 201107422 Ut4] Naph~SNaC〇 r S〇3Na Naph-SH Cers〇3H Naph-2C00H ccc COOH COOH T-595 St-SNa 3PY 5. As claimed in the scope of claim i to further containing a surfactant. A pigment dispersion which is used in any one of the pigment compositions. The pigment composition of any one of the items, there are patent application scopes 1 to 5, and the Yankee Dispersion Point, He Xinhe, will be selected from the 示, 丄 I-square decane Structure and / or 3 substituted or unsubstituted ... Γ The treated pigment is subjected to a dispersion treatment in the presence of an organic hydrazine selected from the group consisting of the obtained group or the unfilved aryl group. The pigment pigment of item 7 of the patent application scope is C.I. Pigment Blue. Knife polity', among them, far away; such as the scope of the patent scope of the seventh patent pigment is CL pigment purple cloth 4 knives loose body, which is not as in the patent application range 7 to 9 box body 'where the organic 睃The pigment of any one of them is a compound selected from the group consisting of compounds shown in Formula 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. Eight, schema · None 18