JPS5924760A - Method for coloring titanium dioxide - Google Patents

Abstract

PURPOSE:To obtain colored TiO2 which has excellent solvent resistance, hardly suffers the elimination of dye, has a clear tint and is useful for cosmetics, paints, etc., by treating TiO2 with a specified titanium coupling agent and dyeing it with an anionic dye. CONSTITUTION:TiO2 is previously treated with a titanium coupling agent having amino groups and/or substd. amino groups, such as isopropyltris(aminoethylaminoethyl)titanate, and dyed with an anionic dye such as C.I. Direct Yellow 8, or C.I. Mordant Orange 1 to color TiO2. The dye is hardly eliminated from the colored TiO2. The colored TiO2 has excellent solvent resistance and a clear tint and is useful as a pigment for cosmetics, paints and ink for marking pen.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for coloring titanium dioxide to obtain colored titanium dioxide having a clear hue and useful for cosmetics, paints, inks for marking pens, and the like.

Titanium dioxide has traditionally been praised as an excellent white pigment, and has been used alone or in combination with other pigments. Particularly, Halft-7, which is used by mixing with color pigments, exhibits a beautiful hue due to the breaking power and hiding power of titanium dioxide.

However, in the case of Shinkai pastel colors in which the amount of one color pigment used is reduced, it is inevitable that the image becomes somewhat unclear due to the particle size of the pigment.

However, unlike pigments, when using bright dyes, there was a problem that they were not water resistant. The present inventors have conducted intensive research on how to fix dyes on the surface of titanium dioxide to obtain vivid pastel-like pigments by coloring titanium dioxide.As a result, the following findings have been made. I got it.

That is, titanium dioxide itself cannot be dyed with ordinary anionic dyes (direct dyes, acid dyes) or cationic dyes (basic dyes). Therefore, there are methods such as forming a dye lake on the surface of titanium dioxide, but since the dye is simply attached to the surface of titanium dioxide, this type of colored titanium cannot be used in paints, inks for marking pens, etc. The dye lake gradually desorbs from the titanium dioxide surface and
It no longer exhibits its original pastel tones. Also, in the case of oil-based solvents, the dye lake may dissolve or bleed into one letter or 20 figures.

Therefore, the present inventors introduced a basic amino group or a substituted amino group onto the titanium dioxide surface in order to bind the dye or dye lake to the titanium dioxide surface more strongly than simply adsorbing it, and then used an anionic dye. The present invention was completed by discovering that dyeing allows for strong dyeing, and that desorption of the dye and bleeding due to solvents can be suppressed.

That is, the gist of the present invention is a method for coloring titanium dioxide, which is characterized in that titanium is previously treated with a titanium coupling agent containing an amino group or/and a substituted amino group, and then dyed with an anionic dye. It is something to do.

Two aspects of the present invention will be described in detail below.

To react titanium dioxide with an amino group-substituted amino group, a titanium compound called a titanium coupling agent is used. For example, by dispersing titanium dioxide in a solvent such as titanium dioxide, adding a titanate having an amino group or/and substituted amino group, and heating as necessary, amino groups and/or substituted amino groups can be easily added to the surface of titanium dioxide. can be introduced into As a titanate (titanium strength, pulling agent) having an amino group or a substituted amino group.

Isopropyl tris (aminoethylaminoethyl) titanate Inopropyl tris (N'N' dimethylaminoethylamine ethyl) titanate Isopropyl tris (2-aminoethyl) titanate Ethylene bis (aminoethylaminoethyl) titanate Ethylene bis anthra Nil titanium 1 ethylene 4
・Aminobenzenesulfonyl stearyl titanate, etc. can be used. The amount used is 1 for titanium dioxide.
~10 The weight clerk is suspicious. If it is less than 1% by weight, it cannot be dyed with an anionic dye, and if it is more than 10% by weight, the dyeing density cannot be increased any further.

Next, titanium dioxide into which an amino group and/or substituted amino group has been introduced is colored with an anionic dye by dispersing titanium dioxide in water at a pH of 3.5 to 4.5. Temperature 80-95
It can be carried out by dyeing at a concentration of 0.5 to 5 at ℃.

Examples of anionic dyes include direct dyes, acid dyes, and acid mordant dyes. Examples of direct dyes include C, 1, Direct Yellow 8. Same 11. Same 12゜ Same 26. Same 27
．． Same 28. Same 63. 39. 44, 50. C,1,
Direct Orange 6° io, 26. 29. 39. 41. 49, 102. C, 1, Direct Red 21 4. 20. 26. Same 24. Same 3
1. 39° 46. Same 62. 66, 75. Same 79
．． 80, 81.゛Same 83. Same 84. Same 113°C,
1, Direct Violet 7, Direct Violet 9. Same 35° Same 4
7. 48. Same 51. C, L Direct Blue 1. Same 15. Same 22. 25. 41. 71, 76, 7
8. 86. 90. Same 98° Same 106. Same 108. 120. 123. 158, 165. 165. Same 168. 226°C, 1, Direct Green 28
．． Same 33. Same 59°C, 1, Direct Brown 44
．． Same ioo, Same 1061 Same 112. C, 1, Direct Black 17, Same 19. Same 22. 32. Same 5
1. 561 71. Same 74. 75. There are 77 etc.

As acidic dyes, C, 1, Acid Yellow 1° and 5. Same 7. Same 11. Same 17. Same 23. 251 29
．． 36. 68. 40. Same 42. 44, 76,
98. 99. C, 1, A/7 de Oren;'1. Same 7. Same 8. Same 10. Same 19゜ Same 20. Same 24. Same 28.
Same 33. 41. 51, 56. Same 74. C, 1, A/Tsudo Red 1, 6. Same 8. Same 9. Same 13. Same 14th
．． 18th, 26th. Same 27. 32. 35. Same 37,
Same 42. Same 51. Same 52. 80. 82, 83. Same 87. 88. 89. 92, 94. 97. Same 1
06. Same 111゜ Same 114. 115. 133. Same 1
34. 145, 154. 155. Same 158. Same 1
80, 183. Same 184. 186. 198, 2
49. 265. C, 1, Add Violet 7
, same 11. Same 15. 34. Same 4 t, M4311 part M491 Same 511 Same 631 C, I.

Ashi de Bleu 1. Same 7. Same 9. Same 15. Same 22, same 23. 25. Same 27. 29. 40, 41. Same 4
6. 45. 59. 62, 74. 78. Same 80
．． Same 83. 90, 92. Same 93. Same 100. Same 1o
2゜same 103. Same 1o4. Same 113. 117. Same 12th
0, 127. 138. Same 158. 161, C,
1. Anne de Green 3. Same 9. Same 12, same 16. Same 19. 20. 25. 27, 35. 36. Same 4
1. 44. (:, I.

Anne de Brown 2. Same 4. 132. Same 14゜ Same 2
0. Same 27. Same 103. C, 1, A/D BRA, RI1. Same 2. Same 7. Same 24. 26. 31, 48. Same 51. 52, etc., and acids are used as mordant dyes.
C, 1, Mordant Erow 1, same 6. Same 5. 26.
30. 38°C, 1, Mordant Orange 1. Same 4. Same 6. 29, 37. C, 1, Mordant Red 3. Same 7, same 6. Same 9. Same 11. Same 13. 21゜26. Same 27. 30, C, 1, Morta: y)
, Hiore, ) 1. Same 5. 44. C, 1, Mordant Blue 1. Same 7. Same 8. Same 13. 29. Same 4
4, 47. 48. C, 1, Mordant Gree: /
11. Same 15. Same 17, C, 1, Morta 7) - Brown 1. Same 14. Same 15. Same 19. 21゜33. 40. C, 1, Mordant Black 1゜6. Same 9.
Same 11. Same 13. Same 17. 38° 51. 54, etc., and can be used alone or in combination.

A basic explanation will be given below using actual examples, and in the examples, "part" indicates "heavy grinding part".

1 0) Surface modification of titanium dioxide TITONEA ~ 150 (anatase type titanium manufactured by Sakaihigaku) to part xylene 5o
Juice 1s KR-44C isopropyl tris (aminoethylaminoethyl) manufactured by Titanate Kenrich] One part was stirred at 50°C for 24 hours and filtered.

Vacuum dry at 50°C.

■Dyeing of modified titanium dioxide■ Modified titanium dioxide 10 parts water
200 parts Kayakuken Tartrazine Conc (C, 1, Acid Yellow 26° manufactured by Nippon Kayakufu Co., Ltd.) 0.5 parts Acetic acid was added to the above ingredients to adjust the pf to 4.0.

By stirring at 85° C. for 1 hour, a vinegar-colored pastel dyed pigment is obtained.

Comparative Example 1 TITONE A-150 10 parts water
200 Part Kayak Tartrazine Conch
While stirring 0.5 parts of the above ingredients at room temperature,
Aqueous solution of chloride/thurium 5 is added dropwise, dye lake 1 is applied to titanium dioxide, and the mixture is filtered and washed with water to obtain a pigment dyed in a yellow pastel tone.

Example 2 (Surface modification of titanium dioxide TITONER-650 (N-chill type titanium, manufactured by Sakai Chemical Co., Ltd.) 10 parts Toluene 100 parts KR-43 [: Inoprovir tris (NN dimethylamine ethylamino 1″ norititanate)] 1 part 8 of the above ingredients
Stir at 0°C for 24 hours, filter and air dry to 50°C.

■ Dyeing of modified titanium dioxide (D modified titanium dioxide 10 parts water
20
0 parts Crampons Amaranth (C, 1, Acid Yellow 27.1 manufactured by Bakudoya Chemical Co., Ltd.) 0.5 parts Acetic acid was added to the above ingredients to adjust the pH to 4.0.

By stirring at 90° C. for 30 minutes, a reddish yellow pastel dyed pigment is obtained.

Comparative Example 2 T I TONle 1l-65010 parts water
20
Part 0 Crampons/Amaranth
While stirring 0.5 parts at room temperature, add 10 parts of calcium chloride.
By dropping an aqueous solution of titanium dioxide and allowing the dye lake to adhere to the titanium dioxide, a pigment dyed in a reddish yellow pastel tone is obtained.

Example 3 Modified titanium dioxide of Example 1 10 parts Mitsui Nylon Fast Blue G 011 parts (
C,,I,Acid Blue25. (Made by Mitsui Toatsu Chemical)
water
Formic acid was added to 150 parts to adjust pf to 4.0, and the mixture was stirred at 80° C. for 2 hours to obtain a yellow pastel dyed pigment.

Comparative Example 3 Kayaku Tartrazine Concrete Rinimitsui Nylon Fast Blue G used in Comparative Example 1 was added to 0.1
A pigment similar to Example 3 was obtained by dyeing in the same manner as in Comparative Example 1.

Example 4 Modified titanium dioxide of Example 2 10 parts Kayanor Brown RO, 1 part (C11, Acid Graph 9 22 manufactured by Nippon Kayaku ■) Water

Formic acid was added to 100 parts to adjust the pH to 4.0, and the mixture was stirred at 90° C. for 45 minutes to obtain a pigment dyed in a brown pastel tone.

Comparative Example 4 A pigment similar to Example 4 was obtained by dyeing in the same manner as in Comparative Example 2, using 1 part of Kayanol Brown R instead of the crampon amaranth used in Comparative Example 2.

The solvent resistance of each pigment of Examples 1 to 4 and Comparative Examples 1 to 4 is shown in Table 1.

*Note: Take 1 g of each pigment in a test tube, add 10 mt of solvent, and after 10 hours at 50°C, judge spots 1 to 1 on Toyo Kuchigami 2.

◎ No bleed ○ Slight bleed ∆ Bleed The coloring of each pigment and the removal of the dye lake in Examples 1 to 4 and Comparative Examples 1 to 4 are as follows.

The test method is to crush each pigment 2I in a mortar, and divide it into water.
Desorption of the colored titanium dioxide from the surface was observed after 2 passes. The results are shown in Table-2.

-2 +g As shown above, titanium dioxide obtained by the coloring method of the present invention has excellent solvent resistance, dyes are difficult to desorb from titanium dioxide, and has a clear hue, making it suitable for use in cosmetics, paints, and marking pens. It is useful as a pigment with inks.

Patent applicant: Bentel Co., Ltd.

Claims (1)

[Claims] A method for coloring titanium dioxide, characterized in that titanium is previously treated with a titanium powder containing an amine group or/and a substituted amino group, a pulling agent, and then dyed with an anionic dye.