JPS5931544B2 - anthraquinone pigment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new anthraquinone pigment, and more specifically, an anthraquinone that easily dissolves in organic materials such as refrigerants, refrigeration oil, organic liquids, and various synthetic resins, and provides excellent coloring effects. The purpose is to provide a series of pigments.

Conventionally, in various types of equipment that use refrigerants, refrigeration oil, or mixtures thereof, these refrigerants have been coated with various pigments so that if the refrigerant leaks from the equipment, the location of the leak can be easily detected. It may become colored.

Examples of such dyes include oil-soluble azo dyes (Japanese Patent Publication No. 18551/1983) and anthraquinone dyes (
Japanese Patent Publication No. 52-39174) etc. have been proposed.
However, the former has insufficient heat resistance and is likely to decompose during use, while the latter has insufficient solubility in refrigerants and also has low coloring power. The present inventors newly synthesized various anthraquinone dyes to solve the drawbacks of the prior art as described above, and found that among these dyes, anthraquinone dyes with specific substituents are resistant to refrigerants and freezing machine oil. The present invention was completed based on the finding that the pigment has sufficient solubility and is significantly superior to conventional pigments in terms of heat resistance, coloring power, hue, etc.

That is, the present invention relates to an anthraquinone dye represented by the following general formula (I), and an embodiment thereof includes a composition in which the dye is blended with a refrigerant or a mixture of a refrigerant and refrigeration oil. (However, during the ceremony,
X1 is an anilino group having a C6 to Cl2 alkoxy group, and any one of X2, X3 and X4
is a C6-ClO alkylamino group, and the rest are hydrogen atoms.

) The present invention and its embodiments will be explained in detail below.
The anthraquinone dye of the present invention is, for example, 1,4-,1
, 5- or 1,8-dihalogenated anthraquinone with C
It can be most advantageously synthesized by reacting a 6-Cl2 alkoxyaniline with a C6-ClO alkylamine.

Such a reaction itself is a known method, and the desired product can be advantageously obtained by reacting in an inert organic solvent using a copper compound as a reaction catalyst. Examples of the anthraquinone dyes of the present invention and their solubility in refrigerating machine oil and fluorocarbons are compared with examples outside the present invention (included in the invention described in JP-A-49-57183). 1st below
It is as shown in the table.

From Table 1, it can be seen that the dyes of the present invention are 1.5 to 2
It turns out that it is double.

The solubility in Table 1 above is the number of 9 dyes dissolved in 100 CC of refrigerating machine oil or dichlorofluoromethane (Flon-12) at 25°C.

Furthermore, the refrigerating machine oil used was refrigerating machine oil [Suniso 4GS] manufactured by Sun Oil Company in the United States. The anthraquinone dye of the present invention as described above easily dissolves in conventional fluorocarbon refrigerants and refrigeration oil, provides clear and strong coloring, and does not decompose at all even with temperature changes under the conditions of use. .

If the refrigerant or the like colored with the above-mentioned dye leaks from the equipment in use, a clear colored spot is formed at the leakage location, so the leakage location can be easily detected. The main uses for the dyes of the present invention are refrigerants and freezing machine oils, or mixtures thereof. Refrigerants include, for example, trichlorofluoromethane, dichlorodifluoromethane, chlorodifluoromethane, 1,1,2-trichloro-1,2,
2-trifluoroethane, 1,2-dichloro-1,1,
2,2-tetrafluoroethane, 1,1-difluoroethane/dichlorodifluoromethane azeotrope, chloropentafluoroethane/chlorodifluoromethane azeotrope, chlorotrifluoromethane, chlorotrifluoromethane/trifluoromethane azeotrope, bromotrifluoromethane , trifluoromethane, chloropentafluoroethane, difluoromethane/chloropentafluoroethane azeotrope, chloropentafluoroethane/1,1
-difluoroethane azeotrope, dichlorofluoromethane, dichloro-difluoromethane/chlorofluoromethane azeotrope, chlorofluoromethane/1,2-dichlorotetrafluoroethane azeotrope, difluoromethane,
1,2-dibromotetrafluoroethane, 1,1,1-
Trifluoroethane, 1,1-difluoro-1-chloroethane, 1,1-difluoroethane, bromotrifluoromethane/difluoromethane azeotrope, 1,2-dichlorotetrafluoroethane/dichlorofluoromethane azeotrope and hexafluoroethane/ A trifluoromethane azeotrope can be created. Trichlorofluoromethane, dichlorodifluoromethane, chlorofluoromethane, 1,1, compared with at least 2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2 , 2-tetrafluoroethane, 1,1-difluoroethane/dichloro-difluoromethane azeotrope, chloropentafluoroethane/chlorodifluoromethane azeotrope, and refrigeration oils include naphthenic oil, paraffin oil, and alkylated benzene. , polyalkyl silicate oil, etc.

Such coloring materials can be colored as a mixture, and the dye of the present invention can also be used as a mixture. There is no particular limit on the amount of dye used, but it is usually about 0.05 to 100 cc per 100 cc of fluorocarbon-based refrigerant, since it is necessary to be able to easily detect the leakage point in the event of a refrigerant leak. It is better to use a dye of 0.19.

The reason why the dye of the present invention has good solubility in refrigerants and the like as described above is because it has a relatively long alkoxy carbon chain in its structure, and according to detailed research by the present inventors, When the number of carbon atoms in this carbon chain is less than 6, the solubility in refrigerants etc. decreases, while on the other hand, when the number of carbon atoms is 1
It has been found that when it exceeds 2, the refrigerant does not have sufficient durability against temperature changes.

Although the primary uses of the dyes of the present invention are as described above, the inventors have recognized that such dyes are also useful for coloring other organic materials, such as various organic liquids and synthetic resins.

Examples relating to the production and use of the dyes of the invention will now be described.

Note that the words in the middle of the sentence or 0/o are based on weight. Example 1 5.5 parts of 1,5-dichloroanthraquinone, 3.0 parts of cyclohexylamine, 3.9 parts of 4-aminophenylhexyl ether, 2.1 parts of sodium carbonate, and 0 parts of copper acetate.
．． 2 parts to 60 parts of orthodichlorobenzene, 13
The reaction was carried out at 0°C for 5 hours and at 170°C for 4 hours.

After the reaction, orthodichlorobenzene was removed by steam distillation, and the resulting reaction product was separated and purified by column chromatography on alumina tetrachloride to obtain 9.0 parts of the compound of Taki 1 in Table 1. Example 2 4-aminophenyl dodecyl ether in place of 4-aminophenylhexyl ether in Example 1 5.5
Table 1/F62 in the same manner as in Example 1.
8.9 parts of the compound were obtained.

Example 3 5.5 parts of 1,5-dichloroanthraquinone, 3.2 parts of n-octylamine, 3.9 parts of 4-aminophenylhexyl ether, 2.1 parts of sodium carbonate, and 0.0 parts of copper acetate.
2 parts to 60 parts of orthodichlorobenzene, 170 parts
'C for 8 hours.

After the reaction, 9.3 parts of compound A63 in Table 1 was obtained in the same manner as in Example 1. Example 4 4-aminophenyl dodecyl ether in place of 4-aminophenylhexyl ether in Example 3 5.5
46 in Table 1 in the same manner as in Example 5.
9.1 parts of compound No. 4 was obtained.

Example 5 5.5 parts of 1,8-dichloroanthraquinone, 3.0 parts of cyclohexylamine, 5.5 parts of 4-aminophenyl dodecyl ether, 2.1 parts of sodium acetate and 0.2 parts of cuprous chloride were dissolved in orthodi In addition to 60 parts of chlorobenzene,
The reaction was carried out at 130°C for 5 hours and at 170°C for 5 hours.

After the reaction, the same procedure as in Example 1 was carried out to prepare Compound 8 of Table 1.
．． I got 6 copies. Example 6 Compound 8. of /F66 in Table 1 was prepared in the same manner as in Example 5 except that 5.5 parts of 1,4-dichloroanthraquinone was used instead of 1,8-dichloroanthraquinone in Example 5. I got 0 copies.

Example 7 To a fluorocarbon refrigerant composition containing 69.95 parts of Freon 12 and 0.05 part of the anthraquinone dye obtained in Example 2, 30 parts of refrigerating machine oil (Suniso 4GS, Sun Oil Co., Ltd., USA) was added. ) was added to the refrigerator, and when the refrigerator was filled with this and operated, leakage of refrigerant and refrigerator oil from the piping connection by the nipple could be immediately detected by the red coloring caused by the dye.

Example 8 When a refrigerator was operated in the same manner as in Example 7 except that chlorodifluoromethane (Freon-22) was used in place of Freon 12 in Example 7, leakage was detected in the same manner.

Example 9 A refrigerating machine was operated in the same manner as in Example 7 except that a mixed refrigerant of chlorodifluoromethane and monochloropentafluoroethane (Freon-502) was used instead of Freon-12 in Example 7. Leakage was detected in the same way.

Claims (1)

[Claims] 1. An anthraquinone dye represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (However, in the formula, X_1 is an anilino group having an alkoxy group of C_6 to C_1_2, and X_2, X_3 and X_4
Any one of them is an alkylamino group of C_6 to C_1_0, and the rest are hydrogen atoms. )2 The dye according to claim 1, which is blended into a fluorocarbon-based refrigerant. 3. The dye according to claim 1, which is blended into a fluorocarbon refrigerant including refrigerating machine oil.