JPS6053566A - Concentrated dye solution - Google Patents

Abstract

PURPOSE:To obtain the titled solution of high stability with time, for use in ball point pen, etc., by dissolving, in an alcohol and/or cellosolve solvent, specific sulfonated metal-contg. phthalocyanine dye amine adduct as the coloring agent to high concentration. CONSTITUTION:The objective solution can be obtained by dissolving to high concentration (e.g., 50wt%) (A) a metal-contg. phthalocyanine dye of formula I (Pc is metal-contg. phthalocyanine; R1 is H, or OH group-contg. 1-4C alkyl; R2 is 10-20C aliphatic hydrocarbon residue; R3 is H, lower alkyl or OH; R4 and R5 are each H or lower alkyl; R6 is lower alkyl or alkoxy; m is 1-2; n is 2-5; m+n=4) (e.g., copper phthalocyanine dye of formula II) in (B) an alcohol and/or cellosolve solvent (e.g., mixed solvent consisting of phenyl cellosolve and benzyl alcohol in a weight ratio 1/4).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to dye concentrate solutions that are highly soluble in alcoholic solvents and cellosolve solvents or mixtures of these solvents and are stable over time. Since metal-containing phthalocyanine has extremely poor performance, it is used in large quantities in pigments and other applications as a mainstay of blue colorants. However, since it has poor solubility in organic solvents, attempts to improve solubility by sulfonating metal-containing phthalocyanine and adding various amines to it to increase solubility have been described, for example, in Japanese Patent Publication No. 3218/1983. It is being done so many times.

However, although the solubility of these aminated metal-containing phthalocyanines in organic solvents has been improved,
Stability over time is not sufficient, and over time dye crystals may precipitate or quality may deteriorate. In particular, copper phthalocyanine is used as a back coloring dye in ballpoint pen ink, and the solvent for this is alcohol-based,
Cellosolve-based and other various solvents have been used, but all of them have problems with stability over time.

Ballpoint pens are currently a leading stationery export product and are exported to various parts of the world, including the United States, Southeast Asia, and the Middle East. Therefore, when exported to hot and humid regions such as Southeast Asia or hot and dry regions such as the Middle East, the dyes used as coloring agents have low solubility in feed thinners and do not have sufficient stability over time. Precipitation occurs and it becomes impossible to record. As a countermeasure to this problem, it may be considered to reduce the amount of dye used relative to the solvent, but this has the disadvantage that the multiplication density becomes lower.

In order to solve these five problems, the present inventors conducted research on metal-containing phthalocyanine dyes that are highly soluble in alcohol-based and/or cellosolve-based solvents and do not change over time. It has been found that the above-mentioned problems can be solved by bonding with specific amines.

That is, the present invention is based on the following general formula (wherein PC is a metal-containing phthalocyanine group, RI is a hydrogen atom or a lower alkyl group having at least one hydroxyl group having 1 to 4 carbon atoms, and R2 is a lower alkyl group having 1 to 1 carbon atoms).
2 or a mixture of these carbon numbers, and Rs represents a hydrogen atom, a lower alkyl group, or a hydroxyl group. R4 and R5 are both hydrogen atoms or lower alkyl groups, and R4 and Rs may be equal or very different. R6 is a lower alkyl group or an alkoxy group. m
is a number from 1 to 2, n is a number from 2 to 3, and m+n=. ) is an amine adduct of a sulfonated metal-containing phthalocyanine dye. These amine addition dyes dissolve in high concentrations in alcohol-based, cellosolve-based solvents, and mixtures of these solvents, and ballpoint pen inks prepared from them do not age at all even when left for long periods of time under hot, humid, or hot dry conditions. There was no change and no quality deterioration was observed. These results are characteristics not seen in ballpoint pen inks using conventional metal-containing phthalocyanine dyes. The reason for such excellent solubility and stability over time cannot be clearly determined, but amines with a relatively low molecular weight are bonded by covalent bonds, while benzalkonium-type quaternary amines with a relatively high molecular weight form salts. This is thought to be because the two amines are bonded together and the mutual ratio of the two amines is appropriate.

These dyes can be easily produced by methods such as those described in Japanese Patent Publication No. 45-7665. That is, a metal-containing phthalocyanine dye is chlorosulfonated with chlorosulfonic acid, this is reacted with the various amines described above, the remaining chlorosulfone group is hydrolyzed to form a di-sulfone group, and the salts of the various amines are reacted with this. It can be manufactured by

The present invention will be further explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A copper phthalocyanine dye represented by the following structural formula (where CuPC represents copper phthalocyanine and R is a mixture of Cl2H25 and Cl0H21 in a ratio of 44% to 56%) was mixed with phenyl cellosolve and benzyl alcohol in 1:4 (When added to the IDK mixture and dissolved, a 50% concentrated solution was obtained. From this result, a ballpoint pen ink with the following composition was prepared.

Haikutsufuna 111 (Hitachi Chemical product) 20F polyvinylpyrrolidone 1t Benzyl alcohol 401 Phenyl cellosolve 10f Iffffi Copper phthalocyanine dye 15f Spill
on Violet C-RH (Hodogaya Chemical Products) 2 8 pjlon Blue C-RH (Hodogaya Chemical Products)
f For comparison, inks with the same composition were prepared except that the dyes of Company A and the copper 7-a cyanine dyes of 3 companies were replaced with copper phthalocyanine dyes. Next, these three inks were packed into two types of ballpoint pen tips and a comparative test of stability over time was conducted. The results are shown in Table-1.

Table 1 In the test, the samples were stored at 60°C and relative humidity of 80%, and their marking properties were tested using a ballpoint pen distribution tester (Auto ■ product).

o:! Good compatibility ×: Poor marking property Also, the concentrated solution using this dye has a maximum absorption wavelength of 667 m.
μ, molecular extinction coefficient (i) of 1.26×10′, and excellent light resistance and heat resistance.

Example 2 When a copper phthalosin dye represented by the following structural formula was dissolved in a 2:3 mixed solvent of phenyl cellosolve and benzyl alcohol, a 55% concentrated solution was obtained. Using this dye, an ink was prepared in the same manner as in Example 1, and Company A,
Inks were similarly prepared using dyes from three companies, and stability tests over time were conducted. The results are shown in 'R-2.

Table 2 A concentrated solution using this dye has a maximum absorption wavelength of 667m.
μ, molecular extinction coefficient (Q 1.24 x 10');
It also had excellent light resistance and heat resistance.

Hodogaya Chemical Industry Co., Ltd.

Claims (1)

[Scope of Claims] 1. As a coloring agent, use the following general formula (where Pc is a metal-containing phthalocyanine group, and RI is a hydrogen atom or a lower alkyl group having at least one hydroxyl group having 1 to 4 carbon atoms s R2 means an aliphatic hydrocarbon residue having 10 to 12 carbon atoms or a mixture of these carbon atoms, and R3 represents a hydrogen atom, a lower alkyl group, or a hydroxyl group. R4 and R5
are both hydrogen atoms or lower alkyl groups, and s R
4 and RS may be equal at the same time or may be different from each other. Horse is a lower alkyl or alkoxy group. m is a number from 1 to 2, n is a number from 2 to '5, m +
n is 4. 1. A stable concentrated dye solution characterized by dissolving a metal-containing phthalocyanine dye represented by ) in an alcohol-based and/or cellosolve-based solvent at a high concentration.