JPH0254865B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a copper phthalocyanine compound and an aqueous recording liquid (ink) containing the same. Direct dyes, acid dyes, basic dyes, etc. are usually used as dyes for aqueous recording liquids used for writing, stamps, jet inks, etc. Among these, acidic dyes and basic dyes have vivid hues, but few are satisfactory in terms of light resistance and water resistance.
Direct dyes generally have good light resistance and water resistance, but many of them have problems in compatibility with solvents for preparing recording liquids. Among direct dyes, blue dyes having the structure of the following formula (2) obtained by sulfonation of copper phthalocyanine are used for aqueous recording liquids, especially ink jets. [CuPc] - (SO ₃ Na) n (2) (In formula (2), CuPc is the copper phthalocyanine nucleus represented by the following formula (the same applies hereinafter), n is 1, 2,
3 or 4 respectively) However, among the dyes represented by formula (2), dyes with n of 2 or less do not have sufficient solubility in the solvent for preparing an aqueous recording liquid, and dyes with n of 3 or more have good solubility but have the disadvantage of poor water resistance. . That is, a copper phthalocyanine pigment (dye) that satisfies both solubility in a recording liquid preparation solvent and water resistance has not been obtained. Therefore, the present inventors conducted research on phthalocyanine compounds for aqueous recording liquids in order to improve these drawbacks, and found that a copper phthalocyanine compound represented by the following formula (1) as a free acid has excellent light resistance and sharpness. The present invention was completed by discovering that this material sufficiently satisfies the requirements in terms of water resistance and solubility. (R ₁ in formula (1) is -HNC ₂ H ₄ NH- group or

[Formula] group, R ₂ and R ₃ are anilino group which may each be independently substituted with a sulfonic acid group, sulfonamide group, carboxyl group or methyl group; N-methylanilino group; amino group; carbon number within 4 mono- or dialkanolamine group; N-
Ethyl-N-hydroxyethylamino group; Morpholino group; Methoxy group; Ethoxy group; Represents a phenoxy group which may be substituted with a sulfonic acid group or a methyl group. And x and y represent 0 or an integer from 1 to 3. However, x+y is 2 or 3. The compound represented by formula (1) is generally produced as follows. For example 120-150 for copper phthalocyanine (CuPc)
A compound represented by the following formula (4) (CuPc) (SO ₂ Cl) m (4) (m represents 3 or 4 in formula (4)) is prepared by reacting 6 to 10 times the mole of chlorosulfonic acid at ℃. Then, aqueous ammonia (not used when y=0 in formula (1)) and formula (5) are added to the compound of formula (4). (In formula (5), R ₁ and R ₂ have the same meanings as above.) The compound represented by formula (6) is reacted under reaction conditions of, for example, a temperature of 30 to 50°C and a time of 2 to 3 hours. (In formula (6), R ₁ , R ₂ , x and y have the same meanings as above.) A compound represented by formula (7) R ₃ −H (7) (in formula (7) (R ₃ has the same meaning as above) is reacted under reaction conditions, for example, at a temperature of 70 to 90°C and a time of 3 to 25 hours, and then crystals are obtained by acid precipitation or salting out as necessary. After taking it out, it is neutralized with an alkaline agent such as caustic soda, caustic potash, sodium carbonate, or potassium carbonate to obtain the compound of formula (1). Also, in the compound of formula (4), aqueous ammonia (not used when y = 0 in formula (1)) and the formula
(8) (In formula (8), R ₁ and R ₃ have the same meanings as above.) Then, this compound is reacted with the compound represented by formula (9) R ₂ −H (9) (In formula (9), R ₂ is (same meaning as above)
are reacted in the same manner as above, and then the crystals are taken out by acid precipitation or salting out as necessary, and then neutralized with an alkaline agent such as caustic soda, caustic potash, sodium carbonate, or potassium carbonate to obtain the formula (1). obtain the compound. It can also be obtained by the following method. Compound represented by formula (10) that is easily available as a reactive dye (In formula (10), R ₁ and R ₂ (or R ₃ ) have the same meanings as above.) A compound of formula (7) (or formula (9)) is added to
The reaction may be carried out at a temperature of 3 to 25 hours. The compound of the present invention can be used in a free form or as a metal salt such as Li, Na, K, etc., ammonium salt, or alkanolamine salt if desired, but in any case, it has high solubility in an aqueous recording liquid solvent and is an aqueous compound with excellent water resistance. Give recording fluid. Among the compounds represented by formula (1), those having particularly excellent effects are those represented by the following formula as free acids. An aqueous recording liquid is prepared using the novel compound of the present invention, water and a solvent. The solvent used to prepare the aqueous recording liquid should preferably be one that is compatible with water and has the property of dissolving dyes well, and further preferably has appropriate hygroscopicity and can appropriately control water evaporation. Examples include ethylene glycol, diethylene glycol, triethylene glycol,
Glycol solvents such as tetraethylene glycol, cellosolve solvents such as methyl cellosolve and ethyl cellosolve, carbitol solvents such as methyl carbitol and ethyl carbitol, alkanolamino solvents such as diethanolamine and triethanolamino, glycerin, etc. can be mentioned. The aqueous recording liquid of the present invention contains 0.5% of the compound of the present invention.
~30% by weight, solvent 2-50% by weight, water 40-90% by weight
It is prepared by mixing so as to contain. At this time, an anionic or nonionic surfactant may be used to further improve the dissolution stability. These are used in an amount of 0.1 to 2% by weight based on the aqueous recording liquid, if necessary. The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded. The middle part of the example represents parts by weight, and λmax was measured in water. Example 1 CIReactive Blue15 (shown by the following formula) Adding copper phthalocyanine to chlorsulfonic acid
The mixture was reacted at 130 to 140°C for 4 hours and extracted into ice water to separate the copper phthalocyanine tetrasulfochloride. Add to this the following monochlortriazine base (obtained by reacting with ammonia water and then neutralizing with an alkali agent), dissolve 50 parts in 200 parts of water and adjust the pH.
= 5.5 to 7.5 and reacted with 3.5 parts of morpholine at a temperature of 70 to 80°C for 3 hours. To this reaction solution, 17 parts of hydrochloric acid was added, and the solid content was separated, neutralized with caustic soda, and dried to obtain 50 parts of dry solid content represented by the following formula. Example 2 10 parts of the compound obtained in Example 1, 20 parts of diethyl glycol, 10 parts of propylene glycol, 0.2 parts of Noigen P (nonionic surfactant manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and 59.3 parts of water were mixed and then stirred. After dissolving, undissolved matter was removed using industrial paper to obtain a blue aqueous recording liquid. At this time, the compound obtained in Example 1 showed excellent solubility. Prints were made using this recording liquid using an inkjet color printer (IO-700 manufactured by Sharp Corporation), and then printed using a carbon fade meter for 5 hours and 20 minutes.
When exposed to light for a period of time, it was rated 4th class light fastness on the JIS blue scale. Moreover, this printed matter had good water resistance. Example 3 CIReactiVe Blue71 (shown by the following formula) Adding copper phthalocyanine to chlorsulfonic acid
The mixture was reacted at 130 to 140°C for 4 hours and extracted into ice water to separate the copper phthalocyanine tetrasulfochloride. This and ammonia water

It is obtained by reacting [Formula] and then neutralizing it with an alkali agent. ) Dissolve 50 parts in 300 parts of water, pH = 6.0 to 8.0, temperature 80 to 90.
The mixture was reacted with 7 parts of methanic acid at ℃ for 4 hours. 15 parts of hydrochloric acid was added to this reaction solution, the solid content was separated, neutralized with lithium hydroxide, and dried to obtain 48 parts of a compound represented by the following formula. Example 4 CIReactive Blue7 (shown by the following formula) Adding copper phthalocyanine to chlorsulfonic acid
The mixture is reacted at 130 to 140°C for 4 hours and extracted into ice water to separate copper phthalocyanine tetrasulfochloride. Then this

It is obtained by reacting [formula] with aqueous ammonia and then neutralizing it with an alkali agent. ) Dissolve 50 parts in 300 parts of water, pH = 5.0 to 8.0, temperature 80
It was reacted with 4 parts of aniline at ~90°C for 3 hours. 17 parts of hydrochloric acid was added to this reaction solution to separate the solid content, neutralized with caustic soda, and then dried to obtain 52 parts of solid content represented by the following formula. Examples 5 to 21 Compounds having the following structures were synthesized by methods similar to Examples 1, 3, and 4. Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 25 parts of copper phthalocyanine in 200 parts of chlorosulfonic acid
After reacting at 130-140°C for 4 hours, the mixture was cooled to 30-40°C, extracted into ice water, and the copper phthalocyanine tetrasulfochloride was separated. This copper phthalocyanine tetrasulfochloride was placed in ice water and heated to below 5°C using the following monochlorotriazine base.

[Formula] Add 19.5 parts and slurry for 30 minutes. After that, adjust the pH to 9-10 with caustic soda, and raise the temperature to 30-40℃ after 1 hour.
The reaction was carried out at PH=10-11 for 3 hours. Add 4 parts of aniline to 80~90℃, pH=5.0~
The reaction was carried out at 8.0 for 3 hours. Add 25% hydrochloric acid to this reaction solution.
The solid content was separated, neutralized with caustic soda, and dried to obtain 45 parts of a dry solid content having the following structure. Example 24 Copper phthalocyanine tetrasulfochloride obtained from 22 parts of copper phthalocyanine in the same manner as in Example 22 was placed in ice water and heated below 5°C to the following monochlorotriazine base.

[Formula] Add 11.7 parts to slurry for 30 minutes, then add ammonia water to pH=
Neutralize to 6-7, raise temperature to 50-60℃ after 2 hours and pH = 9
The reaction was carried out for 4 hours at ~10°C. Further, 3.5 parts of morpholine was added and the mixture was reacted for 23 hours at 80-90°C and pH = 7.0-9.0. 30 parts of hydrochloric acid was added to this reaction solution, and the solid content was separated, neutralized with caustic soda, and dried to obtain 42 parts of a dry solid content having the following structure. (Application example for writing) The aqueous recording liquid according to Example 2 was filled into an ink powder-filled felt-tip pen, and writing was performed on plain paper. The handwriting made with this recording liquid had a clear blue color and was grade 4 in the light fastness test using the carbon fade meter. Also, the water resistance of the handwriting was good.

Claims (1)

[Claims] 1 Formula (1) as a free acid [In formula (1), R ₁ is an -NHC ₂ H ₄ NH- group or a [Formula] group, and R ₂ and R ₃ are each independently substituted with a sulfonic acid group, a sulfonamide group, a carboxyl group, or a methyl group. optional anilino group; N-methylanilino group; amino group; mono- or dialkanolamino group having up to 4 carbon atoms; N-
Represents an ethyl-N-hydroxyethylamino group; a morpholino group; a methoxy group; an ethoxy group; a phenoxy group which may be substituted with a sulfonic acid group or a methyl group. Moreover, x and y represent 0 or an integer from 1 to 3. However, x+y is 2 or 3. ) A copper phthalocyanine compound represented by 2 Formula (1) as free acid [In formula (1), R ₁ is a -HNC ₂ H ₄ NH- group or a [Formula] group, and R ₂ and R ₃ are each independently substituted with a sulfonic acid group, a sulfonamide group, a carboxyl group, or a methyl group. optional anilino group; N-methylanilino group; amino group; mono- or dialkanolamino group having up to 4 carbon atoms; N-
Represents an ethyl-N-hydroxyethylamino group; a morpholino group; a methoxy group; an ethoxy group; a phenoxy group which may be substituted with a sulfonic acid group or a methyl group. Moreover, x and y represent 0 or an integer from 1 to 3. However, x+y is 2 or 3. ) An aqueous recording liquid characterized by containing a copper phthalocyanine compound represented by: