JPS60208365A - Copper phthalocyanine compound and aqueous recording liquid containing the same - Google Patents

Abstract

NEW MATERIAL:A compound, as free acid, of formula I [R1 is -NHC2H4NH-, or formula II; R2 and R3 are each (sulfonic acid, sulfonamide, COOH or methyl- substituted)anilino, N-methylanilino, amino, <=4C mono- or dialkanolamino-, morphorino, (substituted)phenoxy, ethoxy, etc.; x and y are each 0-3; x+y is 2 or 3]. EXAMPLE:A compound of formula III. USE:Coloring matter for aqueous recording liquid. Excellent in resistance to light and water, clearness and solubility. PREPARATION:Copper phthalocyanine is made to react with chlorosulfonic acid to form a compound of formula IV (m is 3 or 4), which is further made to react with both ammonia water and a compound of formula V to obtain a compound of formula VI. A compound of formula R3-H is then made to react with the compound obtained above, taking out crystals, if necessary, by salting out, etc. followed by neutralization using alkaline agent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a copper phthalocyanine compound and an aqueous recording liquid (ink) K containing the same.

Direct dyes, acid dyes, basic dyes, and the like are usually used as dyes for aqueous recording liquids used in inks, jet inks, and the like.

Among these, acidic dyes and basic dyes have vivid hues, but few are satisfactory in terms of light resistance and water resistance.

Furthermore, direct dyes are generally good in terms of light resistance and water resistance, but many of them have problems in compatibility with recording liquid conditioning solvents. 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 and ink jets.

(Cube) (803Na)n (2) (Formula (2)
In Cub (! represents the copper phthalocyanine nucleus represented by the following formula (the same applies hereinafter), n represents 1.2.3° or 4, respectively). However, among the dyes represented by formula (2), n is 2 or less. However, those with n of 3 or more have a disadvantage of having good solubility but poor water resistance. That is.

No copper phthalocyanine pigment (dye) has been developed that satisfies both solubility in the recording liquid preparation solvent and water resistance.

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.

Table 3 (R7 in formula (1) is -HNC2H4NH- group or acid group,
Anilino group which may be substituted with a sulfonamide group, carboxyl group or methyl group iN-methylanilino group;
Amino group; mono- or dialkanolamine group having up to 4 carbon atoms; N-ethyl-N5-monohydroxyethylamino group; morpholino group; nodoxy group; ethoxy group; may be substituted with sulfonic acid group or methyl group Represents a phenoxy group.

x and f represent 0 or an integer from 1 to 3.

However, x+1 is 2 or 3.

The compound represented by formula (1) is generally produced as follows.

Copper phthalocyanine (CupC) lc example 120-1
A compound represented by the following formula (4) (m represents 6 or 4 in formula (4)) was obtained by reacting 6 to 10 times the mole of chlorosulfonic acid at 50°C. Ammonia water (
(not used when y=0 in equation (1)) and equation (
5) (In formula (5), R,, R2 have the same meanings as above. 6
- for example, at a temperature of 50 to 50°C for a time of 2
The reaction was carried out under reaction conditions for ~3 hours to obtain a compound represented by formula (6) (in formula (6), R1, R2, x and Y represent the same meanings as above), and this compound contained formula (7)%. formula%(
7) (In formula (7), R5 represents the same meaning as above), for example, at a temperature of 70 to 90°C for a period of 3 to
After reacting under reaction conditions for 25 hours, crystals are removed by acid precipitation or salting out as required, and then caustic soda, caustic potash, and sodium carbonate are added.

A compound of formula (1) is obtained by neutralization treatment with an alkaline agent such as potassium carbonate.

Aqueous ammonia (formula (
(not used when f=o in b)) is reacted with a compound represented by formula (8) (in formula (8), R, , R3 represent the same meanings as above), and then this is reacted with the compound represented by formula (9).
) % Formula % (9) (In formula (9), R2 has the same meaning as above) is reacted in the same manner as above, and then, if necessary, crystals are taken out by acid precipitation or salting out, and then caustic soda is obtained.

A compound of formula (1) is obtained by neutralization with an alkaline agent such as caustic potash, sodium carbonate, or potassium carbonate.

It can also be grown by the following method.

The compound represented by formula (1o) which is easily available as a reactive dye (in formula (10), R,, R2 (or R3) represents the same meaning as above), and the compound represented by formula (7) (or formula (9) )) may be reacted under reaction conditions, for example, at a temperature of 7° to 90°C for 1 hour to 3 to 25 hours.

The compounds of the invention may be present in free form or optionally with Li,
It is used as a metal salt, ammonium salt, or alkanolamine salt, such as Na, dichloromethane, etc., but in any case, the solubility in the aqueous recording liquid solvent varies, and an aqueous recording liquid with excellent water resistance is obtained.

Among the compounds represented by formula (1), those having excellent effects in percentage are the compounds represented by the following formula as free acids.

9-1゜◎ 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 glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, and 7-) diethylene glycol.

Examples include cellosolve solvents such as methyl cellosolve and ether cellosolve, carpitol solvents such as methyl calpitol and ethyl carpitol, alkanolamine solvents such as ethanolamine and triethanolamine, and glycerin.

The aqueous recording liquid of the present invention is prepared by mixing 0.5 to 30% by weight of the compound of the present invention, 2 to 50% by weight of a solvent, and 40 to 90% by weight of water. 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 C, 1, Reactive, e Blue 15 (represented by the following formula) 1 Copper phthalocyanine t added to chlorosulfonic acid L1!1
The reaction mixture was reacted at 0 to 140°C for 4 hours, extracted into ice water, and the steel phthalocyanine tetrasulfochloride was separated. This was reacted with the following monochlorotriazine base and then neutralized with an alkali agent to dissolve 50 parts of morpholine in 200 parts of water at a pH of 5.5 to 7.5 and a temperature of 70 to 80°C. .5 parts for 3 hours. To this reaction solution, 17 parts of hydrochloric acid was added, and the solid content was separated in a furnace, 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 diethylene glycol, and 59.3 parts of water were mixed, stirred and dissolved, and undissolved matter was removed using industrial filter paper to obtain a blue aqueous recording liquid. In this case, the compound found in Example 1 showed excellent solubility.

Inkjet color printer (Sharp Corporation)
When a printed matter was prepared using this recording liquid at a temperature of 0-700) and exposed for 5 hours and 20 hours using a carbon fade meter, it was found to have light resistance of grade 4 on the JIS blue scale. Moreover, this printed matter had good water resistance.

Example 3 C, ■, ReactiW, e Blue 71 (shown by the following formula, 1 Add copper phthalocyanine in chlorosulfonic acid to 130~
The mixture was reacted at 140°C for 4 hours and extracted into ice water. 14-50 parts of p-cyanine tetrasulfochloride was dissolved in 500 parts of water to pH = 6. Q~8゜0,
The mixture was reacted with 7 parts of methanic acid at a temperature of 80-90°C for 4 hours. 15 parts of hydrochloric acid was added to this reaction solution, and the solid content was separated, neutralized with lithium hydroxide, and dried to obtain 48 parts of a compound represented by the following formula.

(λma! 627.665 parts m) Example 4 C, 1, Reactive Blue 7
React at 60 to 140°C for 4 hours, extract into ice water, and add 300 parts of copper phthalocyanine tetrasulfochloride to 50 parts of copper phthalocyanine tetrasulfochloride.
Dissolved in water at pH = 5. Q~8.01 degree 80~90
It was reacted with 4 parts of aniline at ℃ for 5 hours. 17 parts of hydrochloric acid was added to this reaction solution, and the solid content was separated in a furnace, neutralized with caustic soda, and then dried to obtain 52 parts of solid content represented by the following formula.

(λmax 620.66snm) Examples 5 to 21 Compounds having the following structures were synthesized by a method similar to Examples 1, 3, and 4.

Example 5 Example 6 17 Example 7 Example 8 18 - Example 9 Example 10 Example 11 Example 12 Example 15 Example 14 Example 15 Example 16 Example 17 SO3NIIL Example 18 Example 19 Example 2〇 22 - Example 21 Example 22 Example 23 25 parts of copper phthalocyanine was added to 200 parts of chlorosulfonic acid and reacted at 150 to 140°C for 4 hours, then cooled to 30 to 40°C and extracted into ice water to obtain steel phthalocyanine tetra. Sulfochloride is distributed door to door. f7) Place copper 7 thalocyanine tetrasulfochloride in ice water and slurry it at 5°C or below using the following monochlorotriazine base I for 30 minutes. Then pH = 9 with caustic soda
Adjust to ~10, and after 1 hour raise the temperature to 50~40℃ and pH = 1
The reaction was allowed to occur for 6 hours at a temperature of 0 to 11.

Furthermore, add 4 parts of aniline and heat at 80-90°C, pH = 5.0-
The reaction was carried out at 8.0 for 3 hours. 25 parts of hydrochloric acid was added to this reaction solution, and the solid content was separated, neutralized using a caustic meter, and then dried to obtain 45 parts of a dry solid content having the following structure.

Example 24 Copper phthalocyanine tetrasulfochloride obtained from 22 parts of steel phthalocyanine in the same manner as in Example 22 was placed in ice water and 11.7 parts of the following monochlortriazine base was added at below 5°C to form a slurry for 50 minutes, and then slurried in ammonia water. The mixture was neutralized to pH=6 to 7, and after 2 hours, the temperature was raised to 50 to 60°C, and the reaction was carried out at pH=9 to 10 for 4 hours.

Furthermore, 3.5 parts of morpholine was added and the mixture was heated at 80-90°C, p)l=
The reaction was carried out for 23 hours at a temperature of 7.0 to 9.0. 50 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 dry solid content having the following structure.

-25-O' (Application example for value writing) The aqueous recording liquid according to Example 2 was filled into an unfilled signboard and written on plain paper. The handwriting made with this recording liquid had a clear blue color and was grade 4 in the one-light test using the carbon fade meter. Moreover, the water resistance of the handwriting was good.

Patent applicant: Nippon Kayaku Co., Ltd. 126 completed-

Claims (2)

[Claims] (1) In the formula (1) as a free acid, R1 is a -N)IC2H4N)1- group or an anilino group which may be substituted with an acid group, a sulfonamide group, a carboxyl group or a methyl group iN-methylanilino Group; Amino group; Mono- or dialkanolamino group having up to 4 carbon atoms; N-ethyl-N-hydroxyethylamino group; Morpholino group; Methoxy group; Ethoxy group may be substituted with 1 sulfonic acid group or methyl group Remove the phenoxy group. Moreover, x and P represent 0 or an integer from 1 to 3. However, x+-1
is 2 or 3. ) A copper phthalocyanine compound represented by (2) Formula (1) as a free acid [In formula (1), R1 is a -HNC2H4NH- group or an anilino group optionally substituted with an acid group, a sulfonamide group, a carboxyl group, or a methyl group iN-methylanilino group; amino Group; Mono- or dialkanolamino group having up to 4 carbon atoms; N-ethyl-N゛-hydroxyethylamino group; Morpholino group; Methoxy group; Ethoxy group; Phenoxy group optionally substituted with sulfonic acid group or methyl group Nbf. Moreover, x and y represent 0 or an integer from 1 to 5. However, x+1 is 2 or 3. ) An aqueous recording liquid characterized by containing a copper phthalocyanine compound represented by: