JP2741782B2 - Cationic compound and method of dyeing substrate using the same - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a cationic compound and a method for dyeing a substrate using the same.

(Prior art) Many dyes are used for dyeing and printing of base materials such as fiber materials, leather, paper, pulp, etc., but few are satisfactory in dyeing characteristics (dying speed, dyeing rate, etc.). . In particular, in obtaining clear yellow dyeings such as paper and pulp, the conventional dyes have a problem in dyeing efficiency due to low dyeing speed and dyeing rate, and in addition, the results to be satisfied with the water fastness of the dyed products. Do not give.

(Problems to be Solved by the Invention) Dyeing rate and dyeing rate are high from the viewpoint of shortening dyeing time and environmental protection, dyeing dyeing wastewater is nearly colorless, and waterfastness of dyeing is good. Development of new dyes is desired.

(Means for solving the problems) In dyeing and printing of base materials such as fiber materials, leather, pulp and paper, the dyeing speed is high, the dyeing rate is high, and the water fastness is excellent. As a result of intensive studies to find a clear yellow dye, the present invention has been achieved.

 That is, the present invention relates to formula (1)(R in the formula₁Is hydrogen, chloro, methyl, methoxy, ethoxy
Or methoxycarbonyl, R_TwoIs hydroxyl, carbon number
1-4 alkoxy, halogen, cyano, carbonamido
Or phenyl or phenoxy.
Represents an alkyl having 1 to 3 carbon atoms. Or A
Represents an anion] and a cationic compound represented by
The present invention provides a method for dyeing a substrate using the same.

The cationic compound represented by the formula (1) of the present invention can be produced, for example, as follows.

[In the formula (2), R ₁ and R ₂ represent the same meaning as described above. ] The mixing reaction of 2 moles of the aldehyde compound of the formula (2) and 1 mole ratio of the diamino compound of the formula (3) is performed by a known method. For example, the reaction is carried out in a water solvent which may contain a water-soluble organic solvent, at a temperature of about 0 to 100 ° C, preferably at 10 to 70 ° C, in the presence of an acidic substance HA (A has the same meaning as described above). As the acidic substance, an organic acid such as formic acid, acetic acid or lactic acid or an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid is usually used. After completion of the reaction, the reaction mixture is diluted with water or a water-soluble organic solvent to obtain a concentrated solution of the cationic compound of the formula (1). At this time, if necessary, a solubilizing agent (eg, urea) may be added to stabilize the solution.

Examples of the water-soluble organic solvent used in the reaction include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, dioxane, ethylene glycol, diethylene glycol, triethylene glycol,
Polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, glycerin, methyl cellosolve, carbitol, methyl carbitol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, butyl polyglycol, phenyl glycol, butyrolactone, etc. Can be mentioned.

After the completion of the condensation reaction, the new cationic compound is optionally separated from the reaction medium and dried. If desired and necessary, the anion in the cation compound of the formula (1) can be replaced with another anion having good water solubility by a known method (for example, JP-B-39-4879).

 In addition, A in the equation (1) Specific examples of the anion represented by
Halogen ion, sulfate ion, methyl sulfate ion
, Perchlorate ion, aminosulfonic acid ion, carbonated water
Elementary ion, carbonate ion, phosphate ion, phosphomolybdenum
Acid ion, phosphotungstate ion, phosphorus tungsten
Nmolybdate ion, naphthalene sulfonate ion,
Benzenesulfonate ion, 4-chlorobenzenesulfo
Acid ion, maleate ion, oxalate ion, formic acid
Ion, acetate ion, propionate ion, lactate ion
, Succinate, chloroacetate, tartrate
Methanesulfonate, benzoate, tetra
Like fluoroborate ion or chloride-zinc complex ion
Complex anions. Preferred anion A Hagi
Acid ion, acetate ion, lactate ion, chloride ion, sulfuric acid
Ions and phosphate ions.

Examples of the aldehyde compound represented by the formula (2) include, but are not limited to, the following.

1,3,3-trimethyl-2-methyleneindoline-ω-
Aldehyde, 1,3,3-trimethyl-5-chloro-2-methyleneindoline-ω-aldehyde, 1,3,3-trimethyl-5-methoxy-2-methyleneindoline-ω-aldehyde, 1,3,3- Trimethyl-5-methyl-2-methyleneindoline-ω-aldehyde, 1,3,3-trimethyl-
5-ethoxy-2-methyleneindoline-ω-aldehyde, 1,3,3-trimethyl-5-methoxycarbonyl-2
-Methyleneindoline-ω-aldehyde, 1-ethyl-
3,3-dimethyl-2-methyleneindoline-ω-aldehyde, 1- (β-chloroethyl) -3,3-dimethyl-2
-Methyleneindoline-ω-aldehyde, 1- (β-cyanoethyl) -3,3-dimethyl-2-methyleneindoline-ω-aldehyde, 1- (β-methoxyethyl) -3,
3-dimethyl-2-methyleneindoline-ω-aldehyde, 1- (β-ethoxyethyl) -3,3-dimethyl-2
-Methyleneindoline-ω-aldehyde, 1- (β-butoxyethyl) -3,3-dimethyl-2-methyleneindoline-ω-aldehyde, 1- (β-hydroxyethyl)
-3,3-dimethyl-2-methyleneindoline-ω-aldehyde, 1- (β-aminocarbonylethyl) -3,3-
Dimethyl-2-methyleneindoline-ω-aldehyde,
1- (β-phenoxyethyl) -3,3-dimethyl-2-
Methyleneindoline-ω-aldehyde, 1-benzyl-
3,3-dimethyl-2-methyleneindoline-ω-aldehyde, 1- (2-hydroxypropyl) -3,3-dimethyl-2-methyleneindoline-ω-aldehyde, 1-
(3-methoxy-2-diloxypropyl) -3,3-dimethyl-2-methyleneindoline-ω-aldehyde, 1
-(3-phenoxy-2-hydroxypropyl) -3,3
-Dimethyl-2-methyleneindoline-ω-aldehyde, 1-ethyl-3,3-dimethyl-5-chloro-2-methyleneindoline-ω-aldehyde, 1-ethyl-3,3
-Dimethyl-5-methoxy-2-methyleneindoline-ω
-Aldehyde Next, a method for dyeing a substrate with the cationic compound of the formula (1) of the present invention will be described. This new cationic compound can be used as a dye for dyeing fiber materials, leather, pulp and paper, and as a dye material for preparing color inks for printing on these substrates, and further on glass or transparent synthetic resin films. Can be used to color a thin film of a natural protein such as gelatin or casein or a nitrogen-containing light-curable resin, which is useful as a color filter. A thin film made of a natural protein such as gelatin or casein or a nitrogen-containing photocurable resin is colored (stained) at a temperature of 30 to 100 ° C. by a conventional method from an aqueous bath adjusted to be acidic with, for example, formic acid, acetic acid, hydrochloric acid, or the like. You.

As the fiber material, a material which can be dyed with a cationic dye, for example, acrylonitrile homopolymer and mixed polymer,
Examples include natural nitrogen-containing fibers such as acid-modified polyesters and polyamides, and materials containing cellulose, such as cotton, recycled cellulose fibers, polyvinyl alcohol fibers, and glass fibers.

Dyeing of these fiber materials with the novel cationic compound of the present invention is carried out by a conventional method, preferably by an absorption dyeing method at normal pressure or pressure from a neutral or acidic aqueous medium, or by spray coating with an aqueous ink, padding and printing. Performed by continuous staining. The form of the fibrous material in this case can be a single fiber and its glue, thread, cloth, knit and finished product.

These dyeings and prints have excellent dye fastness, in particular a very high dyeing rate and excellent water fastness.

A further preferred use of the novel cationic compounds is in the dyeing of various pulp and paper, especially bleached or unbleached unsized or sized papers. The new cationic compounds also exhibit a very high dyeing rate and a very high dyeing rate on unsized pulp and paper (napkins, tablecloths, sanitary papers, etc.). This high dyeing makes the dyeing wastewater almost colorless, which is an extremely great advantage in terms of wastewater regulation and environmental conservation.

The dyeing is carried out at a pH of 4 to 8, especially 5 to 7, at a dyeing temperature of 10 to 50 ° C.
It is preferably performed at 15 to 30 ° C.

The resulting dyed product exhibits a vivid yellowish color with high color value, and exhibits excellent color fastness. With regard to water fastness, for example, even when dyed paper and wet white paper are brought into contact under pressure at room temperature, almost no transfer (bleeding) from dyed paper to white paper is observed, and muban, alkali, acid, alcohol, etc. It is also very suitable for paper applications, such as napkins, tablecloths and sanitary paper, which are particularly concerned with color bleeding. The dyes of this novel cationic compound have extremely high affinity for paper and have a high dyeing speed, so they can be applied to continuous dyeing of paper and inks for jet printers, and also dye leather (spray, brush, Immersion).

(Example) Next, the present invention will be described in more detail by way of examples. In the examples, parts are parts by weight and% is% by weight.

Example 1 To a 100-volume flask was added 30 parts of glacial acetic acid, and then at room temperature, 10.8 parts of 9,9-bis (4-anilino) fluorene was gradually added and dissolved. Next, a solution in which 12.1 parts of 1,3,3-trimethyl-2-methyleneindoline-ω-aldehyde was dissolved in 25 parts of glacial acetic acid was added, and the mixture was stirred at room temperature for 24 hours to carry out a reaction. After the completion of the reaction, the content was poured into 200 parts of water, salted out by adding 6 parts of sodium chloride, and the separated precipitate was separated and dried at 60 ° C. 21.5 parts of a pale yellow compound represented by were obtained.

Maximum absorption wavelength in a 50% acetone aqueous solution of this compound, lambda _max was 453 nm.

Example 2 150 parts of water, 30 parts of lactic acid, 60 parts of ethylene glycol and 9,9-
Add 10.8 parts of bis (4-anilino) fluorene and add 55-60 ° C
To dissolve. Then 1,3,3-trimethyl-2-
Add methylene indoline-ω-aldehyde (12.1 parts) at 55 ° C
After stirring for 10 hours at room temperature, removing the insolubles, removing the insolubles, and containing a stable solution containing 25.3 parts of the same compound as in the above formula (4).
264 parts were obtained.

Even when the same amount of diethylene glycol, ethylene glycol mono-n-butyl ether or diethylene glycol mono-n-butyl ether was used in place of the ethylene glycol, a concentrated solution of the same compound as described above could be obtained.

Example 3 30 parts of acetic acid, 60 parts of ethylene glycol and 9,9-
Add 10.8 parts of bis (anilino) fluorene and heat to 55-60 ° C to dissolve. Then, 14.1 parts of 1,3,3-trimethyl-5-chloro-2-methyleneindoline-ω-aldehyde was added, and the mixture was stirred at 55 ° C for 7 hours. Thereafter, 14 parts of urea was added to the reaction solution, and the mixture was dissolved to remove insolubles. Thus, 300 parts of a highly stable concentrated solution containing 25.0 parts of the compound represented by the formula (5) was obtained.

λ _max 421nm (50% acetone water) Example 4 Dry material consisting of 50% unbleached sulphite pulp and 50% mechanical pulp was subjected to 40 ° SR using water in a Beater.
Beat to Freeness, 3% pulp content
Adjust with water so that Example 1 was added to 100 parts of this adjusted liquid.
0.03 part of the compound obtained in the above and 0.02 part of acetic acid are added. The mixture was stirred for about 5 minutes, 0.03 parts of rosin size and 0.06 parts of crystalline aluminum sulfate were added, followed by stirring for 5 minutes. The liquid was further diluted by adding 1400 parts of water, and this was diluted on a sheeter. Paper was made by a conventional method.

In this case, the coloring of the papermaking wastewater with the dye is hardly observed, and the obtained colored paper shows a very clear yellow color,
It showed good light fastness and excellent water fastness.

Example 5 Dry material consisting of 100% bleached sulfite pulp was used in a Beater with water at 25 ° SR Freeness.
s) was beaten to adjust the pulp concentration to 3%. This adjustment liquid 1
To 00 parts, 0.03 part of the compound obtained in Example 2 was added, and the mixture was stirred well for 5 minutes. Further, 1400 parts of water was added for dilution.

In this case, coloring of the papermaking wastewater by the dye was hardly observed. The resulting colored paper showed a bright yellow of high color value and good light fastness and water fastness.

Example 6 Unsized paper was immersed in a solution prepared according to the following composition at 20 to 30 ° C for 2 to 3 seconds.

After squeezing excess solution through two rollers,
Dried paper was obtained by drying at 60-80 ° C. The obtained dyed paper exhibited a vivid yellow color, was excellent in light fastness and water fastness, and bleeding of the dye due to the wet treatment was hardly observed.

Example 7 100 parts of pig leather tanned with vegetable tannin are placed in a bath at 50 ° C. consisting of 250 parts of water and 0.4 part of the compound obtained in Example 3 and stirred for 30 minutes, then in the same bath sulfonated whale oil And treated for 60 minutes with 10 parts of an anionic oil / fat solution containing as a main component. Next, it was dried by a conventional method to obtain a yellow dyed leather. This dyed leather had very good washing fastness.

Example 8 Five parts of scoured and bleached cotton broad were poured into 100 parts of a water bath containing 0.1 part of the compound obtained in Example 1, and the temperature was raised to 100 ° C. in 40 minutes while stirring the dyeing bath and the material to be dyed. Subsequently, it was kept at the same temperature for 20 minutes.

The compounds in the dyebath were completely exhausted to the cotton broad. The yellow dyeings obtained show good lightfastness and excellent waterfastness.

Similarly, the viscose rayon fabric and the cupro fabric were also dyed a bright yellow, showing good lightfastness and excellent waterfastness.

Example 9 A 0.5% aqueous solution of the compound obtained in Example 2 was added with acetic acid to give p.
The glass plate on which the gelatin layer having a thickness of 1 μm is placed is immersed in a dye bath adjusted to H4 and heated to 60 ° C., kept under gentle stirring for 5 minutes, pulled up, washed with water and dried. Gelatin was colored vivid yellow, and a color filter having excellent transparency and light resistance was obtained.

Examples 10 to 24 According to Example 2, a cation compound (lactate, formate, acetate) of the formula (1) is represented by an aldehyde compound represented by the formula (2) and a formula (3) in the following table. It was prepared using a diamino compound. The table also shows the hue when paper was dyed with the obtained cationic compound and the λ _{max of the} obtained cationic compound.
(Value in a 50% acetone aqueous solution).

Effects of the Invention The cationic compound obtained by the present invention has an extremely high dyeing rate and dyeing rate on a substrate, and the obtained dyed or colored substrate has good water fastness.

Claims (2)

(57) [Claims] 1. Equation (1)(R in the formula₁Is hydrogen, chloro, methyl, methoxy, ethoxy
Or methoxycarbonyl with R_TwoIs hydroxyl, charcoal
Alkoxy having 1 to 4 alkoxy, halogen, cyano, carvone
Substituted by amide, phenyl or phenoxy
Each represents an alkyl having 1 to 3 carbon atoms. Or
A Represents an anion]. Expression (1)(R in the formula₁Is hydrogen, chloro, methyl, methoxy, ethoxy
Or methoxycarbonyl with R_TwoIs hydroxyl, charcoal
Alkoxy having 1 to 4 alkoxy, halogen, cyano, carvone
Substituted by amide, phenyl or phenoxy
Each represents an alkyl having 1 to 3 carbon atoms. Or
A Represents an anion].
A method for dyeing a substrate.