JPH03192158A - Cationic compound and method for dyeing substrate material therewith - Google Patents

Abstract

PURPOSE:To obtain a yellow dye exhibiting high dyeing speed and degree of exhaustion in dyeing a textile material, leather, pulp, paper, etc., as well as excellent brightness and fastness to water by selecting a compd. wherein a pyridopyridinium salt is linked to diphenylfluorene through azo groups. CONSTITUTION:A cationic compd. of the formula (wherein R1 is H or 1-4C alkyl; R2 is H, 1-4C alkyl, or alkoxy; and A<-> is an anion) which has a structure wherein a tetrazo compd, of 9,9'-bis(4-anilino)fluorene is coupled with a pyridone deriv. is selected as a yellow dye, which is useful for dyeing an unsized pulp or paper (e.g. a napkin, table cloth, or sanitary paper). The dyeing with the dye is carried out at a pH of 4-8, pref. 5-7, and at 10-50 deg.C, pref. 15-30 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a cationic compound and a method for dyeing a substrate using the same.

(Conventional technology) Although many dyes are used for dyeing and printing base materials such as textile materials, leather, paper, and valves, there are few that are satisfactory in terms of dyeing properties (dying speed, dyeing rate, etc.) In particular, when it comes to obtaining bright yellow dyed products such as 祇 and bulb, conventional dyes have problems in terms of dyeing efficiency due to their slow dyeing speed and dyeing rate, and in addition, the water fastness of the dyed products is also satisfactory. not give.

(Problems to be Solved by the Invention) A dye that has a high dyeing speed and dyeing rate from the viewpoint of shortening dyeing time and protecting the environment, makes dyeing waste water nearly colorless, and has good water fastness of dyed products. The development of dyes is desired.

(Means for solving the problem) When dyeing and printing base materials such as textile materials, leather, pulp, and paper, the dyeing speed is high, the dyeing rate is high, and the water fastness is excellent. The present invention was developed as a result of intensive research to find a bright yellow dye.

That is, the present invention relates to the formula (1) [wherein R1 represents hydrogen, an alkyl group of 01 to 4, R8 represents hydrogen, an alkyl of cl to 4, an alkoxy of C1 to 4, and Aθ represents an anion] The present invention provides a cationic compound represented by the following formula and a method for dyeing a substrate using the same.

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

(2) Tetrazotizing the diamino compound represented by the formula,
-2Aθ (1) Bi1 [In formula (3), R, , R, and Ae represent the same meanings as above] Obtained by coupling with a pyridone compound represented by formula (3).

This tetrazotization and coupling reaction is carried out using, for example, a water solvent which may contain a water-soluble organic solvent and a temperature of about -5 to 30°C.
9,9-bis of formula (2) in the presence of an acidic substance, for example, 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, at a temperature of 0 to 10°C. (4
-anilino)fluorene is tetrazotized, and the general formula (3) is obtained.
After the reaction is completed, the compound is diluted with water or a water-soluble organic solvent to obtain a concentrated solution of the cationic compound of formula (1). At this time, a solubilizing agent (for example, urea, etc.) may be added to stabilize the solution if necessary.

Examples of water-soluble organic solvents used in the reaction include methyl alcohol, ethyl alcohol, propyl alcohol,
Methyl alcohol, dioxane, ethylene glycol,
Diethylene glycol, triethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, glycerin, methyl cellosolve, calpitol, methyl calpitol, ethylene glycol motubutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, butyl Examples include polyglycol, phenyl glycol, butyrolactone, and the like.

After the reaction has ended, the new cationic compound is optionally separated from the reaction medium and dried. The anion Aθ in the final product is introduced by pre-formulation into the pyridone compound. Alternatively, if it is desired to obtain a compound with a particular anion Aθ, this anion can be prepared by conventional methods, e.g. ion exchange or with suitable salts, if necessary in several steps, e.g. with hydroxide or bicarbonate. The desired anion may be exchanged by various reactions.

Specific examples of the anion represented by Ae in formula (1) include halogen ions, sulfate ions, methyl sulfate ions,
Perchlorate ion, aminosulfonate ion, bicarbonate ion, carbonate ion, phosphate ion, phosphomolybdate ion, phosphotungstate ion, phosphotungstomolybdate ion, naphthalenesulfonate ion, benzenesulfonate ion, 4-chlor Benzene sulfonate ion, maleate ion, oxalate ion, formate ion, acetate ion, propionate ion, lactic acid ion, succinate ion, chloroacetate ion, tartrate ion, methanesulfonate ion, benzoate ion, tetrafluoroboric acid ions or complex anions such as chlorine-zinc complex ions. Preferred anions A are formate ion, acetate ion, lactate ion, chloride ion, sulfate ion and phosphate ion.

Next, a method for dyeing a substrate using the cationic compound of formula (1) of the present invention will be described. This new cationic compound can be used as a dye for dyeing textile materials, leather, pulp and paper.
It can also be used as a pigment material for the preparation of color inks used for printing on these substrates, and it can also be used as a thin film of natural proteins such as gelatin or casein or nitrogen-containing photocurable resin provided on glass or transparent synthetic resin films. They are useful as color filters. Thin films made of natural proteins such as gelatin and casein or nitrogen-containing photocurable resins are colored (dyed) using conventional methods in an aqueous bath adjusted to be acidic with formic acid, acetic acid, hydrochloric acid, etc. at a temperature of 30 to 100°C. be done.

Textile materials include materials that can be dyed with cationic dyes, such as homopolymers and mixed polymers of acrylonitrile, natural nitrogen-containing fibers such as acid-modified polyesters and polyamides, materials containing cellulose, such as cotton, recycled cellulose fibers, polyvinyl. Examples include alcohol fibers and glass fibers.

Dyeing of these fiber materials with the novel cationic compound of the present invention can be carried out by conventional methods, preferably by absorption dyeing in a neutral or acidic aqueous medium under normal pressure or pressure, or by spray coating with water-based inks, padding and printing. Performed by continuous staining. The form of the fibrous material in this case can be monofilaments and their glues, yarns, fabrics, knits and finished products.

These dyeings and prints have excellent color fastness properties, in particular very high dyeing rates and excellent water fastness properties.

A further preferred use of the new cationic compounds is the dyeing of various pulps and papers, especially bleached or unbleached, unsized or sized papers.

The new cationic compounds exhibit very high dyeing rates and very high dyeing rates even on unsized pulp and paper (napkins, tablecloths, sanitary paper, etc.). This high dyeing property makes the dyeing wastewater nearly colorless, which can be said to be an extremely large advantage from the standpoint of wastewater regulation and environmental conservation.

Dyeing is done at pl (value 4-8, especially 5-7, dyeing temperature lO-5
It is carried out at 0°C, preferably 15-30°C.

The resulting dyed product exhibits a bright yellow color with a high color value and exhibits excellent color fastness.

In particular, regarding water fastness, for example, even when dyed paper and wet white paper are brought into contact with each other under pressure at room temperature, there is hardly any dye transfer (bleeding) from the dyed paper to the white paper, and even when dyed paper is brought into contact with wet white paper under pressure, there is almost no dye transfer (bleeding) from the dyed paper to the white paper. The dyes based on the new cationic compounds are highly suitable for paper applications where color bleeding is a particular concern, such as napkins, tablecloths, and sanitary paper, as they exhibit excellent fastness to alcohol. Because it has an extremely high affinity for dyes and has a high dyeing speed, it can be applied to continuous dyeing of paper and ink for jet printers, and can also be used to dye leather (spraying, brushing, dipping, etc.).

(Example) Next, the present invention will be explained in more detail with reference to Examples.

In the examples, parts are parts by weight, and % is % by weight.

Example 1 69 parts of 9.9-bis(4-anilino)fluorene was dissolved in 300 parts of glacial acetic acid, 1000 parts of water and 125 parts of 35% hydrochloric acid.
The mixture was added and suspended at room temperature while stirring. The suspension was cooled to 0°C, 30 parts of sodium nitrite was dissolved in 200 parts of water, and the solution was added dropwise at 0 to 5°C over 1 hour. After stirring for 3 hours,
Urea was added to destroy excess nitrite.

102 parts of N-(6-hydroxy-4-methyl-2-oxo-pyrid-3-yl)pyridinium chloride was added to 80 parts of water.
The solution was added to the tetrazotized solution at 0 to 5° C., and stirred for 20 hours with sodium acetate to adjust pi to 4.2. The precipitated dye was filtered off and dried. N-(6-hydroxy-4-methyl-2-oxo-pyrid-3-yl)pyridinium chloride in zero-order formula Example 1 was replaced with N-(6-hydroxy-4-methyl-2-oxo-pyrid-3-yl)pyridinium chloride. -Methyl-2-oxo-
The same procedure was carried out using 112 parts of pyrid-3-yl)-3-methylpyridinium chloride to obtain 200 parts of a dye represented by the zero-order formula % (4). This dye is 439n
s (50% acetone water) with λ, □・21θ
190 parts of the dye represented by (5) was obtained. The dye had a λ□ of 440 parts m (50% acetone in water).

Example 3 Dry product 20 of the disazo compound of formula (4) obtained in Example 1
40 parts of lactic acid, 28 parts of thiodiethylene glycol, and 40 parts of water were mixed and heated to dissolve to obtain 128 parts of a concentrated solution.

Example 4 50 parts of chemically bleached cellulose sulfite (from softwood wood) and 50 parts of chemically bleached cellulose sulfite (from hardwood wood) were ground in a mill in 5000 parts of water. 0.5 part of the dye of Example 1 was dissolved in 1.0 part of a 50% aqueous acetic acid solution and 80 parts of boiling water and poured into the pulp. After mixing for 10 minutes, paper was made from the pulp. The paper thus obtained was dyed yellow and exhibited excellent water fastness. Moreover, the wastewater was almost colorless.

Example 5 3.5 parts of the concentrated dye solution of Example 3 was dissolved in 60 parts of water and injected into pulp in the same manner as in Example 4 to produce paper.

The paper thus obtained was dyed yellow and exhibited excellent water fastness. Moreover, the wastewater was almost colorless.

Example 6 A dye bath was prepared.

100 parts of acrylic fiber yarn was placed in this dye bath, heated to 100''C for 45 minutes, and dyed for 1 hour.

The acrylic fiber thread was dyed yellow, and the weathering and light fastness of this dyed product was grade 7, which was excellent.

Example 7 5000 parts of water, 6 parts of 45% acetic acid, 1 part of sodium acetate,
30 parts of anhydrous sodium sulfate was added, and 100 parts of a cationic dyeable polyester fiber cloth was added thereto, heated to 120° C. for 1 hour using a high-temperature, high-pressure dyeing machine, and dyed for 90 minutes.

The cationic dye-dyeable polyester fiber fabric was dyed yellow.

Examples 8 to 10 According to Example 1, a cationic compound of formula (1) was produced using a diamino compound represented by formula (2) and a pyridone compound represented by formula (3) shown in the following table. The table also shows the hue when paper was dyed with the obtained cationic compound and the λ of the obtained cationic compound (value in 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)

[Claims] (1) Formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, R_1 is hydrogen, C_1_ to_4 are alkyl groups,
R_2 is hydrogen, C_1_~_4 alkyl, C_1_~
_4 represents alkoxy, and A^■ represents an anion] A cationic compound represented by the following. (2) Formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) Use a cationic compound represented by [In the formula, R_1, R_2 and A are as defined in the previous section (1)] A dyeing method for base materials characterized by: