JPS5833262B2 - Cation Senryounoseihou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides polyacrylonitrile fibers, fibers made of copolymers of acrylonitrile and other vinyl compounds,
This invention relates to an improved method for producing cationic dyes useful for coloring modified synthetic fibers dyeable with cationic dyes and acetate fibers.

The present invention is characterized in that it does not contain a sulfonic acid group or a carboxylic acid group, and has the general formula % formula % (1) (wherein Y is a hydrogen atom, a lower alkyl group, a nitro group, or a phenyl group, and R is a hydrogen atom or a methyl Z is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, or an acylamino group.

), R is a general formula (wherein R1 is a lower alkyl group or a substituted lower alkyl group, R2 is a lower alkyl group, a substituted lower alkyl group, a phenyl group or a substituted phenyl group, and R3 is a hydrogen atom or a lower alkyl group) , a lower alkoxy group, a halogen atom or an acylamino group.

) or the general formula (wherein R4 is a hydrogen atom or a lower alkyl group, R
5 is a hydrogen atom or a lower alkyl group.

), Xe is an anion.

] In preparing a cationic dye represented by the general formula % formula % (4) (where Y and Z are the same as defined above).

), and B is the same as defined previously.

] and the general formula % formula % (5) (wherein R is the same as defined above.

) in the presence of an acid and a salt of aluminum, zinc, iron or copper and/or magnesium oxide or zinc oxide. Law.

The method for producing the cationic dye represented by the general formula (1) is disclosed in Japanese Patent Publication No. 15791/1979 and Japanese Patent Publication No. 47-4
No. 5172 discloses a method in which the Ab compound represented by the general formula (4) is reacted with an epoxy compound such as ethylene, oxide or propylene oxide in the presence of an acid.

However, when this manufacturing method is carried out industrially, ethylene oxide, propylene oxide, etc. used as raw materials have a low boiling point and are gaseous at room temperature, and are toxic.
It has many disadvantages in use, including the risk of fire and explosion due to instability.

The present inventors have conducted extensive research to find a manufacturing method that does not have such drawbacks, and as a result, have arrived at the present invention.

That is, by using a dioxolanone compound and a reaction accelerator together instead of an epoxy compound, the above general formula (1
) has been discovered that a cationic dye can be obtained.

Dioxolanone compounds are solid or liquid at room temperature,
It is a non-toxic and extremely stable compound, completely eliminating the above-mentioned problems in industrial use.

A in the general formula (1) is a thiazolium group; a lower alkyl group such as a methyl group or an ethyl group, or a thiazolium group substituted with a phenyl group; a benzothiazolium group or a lower alkyl group such as a methyl group or an ethyl group , a lower alkoxy group such as a methoxy group or an ethoxy group, a halogen atom such as chloro or bromine, or a benzothiazolium group substituted with an acetylamino group.

B in the general formula (1) is a residue of a coupling component, and is represented by the general formula (2) or (3).

In the general formula (2), the substituent R0 includes, for example, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a hydroxyl group, a cyano group, an alkoxy group, a phenoxy group, an acetoxy group, or a phenyl group. lower alkyl groups substituted with, such as β-chloroethyl group, β-bromoethyl group, β-hydroxyethyl group, β-hydroxypropyl group, β-cyanoethyl group,
Examples include β-methoxyethyl group, β-ethoxyethyl group, β-phenoxyethyl group, γ-methoxyβ-hydroxypropyl group, and benzyl group.

Examples of the substituent R2 include, in addition to the lower alkyl group and substituted lower alkyl group exemplified as R1, a phenyl group and a phenyl group substituted with a lower alkyl group or an alkoxy group.

Further, as the substituent R3, halogen atoms such as chloro and bromine, lower alkyl groups such as methyl group, methoxy group,
Examples include alkoxy groups such as ethoxy groups and acetylamino groups.

In the general formula (3), the substituent R4 includes a hydrogen atom and a lower alkyl group such as a methyl group and an ethyl group, and the substituent R5 includes a hydrogen atom and a lower alkyl group such as a methyl group and an ethyl group. alkyl groups and phenyl groups,
can be given.

The azo compound represented by the general formula (4) used as a raw material in the method of the present invention is 2-aminothiazole or 2-aminothiazole.
It can be produced by a method known per se, using an aminobenzothiazole compound as the diazo component and a coupling component represented by the general formula B-H, where B is the same as defined above. .

Suitable diazo components include 2-aminothiazole, 2
-amino-4-methylthiazole, 2-amino-4-phenylthiazole, 2-aminobenzothiazole, 2-
Amino 6-methylpenzothiazole, 2-amino-6
Examples include methoxybenzothiazole, 2-amino-6-nitoxybenzothiazole, 2-amino-6-chlorobenzothiazole, and 2-amino-6-acetylaminobenzothiazole.

Suitable coupling components include N,N dimethylaniline, N,N-diethylaniline, N,N-dimethyl-m-toluidine, N,N-diethyl-m-toluidine, N,N-diethyl-m-chloro Aniline, N,N-diethyl-m-7nisidine, N,N-diethyl-m-phenetidine, N,N-diethylaniline, N-ethyl-N
-β-chloroethylaniline, N-ethyl-N-β-chloroethyl-m-)luidine, N-methyl-Nβ-cyanoethylaniline, N-ethyl-N-β-cyanoethylaniline, N-ethyl-N-β-hydroxyethyl Aniline, N-ethyl-Nbenzylaniline, N,N-di-β-
Chlorethylaniline, N,N-di-β-cyanoethylaniline, N,N-di-β-hydroxyethylaniline, N-ethyl-N-β-methoxyethylaniline, diphenylamine, N-methyldiphenylamine, 2-methylindole , 2-phenylindole, 1,2-dimethylindole, l-methyl, 2-phenylindole, and 1-ethyl-2-phenylindole.

Furthermore, examples of the dioxolanone compound represented by the general formula (5) include ethylene carbonate and propylene carbonate.

According to the method of the present invention, the azo compound of the general formula (4) and the dioxolanone compound of the general formula (5) are reacted in the presence of an acid and an aluminum, zinc, iron or copper salt and/or magnesium oxide or zinc oxide. let

Acids used include, for example, organic acids such as acetic acid, formic acid, trifluoroacetic acid, and inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, and benzenesulfonic acid;
Examples include organic sulfonic acids such as p-toluenesulfonic acid.

Salts of aluminum, zinc, iron, and copper include chlorides, sulfates, and nitrates of the respective metals, but especially aluminum chloride, aluminum sulfate, zinc chloride,
Zinc sulfate, ferric chloride, ferrous sulfate, and copper sulfate are preferred.

When an inorganic acid is used as the acid, the azo compound is dissolved in a suitable solvent, the inorganic acid is added thereto, the resulting salt of the azo compound is isolated, and the process is carried out in an excess of a quaternizing agent. preferable.

The quaternization reaction in the method of the present invention can be carried out in a solvent if desired.

Suitable solvents include, for example, benzene, toluene, xylene, chlorobenzene, dichlorobenzene and the like.

In addition to acting as an acid in this reaction, trifluoroacetic acid is also suitable as a solvent when used in an excess amount.

The quaternization reaction in the method of the present invention can be carried out within the temperature range up to the boiling point of the dioxolanone compound used, but at high temperatures, the azo compound is accompanied by a decomposition reaction.
The reaction must be carried out at a temperature below which decomposition occurs.

The optimum temperature is between 80°C and 120°C.

After the reaction, if the produced dye precipitates in the reaction solvent, it is isolated by filtration.

It is also possible to isolate the dye produced by distilling off the solvent.

If a solvent is not used, the reaction mixture is dissolved in water, the excess quaternizing agent is distilled off by steam distillation, and if necessary, insoluble matter is filtered off, and the filtrate is expressed as sodium chloride*. 20.8 parts of an azo compound (m, p, 160-165'C) were placed in 52 parts of ethylene carbonate, and the internal temperature was 100°C.
Dissolve aluminum chloride while stirring.
After gradually adding 50% of the mixture, the mixture was reacted at an internal temperature of 110° C. for 1.5 hours.

Add a water-soluble salt such as a thin layer chromatography column using formic acid-0-butanol as a developing agent to precipitate the produced dye.

It is also possible to isolate the resulting dye as a double salt with zinc chloride by adding zinc chloride.

To purify the dye obtained as desired, the dye is dissolved in water, the insoluble raw material compounds are filtered out, and impurities are adsorbed and removed by the addition of activated carbon. Salting out is preferred.

The dye of general formula (1) obtained by the method of the present invention can be used as an anion X, for example, inorganic acids such as hydrohalic acid, sulfuric acid, phosphoric acid, arylsulfonic acid, acetic acid, formic acid, oxalic acid, etc. Contains residues of organic acids.

These anions can also be replaced by other acids such as perchloric acid, hydrofluoric acid, lactic acid, tartaric acid, and the like.

Furthermore, the dye can also be obtained in the form of a double salt with zinc chloride or zinc sulfate.

The dyes obtained by the method of the present invention are water-soluble basic dyes that can be used on mordant-treated cellulose fibers, silk, leather, paper, acetate fibers and synthetic fibers, such as modified nylon containing acidic groups, polyester fibers, etc. Suitable for dyeing fibers and fibers made from polyacrylonitrile and its copolymers.

It is particularly suitable for dyeing and printing polyacrylonitrile fibers and modified polyester fibers, and has good dyeing properties, and the dyed products are particularly excellent in light fastness and water resistance.

EXAMPLES Next, the present invention will be explained with reference to examples, but the present invention is not limited to the following examples.

Parts and parts in the text mean parts by weight unless otherwise specified.

Example 1 After confirming by formula test that the azo compound had disappeared, the reaction solution was poured into 1000 parts of water, 10 parts of acetic acid and 2 parts of activated carbon were added thereto, stirred, and then separated.

7 parts of zinc chloride and 150 parts of sodium chloride were added to the filtrate to salt out the dye.

The precipitate was filtered, dried under reduced pressure at 50°C, and the formula 25.5 parts of a dye salt represented by was obtained.

This dye salt exhibits a blue color (λmax 618 nm) when dissolved in water and dyes polyacrylonitrile fibers and modified polyester fibers in a bright blue tone from a weakly acidic bath.

These dyed products had extremely excellent dye fastness properties such as light fastness and water resistance.

Ab compound shown in Example 2 (m, p, 107-10
90C) was put into 60 parts of propylene carbonate, heated to an internal temperature of 100°C to dissolve, and while stirring, 6.8 parts of zinc chloride was added and reacted at an internal temperature of 120°C for 5 hours.

A small amount of water was added to the reaction mixture and the excess propylene carbonate was distilled off by steam distillation. The residue was poured into 100 parts of water, 10 parts of acetic acid was added, followed by 2 parts of activated carbon, stirred, and separated.

150 parts of sodium chloride was added to the filtrate for salting out.

The precipitate was filtered off and dried under reduced pressure at 50°C to obtain 24 parts of a dye salt represented by the formula.

This dye salt dissolves in water and has a reddish blue color (λmax 174
~176°C), and polyacrylonitrile fibers and modified polyester fibers were dyed in reddish-blue tones from a weakly acidic bath.

These dyed products had excellent fastness properties such as light fastness, water resistance, and heat resistance.

Example 3 Azo compound represented by the formula (m, p, 174-17
18.6 parts of 6'C) were placed in 52 parts of ethylene carbonate, heated to an internal temperature of 100°C to dissolve, and 4.1 parts of zinc oxide* and 5 parts of concentrated hydrochloric acid were added thereto and reacted for 5 hours. .

The reactant was placed in 1000 parts of water and treated in the same manner as in Example 1 to obtain 25 parts of the dye salt represented by the formula.

This dye salt exhibits a blue color (λmax 590 nm) when dissolved in water and dyes polyacrylonitrile fibers and modified polyester fibers in a blue tone from a weakly acidic bath.

These dyed products had excellent light fastness and fastness.

Example 4 Water resistant azo compound (m, p, 205-20
6'C) 5.2 parts were dissolved in 100 parts of benzene, and while stirring, hydrobromic acid generated from concentrated sulfuric acid and sodium bromide was introduced until the azo compound hydrobromide was completely precipitated. did.

The precipitated hydrobromide salt was filtered off and dried.

This was placed in 10 parts of ethylene carbonate, and the internal temperature was 12
The reaction was carried out at 0°C for 20 hours.

The reactant was treated as in Example 1 to obtain 7 parts of the dye salt of the formula.

This dye salt exhibits a purple color (λmax 594 nm) when dissolved in water, and dyed polyacrylonitrile fibers and modified polyester fibers in a purple tone* in a weakly acidic bath.

These dyed products had excellent light fastness, heat resistance, and other fastness properties.

Example 5 Azo compound represented by the formula (m, p, 187-190°C,
) in 52 parts of ethylene carbonate,
The mixture was heated to an internal temperature of 100°C to dissolve it, and 7 parts of aluminum chloride was gradually added while stirring, followed by a reaction at an internal temperature of 110°C for 2 hours.

After confirming that the azo compound had disappeared by a thin layer chromatography test using formic acid-n-butan*nol as a developing agent, the reaction solution was poured into 1000 parts of water and treated in the same manner as in Example 1.

In this way, 25 parts of a dye salt represented by the formula was obtained.

This dye salt exhibits a red color (λmax 521 nm) when dissolved in water, and dyed polyacrylonitrile fibers and modified polyester fibers in a bluish red tone from a weakly acidic bath.

These dyed products had excellent light fastness, water resistance, and other fastness properties.

Example 6 Azo compound represented by the formula (m, p, 135-140'C)
16.6 parts of the mixture was added to 88 parts of ethylene carbonate, and while stirring, 15 parts of trifluoroacetic acid was added thereto, followed by heating and reaction at an internal temperature of 120° C. for 10 hours.

The reaction solution was poured into 1000 parts of water with stirring, and 2 parts of activated carbon was added thereto and treated at 50°C for 1 hour.

*Insoluble matter was filtered off, and the filtrate was post-treated in the same manner as in Example 1 to obtain 24 parts of a dye salt represented by the formula.

This dye salt dissolves in water and produces a bluish red color (λm a x516
When polyacrylonitrile fibers and modified polyester fibers were dyed with this dye, a bluish-red dyed product with excellent light fastness, water resistance, and other dye fastness properties was obtained.

Example 7 Abu compound represented by the formula (m, p, 215-220°C) 1
8.4 parts were placed in 60 parts of propylene carbonate, heated to an internal temperature of 100°C to dissolve, and while stirring, 2 parts of magnesium oxide was added and reacted at an internal temperature of 110*°C for 5 hours.

Excess propylene carbonate was removed by steam distillation of the reactant, the residue was placed in 1000 parts of water, 20 parts of acetic acid was added, and dissolved by stirring well. 23 parts of the indicated dye salt were obtained.

This dye salt dissolves in water and has a bluish red color (λmax 520 nm).
), and when polyacrylonitrile fibers and modified polyester fibers were dyed with this dye, a bluish-red dyed product with excellent dye fastness was obtained.

Example 8 Abu compound represented by the formula (m, p, 145-150'C)
9.5 parts were dissolved in 100 parts of benzene, and hydrogen chloride gas was introduced into the solution while stirring until the hydrochloride of the azo compound was completely precipitated.

The precipitated hydrochloride was filtered off, and 9 parts of the azo compound hydrochloride obtained by drying was put into 50 parts of ethylene carbonate and reacted at an internal temperature of 120°C for 10 hours.

The reaction product was dissolved in 200 parts of water, 0.2 part of activated carbon was added thereto, stirred and separated, and the filtrate was salted out by adding 2 parts of zinc chloride and 20 parts of sodium chloride.

The precipitate was filtered, dried under reduced pressure at 50°C, and the formula 10 parts of a dye salt represented by was obtained.

This dye salt exhibits a red color (λmax 518 nm) when dissolved in water, and when polyacrylonitrile fibers and modified polyester fibers were dyed with this dye salt, a red-toned dyed product with excellent color fastness was obtained.

When reacted using azo compounds as shown in the following table, dyes with similar properties were obtained by a method similar to that of the examples.

The color tones in the table represent those on polyacrylonitrile fibers.

Further, the values of λmax within 0 in the color tone column in the table are those when dissolved in water.

Claims (1)

[Claims] 1. General formula % formula (1) containing no sulfonic acid group or carboxylic acid group (wherein Y is a hydrogen atom, a lower alkyl group, a nitro group or a phenyl group, and R is hydrogen atom or methyl group, Z is a hydrogen atom, lower alkyl group, lower alkoxy group, halogen atom or acylamino group), and B is a general formula (wherein R1 is a lower alkyl group or substituted lower alkyl group, R2 is a lower alkyl group, a substituted lower alkyl group, a phenyl group or a substituted phenyl group, and R3 is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom or an acylamino group. is a hydrogen atom or a lower alkyl group, and R
6 is a hydrogen atom or a lower alkyl group. ), and Xe is an anion. In preparing a cationic dye represented by be. ] and a dioxolanone compound represented by the general formula (in which R is the same as defined above) are combined with an acid and a salt of aluminum, zinc, iron or copper and/or magnesium oxide or A method for producing a cationic dye represented by general formula (1), which comprises reacting in the presence of zinc oxide.