JPH0832991B2 - Dyeing method for mixed fibers - Google Patents

Description

TECHNICAL FIELD The present invention relates to a dyeing method for mixed fibers, and more specifically, to a mixed fiber containing two or more kinds of fibers selected from polyester, acetate and nitrogen-containing fibers. The present invention relates to a dyeing method for dyeing at the same time.

(Prior Art) In recent years, with the diversification of fiber materials, various mixed fibers have been widely used. For example, a mixed fiber of polyester or acetate and silk, wool or polyamide is known, but when dyeing these mixed fibers, conventionally, a water-insoluble disperse dye for polyester or disperse dye for acetate is generally used. Then, polyester or acetate is dyed, and then a water-soluble reactive dye or acid dye is used to dye the nitriding fiber such as silk, wool or polyamide. However, in this method, it is necessary to divide the dyeing process into two stages because the dyeing conditions when dyeing polyester or acetate and dyeing nitrogen-containing fibers such as silk, mainly the dyeing temperature and pH range are different. Was troublesome.

(Problems to be Solved by the Invention) In view of the above circumstances, the present inventors have studied a method of simultaneously dyeing mixed fibers containing two or more kinds of fibers selected from polyester, acetate and nitrogen-containing fibers in one step. When a reactive disperse dye used for simultaneous dyeing of polyester and cellulose fibers was used,
It has been found that acetate and nitrogen-containing fibers can be dyed well, and the above mixed fibers can be dyed at the same time.

Means for Solving the Problems) The gist of the present invention is to dye a mixed fiber containing two or more kinds of fibers selected from polyester, acetate and nitrogen-containing fibers, in order to dye the above-mentioned general formulas [I] to [VI]. ] It exists in the dyeing method of the mixed fiber characterized by using the reactive disperse dye shown by these.

 Hereinafter, the present invention will be described in more detail.

The reactive disperse dye that is the object of the present invention is a water-insoluble dye having a specific structure having a specific reactive group, and can be used by selecting from conventionally known reactive disperse dyes. Examples of these dyes include dyes represented by the following general formulas [I] to [VI].

General formula [I] Disazo dye represented by: [In the formula [I], k is Represents, May be substituted with a phenyl group, a lower alkyl group, a lower alkoxy group, a phenoxy group, a nitro group, a cyano group, a halogen atom, a trifluoromethyl group, an acetylamino group, a lower alkylcarbonyl group or a lower alkylsulfonyl group. Represents a phenyl group, Represents a naphthylene group or a lower alkyl group, a lower alkoxy group, a phenylene group which may be substituted with a halogen atom or an acetylamino group, Represents a lower alkyl group, a lower alkoxy group, an acetylamino group or a phenylene group optionally substituted by a halogen atom, -Y ¹ and -Y ² represent an alkyl group optionally substituted by a lower alkoxy group, —Y ³ represents an alkyl group which may be substituted with a lower alkoxy group, an allyl group or an aralkyl group, —V represents a cyano group or a —CONH ₂ group, and —X— represents —O— or —S—. And Q is (-R ¹ and -R ² are a hydrogen atom or a cyano group, a hydroxyl group, a lower alkoxy group or an alkyl group which may be substituted with a dialkylamino group, an alkenyl group,
It represents a cyclohexyl group, an aryl group or an aralkyl group. ) Is represented. ].

General formula (II) Pyridone dye represented by: [In the formula [II], -T represents a hydrogen atom, a lower alkyl group, a nitro group or a halogen atom, -Y ⁴ represents a substituted or unsubstituted alkyl group or an aralkyl group, A ¹
- is CH ₂ - group, -C ₂ H ₄ - group, -OC ₂ H ₄ - group, -CONHC ₂ H ₄ -
A group, a —SO ₂ NHC ₂ H ₄ — group or a —SO ₂ C ₂ H ₄ — group, and
Represents 0 or 1, and -X- and -Q are the same as defined in the above formula [I]. ] General formula [III] In anthraquinone dyes represented: wherein [II], -R ⁴ is an amino group or a hydroxyl group, -R ⁵ and -R ⁶ are hydrogen atom, an amino group, a hydroxyl group, a nitro group, a chlorine atom or bromine Represents an atom,
-R ⁷ represents a hydrogen atom, a chlorine atom, a bromine atom, a cyano group, or -SO ₂ R ⁸ (-R ⁸ represents a methyl group, an ethyl group or a phenyl group), -E- is -O- or -S Represents a linking group consisting of, -X ¹ and -X ² one of which represents a hydrogen atom, the other is (-X- and -Q are the same as defined in the above formula [I],
—R ⁹ represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a chlorine atom or a bromine atom), and k is 0 or 1. However, in the case of -X ² hydrogen atom, k is 0. ] General formula [IV] In quinophthalone dyes represented: wherein [IV], -X- and -Q are as defined in the formula [I], -X ³ represents a hydrogen atom, a chlorine atom or a bromine atom, j is Represents an integer of 0 or 1. ] General formula [V] A phthalocyanine dye represented by the formula: [In the formula [V], -X- and -Q have the same definitions as those in the above formula [I], and [Pc] represents a copper phthalocyanine residue or a nickel phthalocyanine residue; R ¹⁰ , -R ¹¹ and-
R ¹² represents a hydrogen atom, a substituted or unsubstituted alkyl group, a cyclohexyl group, an allyl group or a substituted or unsubstituted aryl group, —W— represents an alkyl group or an arylene group, and n ¹ represents a number of 0 to 2 And m is 1 to 4
, 1 represents a number from 0 to 1, and -Z represents a metal atom or an alkylammonium salt. ] General formula [VI] In benzothiazole monoazo dye represented: [in the formula [VI], -M represents a hydrogen atom or a halogen atom, -L represents a halogen atom, -R ¹³ - and -R
^14- represents an ethylene group or a propylene group, -R ¹⁵
Represents an alkyl group which may be substituted with a lower alkoxy group. The mixed fiber to be used in the present invention is a fiber in which two or more kinds of fibers selected from polyester, acetate and nitrogen-containing fibers are mixed, and particularly, polyester or acetate and silk, wool or polyamide are mixed. It is preferably applied to fibers. Specific examples of each fiber include, in the case of polyester fiber, for example, polyethylene terephthalate, polybutylene terephthalate, anion dyeable polyethylene terephthalate, cation dyeable polyethylene terephthalate, and in the case of acetate fiber, for example, triacetate, Examples thereof include diacetate, heat-resistant diacetate, and the like, and examples of the nitrogen-containing fiber include silk, wool, polyurethane, polyamide (6-nylon, 6,6-nylon), leather and the like.

In dyeing the above mixed fibers, the reactive disperse dyes represented by the above general formulas [I] to [VI] are added to the medium in an amount of 0.
It is desirable to finely disperse it to about 5-2 μ, and as a method therefor, a nonionic surfactant such as a pluronic type surfactant, or an anionic dispersant such as sodium ligninsulfonate or sodium naphthalenesulfonate-formalin condensate is used. Using a water-soluble dispersant such as salt,
A method of finely dispersing in water using a grinder such as a sand grinder, a solvent other than water, such as sulfosuccinate, nonylphenol, or a compound obtained by adding ethylene oxide to a low mole, such as alcohols, ketones, hydrocarbons, Method for finely dispersing in halogenated hydrocarbons, esters, ethers, or a mixed solvent thereof, and finely dispersed in a mixed system of water and a solvent of the above solvents which can be arbitrarily mixed with water And so on.

Further, in the above fine dispersion process, a high molecular compound soluble in each dispersant or a surfactant having a function other than the dispersing action may be added.

This fine dye dispersion can be used as it is as a dyeing bath for a dip dyeing method and a padding dyeing method, and as a color paste in a printing dyeing method.

Generally, the dye fine dispersion produced by the above,
O / W type or W / O type emulsion of water and water of organic solvent or petroleum hydrocarbon, halogenated hydrocarbon, etc. and water, diluted to the target dyeing concentration, and dyeing bath, padding bath or printing dyeing Used as glue.

In the preparation of the dipping bath, the padding bath and the printing dye paste, an alkali metal compound or an alkali precursor compound which generates an alkali when heated in the presence of water can be added as an acid binder.

The amount of these acid binders to be used may be such that the pH of the dyeing bath, the padding bath or the printing dye paste is in the range of 6.5 to 9.0.

When continuous dyeing or printing of mixed fibers is performed, urea such as N, N, N ', N'-tetramethylurea, polyhydric alcohols such as polyethylene glycol, polypropylene glycol, etc. are added to the dye bath or color paste. Alternatively, it is preferable that a derivative thereof is present. In particular, among these, the average molecular weight is 200
Polyhydric alcohol derivatives, such as polyethylene glycol and polypropylene glycol of about 500 to dimethylated and diacetylated hydroxyl groups at both ends, which do not react with the reactive groups of the dye are suitable. The amount used is usually in the range of 4 to 15% by weight, preferably 5 to 10% by weight in the dye-particulate solution.

In order to dye the fibers by the padding method or the printing method with the dyes represented by the above-mentioned general formulas [I] to [VI], the mixed fiber is impregnated with the padding bath or the printing dye paste prepared by the above method according to a conventional method. Or, after printing and drying, hot air or superheated steam at 160 ° -220 ° C for 30 seconds-10
Heat treatment for 1 minute, or treatment in high-pressure saturated steam at 120 ° -150 ° C for 3-30 minutes, and wash with hot water containing surfactant, or O / W type where the oil layer is a halogenated hydrocarbon such as tetrachloroethylene. Alternatively, it is completed by washing with a W / O type emulsion washing bath or washing with a usual dry cleaning method. For dyeing by the dip dyeing method, the mixed fiber is heated at 80 to 140 ° C according to the usual method.
Then, it can be carried out by soaking for 20 to 60 minutes.

By the above method, it is possible to obtain a dyed product which is dyed vividly and uniformly and has good light fastness and wet fastness.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

 In the examples, "part" means "part by weight".

Example 1 The following structural formula 15 g of a reaction-dispersion type monoazo dye represented by, naphthalenesulfonic acid-formaldehyde condensate 15 g and water 70 ml
Was finely dispersed using a paint shaker as a fine disperser to prepare a dye dispersion liquid. Using this dye dispersion, the following dye dispersion 6.5 g 5% sodium alginate aqueous solution 55 g polyethylene glycol dimethyl ether having an average molecular weight of 400 5 g water residual amount 100 g of printing dye paste (pH 8.0) was prepared, Polyethylene terephthalate / silk (mixing ratio 75/25) mixed woven fabric was printed using a screen printing machine, intermediately dried at 80 ° C for 30 minutes, and then 180 ° C.
It was fixed by steaming for 7 minutes. After washing this with water, using a cleaning solution containing 2 g / nonionic surfactant [Score Roll # 900 (trademark), manufactured by Kao Soap Co., Ltd.], a bath ratio of 1: 3.
Soaping was performed at 0 ° C. for 20 minutes at 80 ° C. to obtain a yellow dyed product having a light fastness grade 5 and a wash fastness grade 5. This dyed product is made of polyethylene terephthalate and silk,
It was dyed well.

Example 2 The following structural formula Reaction dispersion type disazo dye 16g, polyoxyethyne glycol nonyl phenyl ether (HLB 13.3) 7
g, naphthalenesulfonic acid-formaldehyde condensate 3g
And 74 ml of water were finely dispersed using a sand glider to prepare a dye dispersion. Using this dye dispersion, prepare a padding bath (pH 8.0) with the following composition: Dye dispersion 6 g Tetraethylene glycol dimethyl ether 15 g Water balance 100 g, Polybutylene terephthalate / wool (mixing ratio 70/30) blended cloth Impregnated into
After squeezing to a squeezing ratio of 45%, it was dried at 100 ° C. for 2 minutes and fixed by dry heat at 190 ° C. for 1 minute. By washing this with a hot ethanol bath, light fastness grade 5-6 and washing fastness 5
A graded orange dyeing is obtained. The dyed product was dyed well with both polybutylene terephthalate and wool.

Example 3 The following structural formula Reaction-dispersion type anthraquinone dye represented by 10 g, naphthalenesulfonic acid-formaldehyde condensate 25 g, water 65 m
l was finely dispersed using a sand grinder as a differential acid machine to prepare a dye dispersion liquid. Using this dye dispersion, prepare a dyeing bath (pH 8.0) of the following composition: 2 g of water, 300 g of water balance, and put 10 g of nylon / diacetate (mixing ratio 50/50) into the dyeing bath. Room temperature gradually 12
It was heated to 0 ° C. and dyed at this temperature for 1 hour.

When the washing treatment was carried out in accordance with the method described in Example 1 below, a dyed product having a level of light fastness of Grade 5 and a dry cleaning fastness of Grade 5 and having a good levelness of bluish red was obtained. The dyed product was dyed well with both nylon and diacetate.

Example 4 The following structural formula 15g of reaction dispersion type anthraquinone dye, Pluronic type surfactant [Pluronic L64 (manufactured by Asahi Denka Kogyo Co., Ltd.)] and 75 ml of water are finely dispersed using a sand grinder as a fine disperser to give a dye dispersion. Prepared. Using this dye dispersion, the following dye dispersion was prepared: 7 g 5% sodium alginate aqueous solution 55 g Polypropylene glycol diacetate with an average molecular weight of 300 10 g Water residue 100 g of printing dye paste (pH 8.0) was prepared. Silk (mixing ratio 75/25) woven cloth was printed using a screen printing machine, intermediately dried at 80 ° C for 3 minutes, and then at 185 ° C for 7 minutes.
It was treated with superheated steam. Then, when the washing treatment was carried out according to the method described in Example 1, a dyed product of blue having a fastness to light of grade 5 and a fastness to washing of grade 4 to 5 with good levelness was obtained.

Example 5 The following structural formula 10 g of the reaction-dispersed monoazo dye represented by the formula (1), 10 g of naphthalenesulfonic acid-formaldehyde condensate, and 80 ml of water were finely dispersed using a paint shaker as a fine disperser to prepare a dye dispersion liquid. This dye dispersion was used to prepare the following dye dispersion 10 g triethylene glycol dimethyl ether 40 g 6% sodium alginate aqueous solution 550 g water residual amount 1000 g printing dyeing paste (pH 8.0), polyester / nylon / wool (mixing ratio) 70/10/20) The mixed spinning fabric was printed using a screen printing machine, intermediately dried at 80 ° C. for 3 minutes, and then treated with superheated steam at 180 ° C. for 6 minutes. When this was washed according to the method described in Example 1, a uniformly dyed red-dyed product having a dry cleaning fastness of grade 5 and good levelness was obtained.

Example 6 Polyethylene terephthalate / silk interwoven fabric was printed using the reactive disperse dyes shown in Table 1 in the same manner as in Example 1, and as a result, uniform printed products were obtained.

(Effect of the Invention) According to the present invention, a mixed fiber containing two or more kinds of fibers selected from polyester, acetate and nitrogen-containing fibers, which have been conventionally dyed in two stages, by using a reactive disperse dye. Can be satisfactorily performed in a single step.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yukiharu Shimizu 1 2447 Fujita, Hachimansai Ward, Kitakyushu, Fukuoka Prefecture Mitsubishi Kasei Kogyo Co., Ltd. Kurosaki Plant (56) Reference JP-A-49-12182 (JP, A) JP-A-61-266686 (JP, A) JP-A-55-133456 (JP, A) JP-A-55-135164 (JP, A) JP-A-55-152875 (JP, A) JP-A-55-164250 (JP, A)

Claims (2)

[Claims] 1. A dye containing a reactive disperse dye represented by the following general formulas [I] to [VI] when dyeing a mixed fiber containing two or more kinds of fibers selected from polyester, acetate and nitrogen-containing fibers. A method for dyeing mixed fibers, characterized by using a bath or printing dye paste. General formula [I] [In the formula [I], K is Represents, May be substituted with a phenyl group, a lower alkyl group, a lower alkoxy group, a phenoxy group, a nitro group, a cyano group, a halogen atom, a trifluoromethyl group, an acetylamino group, a lower alkylcarbonyl group or a lower alkylsulfonyl group. Represents a phenyl group, Represents a naphthylene group or a lower alkyl group, a lower alkoxy group, a phenylene group which may be substituted with a halogen atom or an acetylamino group, Represents a lower alkyl group, a lower alkoxy group, an acetylamino group or a phenylene group optionally substituted by a halogen atom, -Y ¹ and -Y ² represent an alkyl group optionally substituted by a lower alkoxy group, —Y ³ represents an alkyl group which may be substituted with a lower alkoxy group, an allyl group or an aralkyl group, —V represents a cyano group or a —CONH ₂ group, and —X— represents —O— or —S—. And Q is (-R ¹ and -R ² are a hydrogen atom or a cyano group, a hydroxyl group, a lower alkoxy group or an alkyl group which may be substituted with a dialkylamino group, an alkenyl group,
It represents a cyclohexyl group, an aryl group or an aralkyl group. ) Is represented. ]. General formula (II) [In the formula [II], -T represents a hydrogen atom, a lower alkyl group, a nitro group or a halogen atom, -Y ⁴ represents a substituted or unsubstituted alkyl group or an aralkyl group, and -A ¹
- is CH ₂ - group, -C ₂ H ₄ - group, -OC ₂ H ₄ - group, -CONHC ₂ H ₄ -
A group, a —SO ₂ NHC ₂ H ₄ — group or a —SO ₂ C ₂ H ₄ — group, and
Represents 0 or 1, and -X- and -Q are the same as defined in the above formula [I]. ] General formula [III] [In the formula [III], -R ⁴ represents an amino group or a hydroxyl group, -R ⁵ and -R ⁶ represent a hydrogen atom, an amino group, a hydroxyl group, a nitro group, a chlorine atom or a bromine atom, and -R ⁷ It represents a hydrogen atom, a chlorine atom, a bromine atom, a cyano group, or -SO ₂ R ⁸ (-R ⁸ represents a methyl group, an ethyl group or a phenyl group), -E- represents -O- or -S-
Represents a linking group consisting of, -X ¹ and -X ² one of which represents a hydrogen atom, the other is (-X- and -Q are the same as defined in the above formula [I],
—R ⁹ represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a chlorine atom or a bromine atom), and k is 0 or 1. Is provided that when -X ² is a hydrogen atom k is 0. ] General formula [IV] Wherein [IV], -X- and -Q are as defined in the formula [I], -X ³ is a hydrogen atom, likeness Table chlorine atom or a bromine atom, j represents an integer of 0 or 1 Represent. ] General formula [V] [In the formula [V], -X- and -Q are the same as the definition of the above formula [I], [Pc] represents a copper phthalocyanine residue or a nickel phthalocyanine residue, and -R ¹⁰ , -R ¹¹ and −
R ¹² represents a hydrogen atom, a substituted or unsubstituted alkyl group, a cyclohexyl group, an allyl group or a substituted or unsubstituted aryl group, —W— represents an alkylene group or an arylene group, and n ¹ represents a number of 0 to 2 And m is 1 to
Represents a number of 4, l represents a number of 0 to 1, and -Z represents a metal atom or an alkylammonium salt. ] General formula [VI] [In the formula [VI], -M represents a hydrogen atom or a halogen atom, -L represents a halogen atom, -R ¹³ -and -R
^14- represents an ethylene group or a propylene group, -R ¹⁵
Represents an alkyl group which may be substituted with a lower alkoxy group. ] 2. The dyeing method according to claim 1, wherein the mixed fiber is a mixed fiber of polyester or acetate and silk, wool or polyamide.