JPH0651955B2 - Method for dyeing cellulosic fibers - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for dyeing cellulosic fibers. More specifically, it relates to a method for improving dyeability by using a specific water-soluble copolymer when dyeing cellulosic fibers such as cotton and hemp.

(Prior Art) When dyeing a cellulosic fiber, a dyeability improver has been used to obtain uniform dyeability. The performance required as a dyeability improver includes solubilization / dispersion ability of dyes and chelating ability for various polyvalent metal ions such as calcium ion, magnesium ion, iron ion, aluminum ion, manganese ion in water. There is.

For dyeing cellulosic fibers, direct dyes, sulfur dyes, slene dyes, naphthol dyes, reactive dyes, basic dyes, acid dyes and the like are used as dyeing agents. And for direct dyes, acid dyes, reactive dyes, etc., dyes of the type containing metals such as chromium, copper, cobalt, iron, and aluminum are often used. There was a problem that uniform dyeing could not be obtained because of poor solubility and dispersibility.

In addition, since the slene dye that is often used for dyeing cellulosic fibers is composed of a water-insoluble compound having two or more carbonyl groups, the dyeing is performed by using an alkaline agent and a reducing agent. Is carried out in the form of a water-soluble sodium leuco salt, and it is fixed by oxidizing the water-soluble sodium leuco salt into a quinone body after dyeing to make it water-insoluble again. However, when the hardness of water used for dyeing is high, the hardness component of water binds to the dye to form a dye dimer, which is insoluble in water and has no affinity with cellulosic fibers. There is a problem in that the color density that should be obtained from the dye density used cannot be obtained.

In order to overcome these problems, in the dyeing process, aminocarboxylic acid dyes such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxylethylenediaminetriacetic acid and nitrilotriacetic acid, and condensed phosphoric acid dyes such as tripolyphosphoric acid, hexametaphosphoric acid and pyrophosphoric acid are dyed. Enhancers have been used.

However, when dyeing with an aminocarboxylic acid-based agent, for example, using a metal-containing dye, uniform dyeing is difficult because the solubilizing ability and dispersing ability of the dye are poor. In addition, the aminocarboxylic acid type agent strongly exerts the action of forming a complex salt with a metal as a coloring group in the dye, so that the dye-metal coordinate bond is out of balance and the hue of the dyed cloth is used. It had a fatal problem that it was out of phase with the dye that had been obtained.

In addition, the condensed phosphoric acid-based agent becomes a causative agent of red tide when it flows into the sea or lake through wastewater such as rivers.
In recent years, its use is about to be restricted.

In order to eliminate the drawbacks of the aminocarboxylic acid-based and condensed phosphoric acid-based dyeability improving agents, JP-A-59-2
11688, JP-A-59-216987, JP-A-6
0-162882, JP-A-61-266683, JP-A-62-90382, etc., one or more unsaturated carboxylic acid type monomers such as (meth) acrylic acid and maleic acid are used ( The use of (co) polymers has been proposed. However, since these (co) polymers are likely to be insolubilized by binding with polyvalent metal ions in the water, it is necessary to add a large amount of agent in order to exert the effect. In addition, these (co) polymers have not yet been radically solved, for example, it is difficult to dye uniformly because the solubilizing ability and dispersing ability of the dye are not sufficient.

Further, JP-A-61-289186 proposes the use of a water-soluble salt of a copolymer of an olefin and an ethylenically unsaturated dicarboxylic acid anhydride, and these copolymers also have the above-mentioned (meth) acrylic acid. And had the same problems as maleic acid (co) polymers.

Further, JP-A-60-162882 proposes the use of a copolymer of an unsaturated carboxylic acid type monomer and a polyoxyalkylene monoallyl ether type monomer. But,
This copolymer has a relatively good chelating ability, which is one of the performances that the dyeability improver should have, but is insufficient in the solubilizing ability and dispersing ability with respect to the dye, and therefore, in achieving uniform dyeing. It was still a problem. In addition, since polyoxyalkylene monoallyl ether-based monomers have poor copolymerizability with unsaturated carboxylic acid-based monomers, a relatively large amount of unreacted monomer remains, resulting in a product with high purity. There was also a drawback that it was difficult to obtain.

(Problems to be Solved by the Invention) The present invention solves the above problems that conventional dyeability improvers have when dyeing cellulosic fibers.

Therefore, an object of the present invention is to enhance the solubility and dispersibility of a dye in a bath and remove the adverse effects of various polyvalent metal ions in water by dyeing a cellulosic fiber with a specific dyeability improver. Therefore, it is an object of the present invention to provide a method for uniformly dyeing a fiber to a desired hue.

(Means and Actions for Solving the Problems) The present invention provides a general formula for dyeing a cellulosic fiber. (In the formula, A ¹ and A ² each independently represent hydrogen, a methyl group or —COOX ² and A ₁ and A ₂ do not become —COOX ² at the same time, and A ³ represents a hydrogen, a methyl group or —CO ^2). CH ₂ COOX ³ and when A ³ is CH ₂ COOX ³ , A ¹ and A ² each independently represent hydrogen or a methyl group, and X ¹ , X ² and X ³ each independently or together represent hydrogen. ,
It represents a monovalent metal, a divalent metal, an ammonium group or an organic amine group. Unsaturated carboxylic acid type monomer (I) 40-99.
5 mol% and general formula (In the formula, R ¹ represents hydrogen or a methyl group, and a,
b, d and f each independently represent 0 or a positive integer and a + b + d + f = 0 to 100, and OC ₂ H ₄
The units and the OC ₃ H ₆ units may be bonded in any order, and when d + f is 0, Z is a hydroxyl group, a sulfonic acid group or a monovalent metal salt thereof, a divalent metal salt, an ammonium salt, an organic salt. It represents an amine salt or a (phosphite) group or a monovalent metal salt thereof, a divalent metal salt, an ammonium salt or an organic amine salt, and when d + f is a positive integer of 1 to 100, Z represents a hydroxyl group. ) Unsaturated (meth) allyl ether monomer (II)
A method for dyeing a cellulosic fiber, which comprises using a water-soluble copolymer (A) having an average molecular weight of 1,000 to 100,000 derived from a monomer component consisting of 0.5 to 60 mol% It is a thing.

Examples of the unsaturated carboxylic acid-based monomer (I) represented by the general formula used in the present invention include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid or the like. Acid monovalent metal, 2
Partially neutralized products or fully neutralized products with valent metals, ammonia and organic amines can be mentioned. Examples of the monovalent metal include sodium and potassium, and examples of the divalent metal include calcium, magnesium and zinc. Further, as the organic amine, monomethylamine, dimethylamine,
Examples thereof include alkylamines such as trimethylamine, monoethylamine, diethylamine and triethylamine; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine and dimethylethanolamine; pyridine and the like.

Examples of the unsaturated (meth) allyl ether-based monomer (II) represented by the general formula include glycerol mono (meth) allyl ether and 3- (meth) allyloxy-2.
-Hydroxypropane sulfonic acid (salt), 3- (meth)
Examples thereof include compounds in which 1 to 100 mol of ethylene oxide and / or propylene oxide is added to 1 mol of allyloxy-2-hydroxypropanephosphoric acid (salt) and the (meth) allyl ether-based monomer. The number of kinds of ethylene oxide and propylene oxide may be one or two, and in the case of adding many kinds, there is no limitation on the bonding order. The added mole number of alkylene oxide is 0 to 100 moles, preferably 0 to 50 moles. The number of added moles of alkylene oxide is 100.
If it exceeds the molar amount, a large amount of addition is required, which is not preferable.

The water-soluble copolymer (A) used in the present invention is an unsaturated carboxylic acid-based monomer (I) represented by the general formula 40 to 9
The average molecular weight derived by polymerizing a monomer component composed of 9.5 mol% and 0.5 to 60 mol% of an unsaturated (meth) allyl ether monomer (II) is 1,000 to 10
It is a copolymer of 50,000, and if it is out of any of these ranges, the dyeability is not good.

To obtain the water-soluble copolymer (A) used in the present invention, a monomer composed of these unsaturated carboxylic acid type monomer (I) and unsaturated (meth) allyl ether type monomer (II) The components may be polymerized by known techniques. For example, in the case of water-soluble polymerization, persulfates such as sodium persulfate and potassium persulfate;
Hydrogen peroxide; a water-soluble azo compound such as 2,2'-azobis (2-amidinopropane) hydrochloride or 4,4'-azobis-4-cyanovaleric acid can be used as a polymerization catalyst to be produced by a conventional method. Further, alcohols such as methanol and isopropyl alcohol, ethers such as tetrahydrofuran and dioxane, benzene, xylene,
In the case of polymerization in an aromatic solvent such as toluene or a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, organic peroxide such as benzoyl peroxide, lauroyl peroxide, peracetic acid; azobisisobutyronitrile ,
An oil-soluble azo compound such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) or the like can be produced by a conventional method as a polymerization catalyst.

Further, in obtaining the water-soluble copolymer (A), unsaturated carboxylic acid monomer (I) and unsaturated (meth) allyl ether monomer (II) within a range not impairing the effects of the present invention. It is of course possible to polymerize other monomers copolymerizable with
Other copolymerizable monomers include, for example, amide-based monomers such as (meth) acrylamide and t-butyl (meth) acrylamide; (meth) acrylic acid ester, styrene, 2-methylstyrene, vinyl acetate, etc. Hydrophobic monomer of vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, 2-acrylamide-
2-Methylpropanesulfonic acid, sulfoethyl (meth)
Acrylate, sulfopropyl (meth) acrylate,
2-hydroxysulfopropyl (meth) acrylate,
Sulfoethylmaleimide or monovalent metal thereof, 2
Unsaturated sulfonic acid-based monomers such as partially neutralized products and completely neutralized products with valent metals, ammonia, and organic amines; 2-hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth ) Acrylate, allyl alcohol, polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 3-methyl-3-
Butene-1-ol (isoprenol), polyethylene glycol monoisoprenol ether, polypropylene glycol monoisoprenol ether, 3-methyl-2-buten-1-ol (prenol), polyethylene glycol monoprenol ether, polypropylene glycol mono Prenol ether, 2-methyl-3-
Butene-2-ol (isoprene alcohol), polyethylene glycol monoisoprene alcohol ether,
Polypropylene glycol monoisoprene alcohol ether, α-hydroxyacrylic acid, N-methylol (meth) acrylamide, glycerol mono (meth) acrylate, vinyl alcohol and other hydroxyl group-containing unsaturated monomers; dimethylaminoethyl (meth) acrylate,
Cationic monomers such as dimethylaminopropyl (meth) acrylamide; nitrile monomers such as (meth) acrylonitrile; (meth) acrylamidomethanephosphonic acid, (meth) acrylamidomethanephosphonic acid methyl ester, 2- (meth) Phosphorus-containing monomers such as acrylamido-2-methylpropanephosphonic acid; ethylene, propylene, 1-butene, isobutylene, α-amylene, 2
-Methyl-1-butene, 3-methyl-1-butene (α-
Α such as isoamylene), 1-hexene, 1-heptene
-Olefin-based monomers can be mentioned.

In the present invention, as the cellulosic fibers that can be suitably dyed using the water-soluble copolymer (A), for example, cellulosic natural fibers such as cotton and hemp, rayon, cellulosic regenerated fibers such as cupola, etc. In addition, there are mixed fibers of these with nylon, polyester, synthetic fibers such as acrylic, and further mixed fibers with semi-synthetic fibers such as acetate, and the form at the time of dyeing is also fiber, thread, cheese, woven fabric, knitted fabric, It does not matter whether it is a non-woven fabric or a final textile product such as clothes and bedding products.

Further, in the present invention, conventionally used aminocarboxylic acid type, condensed phosphoric acid type, (co) polymers of unsaturated carboxylic acid type monomers such as acrylic acid and maleic acid,
Water-soluble copolymers (A) of sugar alcohols, aldonic acids, sulfonated monocyclic or polycyclic aromatic compounds, etc.
Of course, it can be used together with.

(Effects of the Invention) According to the method for dyeing a cellulosic fiber of the present invention, when dyeing a cellulosic fiber with any dye such as a metal-containing dye or a slene dye, dyeing is performed as compared with a method using a conventional dyeability improving agent. The property can be greatly enhanced, and the fiber can be uniformly dyed to a desired hue even when water having high hardness is used.

(Examples) Hereinafter, the present invention will be described with reference to Reference Examples and Examples, but the present invention is not limited to these Examples.
Unless otherwise specified, all parts are parts by weight and%
All represent% by weight.

Examples 1 to 13 g of the salt of the copolymer shown in Table 1 was used as a dyeing agent.
The cotton twill fabric was dyed under the following conditions. The obtained results are shown in Table 1.

(Dyeing conditions) Hardness of water used 30 ° DH Dye Kayaras Supra Blue 4BL conc 1%
owf (metal-containing direct dye manufactured by Nippon Kayaku Co., Ltd.) Sodium sulfate decahydrate 10% owf bath ratio 1:30 temperature 95 ° C time 30 minutes After dyeing, soaping was carried out by a conventional method.

(Evaluation) The dyed cloth was subjected to color measurement with an SM color computer SM-3 type manufactured by Suga Test Instruments Co., Ltd., and a Hue value (value on the Munsell hue circle) was determined to be a scale of hue. In addition, the level unevenness was evaluated by visually observing partial dark color unevenness.

Further, 300 g of a mixed liquid (dyeing liquid) of water having a hardness of 30 ° DH, a dye (0.1%) and a dyeability improving agent (0.1%) was prepared, and left for 24 hours, then, 5C paper manufactured by Toyo Paper Co., Ltd. And the state of over-residue was visually judged and used as a scale of dye dispersibility.

Comparative Examples 1 to 15 Dyeing was performed in exactly the same manner as in Examples 1 to 13 except that the polymer salts shown in Table 2 were used as the dyeability improver. The results obtained are shown in Table 2.

Comparative Example 16 Dyeing was performed in exactly the same manner as in Examples 1 to 13 except that sodium ethylenediaminetetraacetate was used as the dyeability improver. The results obtained are shown in Table 2.

Comparative Example 17 Dyeing was performed in exactly the same manner as in Examples 1 to 13 except that sodium tripolyphosphate was used as the dyeability improver. The results obtained are shown in Table 2.

Comparative Example 18 Dyeing was carried out in exactly the same manner as in Examples 1 to 13 except that no dyeability improver was used. The results obtained are shown in Table 2.

The meanings of the monomer abbreviations in Tables 1, 2, 3 and 4 are as follows.

MA: maleic acid FA: fumaric acid IA: itaconic acid AA: acrylic acid MAA: methacrylic acid CA: crotonic acid SEM: sulfoethyl methacrylate VS: vinyl sulfonic acid Examples 14 to 26 2 g of the salt of the copolymer shown in Table 3 as a dyeability improver
/ Was used to dye a cotton twill fabric under the following conditions. The results obtained are shown in Table 3.

(Dyeing conditions) Hardness of used water 50 ° DH Dyeing Mikethren Blue RSN s / f1% owf (Slen dye manufactured by Mitsui Toatsu Chemicals, Inc.) Hydrosulfite 4 g / sodium sodium hydroxide 5 g / temperature 70 ° C. Interval: 20 minutes After dyeing, oxidation was carried out by a conventional method, and then soaping.

(Evaluation) The dyed cloth was subjected to color measurement with an SM color computer SM-3 type manufactured by Suga Test Instruments Co., Ltd., and a C ^* value was obtained and used as a scale of color density.

In addition, the partial dark color unevenness was measured by the naked eye and used as a scale of the level dyeing property.

Comparative Examples 19 to 33 Dyeing was performed in the same manner as in Examples 14 to 26 except that the polymer salts shown in Table 4 were used as the dyeability improver.
The results obtained are shown in Table 4.

Comparative Example 34 Dyeing was carried out in the same manner as in Examples 14 to 26 except that sodium ethylenediaminetetraacetate was used as the dyeing agent. The results obtained are shown in Table 4.

Comparative Example 35 Dyeing was performed in the same manner as in Examples 14 to 26 except that sodium tripolyphosphate was used as the dyeability improver.
The results obtained are shown in Table 4.

Comparative Example 36 Examples 14 to 26 except that no dyeability improver was used at all.
Dyeing was performed in exactly the same manner as in. The results obtained are shown in Table 4.

Claims (5)

[Claims] 1. A general formula for dyeing a cellulosic fiber (In the formula, A ¹ and A ² each independently represent hydrogen, a methyl group or —COOX ² and A ¹ and A ² do not become —COOX ² at the same time, and A ³ represents a hydrogen, a methyl group or —CO ^2). CH ₂ COOX ³ and when A ³ is CH ₂ COOX ³ , A ¹ and A ² each independently represent hydrogen or a methyl group, and X ¹ , X ² and X ³ each independently or together represent hydrogen. ,
It represents a monovalent metal, a divalent metal, an ammonium group or an organic amine group. Unsaturated carboxylic acid type monomer (I) 40-99.
5 mol% and general formula (In the formula, R ¹ represents hydrogen or a methyl group, and a,
b, d and f each independently represent 0 or a positive integer and a + b + d + f = 0 to 100, and OC ₂ H ₄
The units and the OC ₃ H ₆ units may be bonded in any order, and when d + f is 0, Z is a hydroxyl group, a sulfonic acid group or a monovalent metal salt thereof, a divalent metal salt, an ammonium salt, an organic salt. It represents an amine salt or a (phosphite) group or a monovalent metal salt thereof, a divalent metal salt, an ammonium salt or an organic amine salt, and when d + f is a positive integer of 1 to 100, Z represents a hydroxyl group. ) Unsaturated (meth) allyl ether monomer (II)
A method for dyeing cellulosic fibers, which comprises using a water-soluble copolymer (A) having an average molecular weight of 1,000 to 100,000 derived from a monomer component of 0.5 to 60 mol%. 2. The dyeing method according to claim 1, wherein a water-soluble copolymer (A) in which a + b + d + f is 0 and Z is a hydroxyl group is used. 3. The dyeing method according to claim 1, wherein a water-soluble copolymer (A) in which a + b + d + f is 0 and Z is a sulfonic acid (salt) group is used. 4. The dyeing method according to claim 1, wherein the water-soluble copolymer (A) in which b + f is 0 and a + d is a positive integer of 1 to 50 is used. 5. The dyeing method according to claim 1, wherein the water-soluble copolymer (A) having an average molecular weight of 2,000 to 70,000 is used.