JPH02104780A - Method for unevenly dyeing a cellulose fiber under non-existence of an alkali or a reducing agent - Google Patents

Abstract

PURPOSE: To dye cellulose-based fibers clearly and in fast color by pre-treating the cellulosic fibers with a solution containing a wetting agent, a reaction product of a polyethyleneimine with a bifunctional alkylating agent and an ionic surfactant, and dying the fibers with a reactive dye, etc., without using an alkali or a reducing agent. CONSTITUTION: Cellulosic fibers are pre-treated with a pre-treatment solution containing a wetting agent, a quaternized reaction product of a polyethyleneimine with a bifunctional alkylating agent (e.g. epichlorohydrin, 1,3-dichaloropropane-2-ol, etc.), and an anionic surfactant, thereafter dyed in fast color by using a reactive dye or a sulfur dye without the addition of an alkali or a reducing agent. A dyed product in which warp yarns are nonuniform is obtained by treating a warp yarn consisting of cellulose fibers with a sizing liquor containing the pre-treating agent, weaving them with a white cotton weft yarn, dying them with a reactive dye without the addition of alkali and the weft yarn without pre-treated become white by soaping, etc., to present a mottled fabric expressing denim effects.

Description

DETAILED DESCRIPTION OF THE INVENTION The dyeing of textile materials, such as textiles, knitted fabrics or yarns, consisting of or containing cellulose fibers, with reactive dyes can be carried out by applying reactive dyes to the textile material by exhaustion in a known manner. It can be carried out by treatment in the presence of alkali, usually at high temperatures and with most types of commercially available reactive dyes, depending on the dye liquor containing, or by continuous or batch-type processes, such as so-called pads. - Can be carried out by applying a steam method or a cold batch method. In the band-steam process as well as the cold-pad-batch process, the fiber material is first bubbled with a reactive dye liquor, the alkali required for fixation being usually applied in a side impregnation step. Bad-
In the steam method, fixation of the dye is then completed by steaming, and in the case of the cold batch method, by placing the impregnated material on a take-up roll and leaving the material at room temperature for several hours. . Other possible fixing methods are known and have industrial application, for example the treatment of materials badged with alkali-free reactive dye liquors with sodium hydroxide/water glass.

These total dyeing methods are designed to achieve as uniform a distribution of the dye over the warp and width of the fabric as possible.

In all the above-mentioned reactive dyeing methods, chemical covalent bonds are formed between the dye and cellulose molecules during the dyeing process. The presence of an alkali is absolutely necessary for this in all cases.

No. 4,806,126 describes a method for dyeing cellulose fibers with reactive dyes, which does not require the presence of alkali. Fixation of the dye on the fibers is achieved in this method by pretreating the fibers with a reaction product consisting of polyethyleneimine and a difunctional alkylating agent before dyeing.

Further developing this method, the inventors have found that asymmetric dyeings can be obtained by additionally adding another anionic surfactant to the processing liquor containing the pre-mordant.

In this way dyeings with a light-dark effect are obtained which open new possibilities for the fashion design of textile materials.

The present invention provides a method for asymmetrically dyeing cellulose fibers in the absence of an alkali or reducing agent, in which cellulose fibers are dyed with a wetting agent, polyethyleneimine, which may be quaternized, and a bifunctional alkylating agent. A process comprising treating the fiber with a treatment liquid containing a reaction product and an anionic surfactant, drying the fiber and dyeing the fiber with a reactive, direct or water-soluble sulfur dye without addition of alkali. .

Necessary auxiliaries for pretreatment are described in U.S. Pat. No. 4, s8e, 4.
It is described in the specification of No. i3. There, auxiliaries are used exclusively for the post-treatment of dyeing with reactive dyes. Pretreatment with this auxiliary agent and no alkali or reducing agent are used.

Subsequent staining is not described there. A process for exclusively after-treating reactive dyes with compounds having a similar structure is also described in GB 2,006,279.

The polyethyleneimine necessary for producing the pretreatment agent to be used according to the invention has the general formula % (where χ is a residue of the formula -(CHz-CL-NH)c-H) , a and b independently of one another are numbers from O to 600, the sum of a+b being a number from 50 to 600, and C is a number from O to 50).

The polyethyleneimine used is therefore a molecule in which there are -N1]2, >NH and -N constituent units linked to each other by ethylene groups. In total, the polyethyleneimine contains about 50 to 600 ethyleneimine units. In typical commercial products, the primary, secondary and tertiary nitrogen functionality is present in a numerical ratio of about 1:2:1.

In principle, all known difunctional alkylating agents can be used for the reaction with ethyleneimines of the general formula I. These known bifunctional alkylating agents correspond to the general formula (II).

In this formula A is the residue of the alkylating agent and Z
is a direct bond or a bivalent bridge rung link.

General formula ■ [Into the general formula -CIl□-Y (where Y is a substituent that can be eliminated as an anion, especially chlorine, bromine, iodine or -〇■ or that can be eliminated as an anion) In particular, a sulfato group or a sulfonyloxy group, especially a group represented by the following formula: nylsulfonyloxy or l)-tolyl-sulfonyloxy or an epoxy group 10\ -CH-C8z and if Z is not a direct bond, -i2■-C, +1
□1-(III) (wherein n is a number from 1 to 4) Divalent straight chain or branched residues, general 2■ -CIIl(2-D-C-)+2-( IV) (m in the formula
is 1 or 2 and D is 10-1-S-1-Nl (
-, -GO-1-SO- or -307-) or phenylene] are reacted with polyethyleneimine and used according to the invention. Particularly suitable for obtaining auxiliaries to be processed.

General formula -C11, in which one of these bifunctional alkylating agents or residues A is bonded directly to an epoxy group, where A is a group of general formula -C11, -Y, which are bonded to each other by a bridging link of general formula (2); These difunctional alkylating agents, which are the group Y 2 , are particularly suitable for reacting with polyethyleneimine to obtain the auxiliaries to be used according to the invention.

Examples of such difunctional alkylating agents are epichlorohydrin, glycidol, 1,3-dichloropropan-2-ol, β,β'-dichlorodiethyl ether, β,β'
-dichlorodiethylamine, β, β'-dichlorodiethylsulfide, β, β'-dichlorodiethylsulfoxide, β, β'-dichlorodiethylsulfone, β, β'-
Disulfatoethyl ether, β, β'-diphenylsulfonyloxyethyl ether, meta- or para-jepoxyethylbenzene, meta-5 or para-jepoxypropylbenzene, jepoxybutane, jepoxy-2-
Methylbutane and jepoxypropylamine.

The pretreatment agent to be used according to the invention comprises polyethyleneimine and a difunctional alkylating agent at 100:o, ox
to 100:2. o Preferably 100:0.1 to 100:1. They are produced by reacting with each other in a weight ratio of O.

It is assumed that the incorporation of reticulating bridging links between the polyethyleneimine chains takes place during this reaction. The superficial manifestation of this is that the viscosity of the aqueous solution increases significantly when unreticulated polyethyleneimine is converted to a reticulated product by a difunctional alkylating agent. In principle, the reaction of polyethyleneimine with difunctional alkylating agents can be carried out without the use of solvents. However, for better control of the reaction and better removal of heat, it is advantageous to carry out the reaction in the presence of an inert solvent. Suitable solvents are organic solvents which dissolve the reaction components, such as lower alcohols, but also especially water. The reaction can be carried out at a temperature range of -10 to about 100°C. The reaction was carried out at approximately standard room temperature, i.e.
It is particularly advantageous to carry out in the range from 5 to 45°C. This leads to reactions that can be easily controlled, very good product quality and minimal costs of energy. When carried out in this manner, the reaction is substantially complete in about 1 to 2 hours.

In order to obtain the auxiliary agents which can be used according to the invention with particularly narrow specifications, i.e. to achieve particularly good reproducibility of the preparation process, the reaction mixture is adjusted to a pi of 9 to 10 after the main reaction has ended. It is advantageous to stir for several hours, usually from 2 to 6 hours, at elevated temperature, preferably from 60 to 100"C.

The reaction product of polyethyleneimine and a difunctional alkylating agent used according to the invention has an alkyl group of 01-64, preferably 01-C.

It can also be quaternized by an alkyl group. Quaternization can be carried out in conventional manner with alkyl halides, preferably alkyl chlorides or dialkyl sulfates.

These auxiliaries are applied to the textile material to be dyed from the aqueous processing liquor together with the wetting or padding agents and anionic surfactants customary in the textile industry. An example of a suitable wetting agent or padding aid of this type is propylene oxide/propylene oxide containing 40-80% by weight of ethylene oxide.
Ethylene oxide block polymers, especially oxyethylated nonylphenols.

Suitable anionic surfactants are all known compounds of this type, such as secondary alkanesulfonates, alkyl sulfates, alkyl ether sulfates, fatty acids,
an alkylbenzene sulfonate, a dialkyl sulfosuccinate or a dialkyl phosphate. The presence of anionic surfactants is critical to the method according to the invention. This is because anionic surfactants form aggregates and precipitates with the reaction products of polyethyleneimine and difunctional alkyl agents, which can be quaternized, and the precipitates are distributed asymmetrically on the fibers. This is because it deposits on the surface and thus provides uneven staining.

Pretreatment with adjuvants along with nonionic wetting agents and anionic surfactants can be carried out by padding in a conventional manner from the aqueous processing solution or from about 20 to 70"C, preferably from 40 to 60°C.
It is carried out by the exhaustion method in C. The processing liquid is weakly acidic p
t+ preferably adjusted to pH 6. The amount of auxiliary agent is approximately 5 to 100 g/f, preferably 30 to 80 g/f! It is. The amount of wetting agent is preferably 0.5 to 4 g/! It is.

Next, the pretreatment liquid is squeezed and the textile is dried. Suitable fiber materials are raw or pretreated cotton or mixed fibers containing cotton.

The material thus pretreated is then dyed in a conventional manner and on a conventional dyeing machine with direct dyes, reactive dyes or sulfur dyes containing sulfo groups, for example by the cold pad-batch method or the exhaust method. . The bath ratio in this method is approximately 3:
1 to 40:1. However, in this case, unlike conventional methods, it is important that no alkali or reducing agent is used.

Reactive dyes suitable for this method contain groups reactive towards the hydroxyl groups of cellulose and react under the above dyeing conditions according to the invention or by reaction with the above polymer fixed on the cellulosic material. All known reactive dyes. The reactive group leaves an electrophilic residue, e.g.
Groups with easily removable substituents, such as reactive groups of the vinylsulfone type, halogens, substituents of the cyclic quinoxalines, phthalazines, triazines, pyrimidines or pyridazones, or alkyls in the case of sulfonylpyrimidine or sulfonylbenzothiazole dyes. Sulfonyl
It is a substituted reactive group. A specific example is the fiber-reactive group β-
Sulfatoethylsulfonyl, β-chloroethylsulfonyl, β-thiosulfatoethylsulfonyl, β-phosphatoethylsulfonyl, chlorotriazinylamino,
Dichlorotriazinylamino, chlorotriazinyldiamino, dichloropyridazinylamino, trichloropyridazinylamino, dichloropyridazinylcarbonylamino, 2-chlorobenzothiazol-6-ylamino, 2,
3-dichloroquinoxalin-6-ylcarbonylamino or 4-chloro-5-methyl-2-methylsulfonyl-
3-pyrimidinylamino.

Suitable dye bases for fiber-reactive dyes are, for example, water-soluble azo, disazo, formazan, anthraquinone, dioxazine or phthalocyanine dyes. Water-soluble azo- and disazo-reactive dyes, which can also be metal complex-reactive dyes, are preferably used. After dyeing, the material is rinsed and optionally finished by soaping and drying.

The process according to the invention can also be carried out with other types of dyes, such as direct dyes and water-soluble sulfur dyes, which not only depend on their fiber reactivity but also contain anionic groups, such as sulfo groups. These dyes provide similar effects and fastness properties as reactive dyes. Additionally, metal-free organic pigments such as vat dyes and sulfurized vat dyes can also be used in the process.

An embodiment of the method according to the invention is that, rather than pretreating and dyeing the fully finished fabric, only the warp yarns are treated as described above, advantageously in combination with a gluing treatment. In this embodiment, the cellulose warp yarns are treated in a conventional manner with a gluing solution containing, in addition to the usual wetting agents, an anionic gluing agent and the pretreatment agents described above. The amount of glue is usually 10
100 to 100 g/l, preferably 20 to 40 g/l. The warp yarns are then dried and woven together with white weft yarns. Cross-dying of this fabric by conventional methods but in the absence of alkali gives a denim fabric which gives an important fashion effect due to the uneven dyeing of the warp yarns. In this method, which combines pretreatment with a special pretreatment agent with gluing, the anionic surfactant is replaced by an anionic glue agent.

Suitable anionic glues of this type are, for example, carboxymethyl cellulose, carboxymethyl starch, degraded starch, polysaccharides, galactomannans, acrylates or polyesters.

A washing step with a perborate-containing detergent carried out immediately after the soaping step can significantly increase the gloss of the dyeing and, depending on the shade of the dye,
The slightly soiled weft threads are whitened, so that a dyeing with high gloss and white weft threads is obtained. The use of optical brighteners in the wash liquor further increases the shine of the dyeing and weft threads.

These effects are particularly obtained when the washing is carried out at 20-50'C. If the washing with perborate-containing detergents is carried out at high temperatures, e.g. 50'C-100'C, the dyeing is The whitening can be done step by step until substantially complete bleaching is achieved.

In this way, mottled dyeing or fashionable color changes can be obtained on the fibers in a very gentle manner. This effect can only be achieved in another way by washing in the presence of pumice.

However, stones, sand and/or surfactants can be added to the treatment bath to modify the coloring or cleaning effect.

Example 1 Cotton warp threads are treated on a gluing roll in a phase prepared for this purpose as follows: 30 g/l of sodium carboxymethylcellulose (
CMC) 3g/Il non-ionic wetting agent (nonylphenol + 10
EO) 100g/1, European Patent Application No. 0.133.93
Polyethylene condensation product treatment liquid absorption rate 100 to 120% (high performance squeezing roll) according to the end line 11 on the front side of the publication.

The sodium carboxymethyl cellulose used was
It has a viscosity of 300 mPa,s at 20°C in a 2% aqueous solution, as measured by a falling ball viscometer (commercial product T
ylose C300).

The thread runs at a speed of 60 m/min, and the temperature of the gluing liquid is 8
0-90°C. After removal from the gluing box, the yarn runs through a drying cylinder and is dried at approximately 130° C. by contact heat.

Instead of CMC glue, it is also possible to use a mixture of CMC and modified starch.

The cotton warp threads pasted in this way are then woven together with coarse, white cotton weft threads, and the resulting fabric is woven on a cold bud-batch machine consisting of a padder and a winding roll at a density of 10 g/l (D C,l Reactive Blue 19(
C,! , No. 61200) and 3 g/l of a nonionic humectant (nonylphenol + t
o Buzzing with a solution containing EO).

The material thus badged is wrapped airtight with polyethylene film on a winding roll and left on rotation for up to 24 hours.

Post-treatment, common for reactive dyes by rinsing, soaping at boiling temperature with surfactants and rinsing again, provides good wear fastness without the amount of alkali normally required to fix reactive dyes. Gives uneven dyeing of cotton warp yarns. Furthermore, this process substantially recolors the weft threads which have not been premordanted by the polyethyleneimine condensation product. A fabric with a denim effect is therefore obtained.

Example 2 Cotton warp threads are treated on a pasting roll in a phase prepared for this purpose as follows: 60 g/ffi of carboxymethyl starch ((:MS)
3g/l nonionic wetting agent (nonylphenol + 10
EO) 80 g/f of a reaction product of polyethyleneimine and a bifunctional alkylating agent (Ichisaka product: "' Solidogen FFL), quaternized with dimethyl sulfate, processing liquid absorption rate of 100-130% (high performance) squeeze roll).

The thread runs at a speed of 60 m/min, and the temperature of the gluing liquid is 8
0-90°C. After removal from the gluing box, the yarn runs through a drying cylinder and is dried at approximately 130° C. by contact heat.

The cotton warp threads thus pasted are then woven together with coarse, white cotton weft threads. The resulting fabric is padded on a pangu with an aqueous solution containing 40 g/42 of C,1, solbilized sulfuric acid 11 and 3 g/l of wetting agent (oxyethylated nonylphenol).

Steaming is carried out in a continuous dyeing steamer at 102-104°C for 60 seconds.

Post-treatment, common even for reactive dyes, by rinsing, soaping at boiling temperature with surfactants and rinsing again, is even without the amounts of reducing agents and alkalis normally required for dyeing and without the chemicals necessary for oxidation. Gives an uneven, mottled light-dark dyeing of cotton warp yarns with good wear fastness even without chemicals. Furthermore, this method
The FFL substantially turns the non-premordanted weft threads white again. A mottled fabric with a denim effect is therefore obtained.

Example 3 Cotton warp threads are treated on a gluing roll in a phase prepared for this purpose as follows: 50 g/3 g of 42 polyvinyl alcohol (PVA)
/ wetting agent (nonylphenol + IOEO) 20g/l
alkanesulfonate (commercial product: ”' l1o
Stapur SAS) 100 g/l of polyethylene condensation product treatment liquid absorption rate 100-120% according to European Patent Application No. 0.133.93.

The thread runs at a speed of 60 m/min, and the temperature of the gluing liquid is 8
It is 0 to 90°C. After removal from the gluing box, the yarn runs through a drying cylinder and is dried at approximately 130° C. by contact heat.

The cotton warp threads thus pasted are then woven together with coarse, white cotton weft threads, and the resulting fabric is processed into clothing. Garments such as men's trousers are dyed in a pad dyeing machine in an aqueous bath containing 771% by weight of Reactive Blue.
: Treated at a bath ratio of 1.

The post-treatments customary for reactive dyes by rinsing, soaping and rinsing give a turquoise blue tone with mottling of light and dark. The dyeing has good fastness properties.

A bleached cotton fabric was coated with 60 g/l of polyethyleneimine condensation product (3 g//!) on a 2- or 3-roll padder.
of wetting agent (nonylphenol + 10EO) and a solution containing 14 g/ffi of degraded starch and drying.

The 30°C warm batch processing solution for this auxiliary padding step is mixed for 30 minutes before use, and this retention is carried out by a stirrer operating at low speed (approximately 60 times/min) to achieve coagulation of the auxiliary agent. Keep it moving all the time.

After drying, 30g of the fabric was coated with #2 C, 1, Reactive Yellow 15 and 4.
Pad with a treatment solution containing 2 g/2 of wetting agent (nonylphenol ± 10 EO).

The staining is left to stand and worked up according to the conditions of Example 1.

A yellow dyeing with light and dark mottling and good fastness properties is obtained.

Claims (1)

[Claims] 1. In a method for asymmetrically dyeing cellulose fibers without using an alkali or reducing agent, cellulose fibers are dyed with a wetting agent, polyethyleneimine, which can be quaternized, and A process comprising treating the fiber with a treatment liquid containing a reaction product with a functional alkylating agent and an anionic surfactant, drying the fiber and dyeing the fiber without addition of alkali. 2. In a method of unevenly dyeing cellulose fibers without using alkali or reducing agents to achieve a special denim effect, the warp yarns made of cellulose fibers are dyed with a wetting agent,
treated with a gluing solution containing a reaction product of polyethyleneimine and a difunctional alkylating agent, which may be quaternized, and an anionic gluing agent, drying the fiber, weaving the warp yarns together with the weft yarns, and A method consisting of dyeing these fibers without adding alkali. 3. Process according to claim 1 or 2, characterized in that the reaction product is used in an amount of preferably 5 to 100 g/l. 4. The method according to claim 1 or 2, wherein the anionic surfactant is used in an amount of 1 to 80 g/l. 5. Polyethyleneimine and epichlorohydrin, 1,3
3. The process as claimed in claim 1, wherein the reaction product with -dichloropropan-2-ol or a mixture thereof is used. 6. The method according to claim 1 or 2, wherein the reaction product of polyethyleneimine and a difunctional alkylating agent is used in a reaction component weight ratio of 100:0.01 to 100:2.