JPH0274684A - Soaping agent and treatment - Google Patents

Abstract

PURPOSE:To obtain a soaping agent showing effects having clarity and high fastness and few white stain by soaping cellulosic cloth dyed with reactive dye, vat dye, etc., at low temperature, comprising a specific quaternary nitrogen- containing surfactant. CONSTITUTION:Cellulosic cloth dyed with reactive dye, vat dye, etc., is soaped at low temperature of 60-70 deg.C by using a soaping agent comprising (A) a quaternary nitrogen-containing surfactant of aliphatic amine base shown by formula I or formula II (R1 to R3 are 1-9C alkyl, acrylaminoalkyl, acyloxyalkyl, etc.; R4 is 1-4C alkyl, 2-4C hydroalkyl, etc.; X is anionic ion; Y is cationic agent containing p functional groups; m is 0 or 1-3; n is 2-3; p is 2-4) or (B) an alkali compound comprising a quaternary nitrogen-containing surfactant of heterocyclic amine base (preferably example, pyridine-ring derivative) and an alkali metallic hydroxide to give effects corresponding to conventional 90 deg.C high-temperature soaping.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a soaping agent for dyed products based on cellulose fibers and a method for treating dyed products. More specifically, the present invention relates to a soaping agent and a treatment method for removing undyed dyes after dyeing textile products containing cellulose fibers with reactive dyes, vat dyes, or dyes containing sulfur dyes.

[Prior Art] Conventionally, dyed cellulose fibers are dyed using soaping agents such as ethylene oxide adducts of higher amines, soda salts of higher fatty acids, ethylene oxide adducts of higher fatty acids, and sodium polyacrylate salts, and are dyed in aqueous solutions at 90°C or higher. soaping or washing.

[Problems to be solved by the invention] In recent years, the dyeing process of textile products has been forced to be streamlined to save energy and labor, and for example, there is a demand for soaping or washing at a low temperature of GO~70°C.
The above-mentioned conventional soaping agents cannot provide the same soaping effect when used at 90''C.

[Means for Solving the Problems] The present inventors soaped or washed textile dyed products containing cellulose fibers at a low temperature of 60 to 70°C, which is the same as when soaping or washing was carried out at a temperature of 90°C or higher. As a result of extensive research to find an effective soaping agent and treatment method, the present invention was achieved. That is, the present invention provides an acylaminoalkyl group, an acyloxyalkyl group, an alkoxyalkyl group, an aralkyl group optionally substituted with alkyl, an alkylpolyoxyalkylene group, an alkylarylpolyoxyalkylene group, a hydroxyalkyl group, or a polyol group. quinalkylene group; R4 is an alkyl group having I to 4 carbon atoms, a hydroxylalkyl group having 2 to 4 carbon atoms, or an aralkyl group having 7 to I4 carbon atoms; X is an anionic counterion; Y is p functional groups m is O or an integer of 1 to 3, n is an integer of 2 to 3, and p is an integer of 2 to 4. However, R1, R in the above formula
2 and R3 may be the same or different. ) Aliphatic amine-based quaternary nitrogen atom-containing surfactant (A), or (A) and an alkaline compound (C); Heterocyclic amine-based quaternary nitrogen atom-containing surfactant (B), or a soaping agent for dyeing cellulose fibers using a reactive dye, vat dye or sulfur dye consisting of (B) and an alkaline compound; This is a method for treating dyed cellulose fibers, which is characterized by soaping the dyed cellulose fibers with reactive dyes, vat dyes, or sulfur dyes.

R1 and R2 of general formulas (1) and (2) in the present invention
and R1 alkyl group, acylaminoalkyl group, (
alkylamidoalkyl group), acyloxyalkyl group and alkoxyalkyl group, formula R or R-Z
The group represented by -A (in the formula, R is an alkyl group having 1 to 9 carbon atoms, 2 is -CON) I, -COO- or -0-1A is 1
-4 alkylene groups).

Examples of the alkyl group for H in the above formula include saturated or unsaturated linear or side chain alkyl groups (including alkenyl groups) having 1 to 9 carbon atoms, such as methyl, ethyl, n- and 1-propyl, butyl, Hexyl, propenyl, butenyl, octyl, 2-ethylhexyl, nonyl groups; examples of A include methylene, ethylene, propylene, butylene groups, and the like.

Examples of the group represented by R-Z-^ include an alkylamidoalkyl group such as a hexylamidoethyl group; an acyloxyalkyl group such as an offthyloyloxymethyl group; and an alkoxyalkyl group such as a butoxyethyl group.

Examples of aralkyl groups which may be alkyl-substituted include pen, zyl, and benzyl groups substituted with alkyl groups such as those mentioned above; alkylpolyoxyalkylene groups and alkylarylpolyoxyalkylene groups, and R' ) r and R'-Ar-(OA'
) a group represented by r- [wherein R' is an alkyl group, Ar is an aryl group (benzene ring, etc.), A' is an alkylene group with carbon number Z ~ 4 (ethylene, propylene, butylene, r
represents an integer from 1 to 50. Examples include:

Hydroquine alkyl groups include hydroxyethyl, hydroxypropyl, and hydroxybutyl groups.

The polyoxyalkylene group is a group represented by H(A'O), - [wherein A' is an alkylene group having 2 to 4 carbon atoms (
Examples include ethylene, propylene, butylene, and S represents an integer of 2 to 50.

In general formula (1), examples of the alkyl group having 1 to 4 carbon atoms for R4 include methyl, ethyl, propyl, and butyl groups. Examples of the aralkyl group having 7 to 14 carbon atoms include a benzyl group. Examples of the hydroxyalkyl group include those mentioned above.

The anionic counter ions of X in general formulas (1) and (2) include halogen ions (CI-1Br-1I-, etc.),
Hydroxyl ion, alkyl sulfate ion (e
lf30SO3-1C2Its 05O3-, etc.).

Among X, preferred are chlorine ion, hydroxyl ion and methyl sulfate ion.

Y in the general formula (2) may be a residue of a cationizing agent having 2 to 4 functional groups. The cationizing agents constituting the residue of this cationizing agent include, for example, α,α'-cyclo-m-oxylene, α,α'-dibromo-m-xylene, α,α'-dichloro-p-xylene, α, α'-syflomu-p-xylene, β, β'-dichloroethyl ether, etc.; or polyhalogenated cationic agents obtained from a polyhydric alcohol and a halogenated fatty acid by a conventionally known esterification reaction.

Polyhydric alcohols include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-phthanediol, neopentyl glycol, 1, G-hexanediol, glycerin, trimethylpropane, sorbite, etc. Examples include triols, and tetraols such as erythritol, pentaerythritol, diglycerin, and sorbitan.

Examples of halogenated fatty acids include monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, chloropropionic acid, α- or β-chloropropionic acid, and the like.

Specific examples of the quaternary nitrogen atom-containing surfactant represented by the general formula (+) include the following.

In the following, Ph represents a phenyl group.

Cll2CKtOII / CH20H20H HOCItel12-N'-CH3・0)1-C11
(3) When m=2) :Ihelfs-N"-CL
CH20H・2CI-CIIaCIhOII CI
hC1HzOH(ljhcI120)+ all [;) 12 to ■2Uノ+1111 (4) When m=3, 30■- etc. The quaternary nitrogen atom-containing surfactant represented by the general formula (1) is usually polyalkylene. It can be produced by alkylating a polyamine compound with an alkylating agent (cationizing agent) by a known method. For example, N, N, N, N,
A method for producing 'N',N'-hexaethylethylenediammonium dichloride will be explained.

1 molecular weight of tetraethylethylenediamine was put into an autoclave reaction tank, and 2 molecules of ethyl chloride was added dropwise under cooling to 120~! React at 30°C to obtain the desired product.

Specific examples of the quaternary nitrogen atom-containing surfactant represented by the general formula (2) include the following.

Such 211s C1(3 obtain.

As the heterocyclic amine type quaternary nitrogen atom-containing surfactant in the present invention, the quaternary nitrogen atom-containing surfactant represented by the general formula % formula % (3) and the general formula (2) is usually a tertiary amine It can be produced by a known quaternization reaction from a compound and the above-mentioned cationizing agent having 2 to 4 functional groups. For example, a method for producing N,N,N',N'-tetrakispolyoxyethylene (10 mol) N,N'-dioctyl m-xylene diamine diammonium dichloride will be explained. 2 molecules m of N,N'-dipolyoxyethylene (10 mol) octylamine were placed in a reaction tank, and 1 molecule m of α,α'-dichloro-m-xylene was added dropwise to react, and the reaction was continued at 120 to 130°C. The object is a Lamb ring,
It is a heterocyclic ring such as a morpholine ring, and R5 and R6 are an alkyl group having 1 to 8 carbon atoms, an aralkyl group which may be substituted with alkyl, and H1! having 2 to 4 carbon atoms. loxylalkyl group; X is an anionic counterion; when Q is a pyridine ring or a quinoline ring, V is 0. When Q is an imidazolinium ring or a morpholine ring, Y represents f. However, R5 and R6 in the above formula may be the same or different. )
Examples include compounds represented by:

Specific examples of the heterocyclic amine quaternary nitrogen atom-containing surfactants represented by the general formula (3) are as follows.

4) morpholine derivatives, etc. 2) quinoline derivatives 3) imidazolilam derivatives These quaternary nitrogen atom-containing surfactants (A) may be used by mixing them in one or more plates.

Preferred among the quaternary nitrogen atom-containing surfactants (A) are those in which n in general formula (1) is θ~2 and p in (2) is θ~2.
It is a compound of

Among (R), preferred are pyridine ring derivatives.

In the present invention, the alkaline compound (C) includes alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, carbonates such as sodium carbonate, sodium bicarbonate, and sodium sesquicarbonate, sodium orthosilicate,
Silicates such as sodium metasilicate, sodium sesquisilicate, water glass, phosphates such as tribasic sodium phosphate, sodium pyrophosphate, and sodium tripolyphosphate, methylamine, dimethylamine, triethylamine, monoethanolamine, jetanolamine , amines such as triethanolamine.

Preferred among the alkaline compounds are alkali metal hydroxides and silicates.

Cellulosic fiber products to which the soaping agent of the present invention can be applied include natural fibers such as cotton and hemp, and recycled fibers such as viscose rayon and copper ammonia rayon.

It may also be a blended or interwoven fabric of the above fibers and other natural fibers (for example, wool, M) or synthetic fibers (for example, polyester fibers, polyamide fibers, polyacrylic fibers, acetate fibers). The fiber form may be cotton, tow, tape, cheese, cake, cloth yarn, or the like.

When dyeing these textile products, if only cellulose fibers are used, reactive dyes, sulfur dyes, and vat dyes can be used. On the other hand, dyes such as acid dyes, metal-containing complex salt dyes, reactive dyes, disperse dyes, and cationic dyes can be used to dye the fibers 81 when fibers other than cellulose fibers are included in blended or interwoven fabrics.

When dyeing textile products using these dyes, the dyeing methods are one-bath one-stage method (single am>), - two-bath method (polyester/cotton blend, etc.), and one-bath two-stage method (- one-bath one-stage method or one-bath method). Examples include blended fabrics, interwoven fabrics, etc. that are difficult to produce using the two-step process.

These dyeings can be carried out in a conventional manner using a cheese dyeing machine, a drum dyeing machine, a wince dyeing machine, or a jet dyeing machine.

The dyed article thus dyed is subjected to soaping.

When the quaternary nitrogen atom-containing surfactant (A) or (B) and the alkaline compound (C) are used in combination in the soaping agent of the present invention, there are no restrictions on how they can be used together.

For example, (A) or (B) and (C) are mixed in advance and (A) or (B) and (C) are mixed in a bath (water bath).
You may create a soaping agent solution consisting of: Also (A
) or (B), and (C) as they are, or a method in which they are dissolved in water and added to the bath simultaneously or sequentially.

The mixing ratio of (A) or (B) and (C) is usually 100:0
~30 near 0, preferably 100: O~50
: 50. If (A) or (B) does not have 30 grooves, the soaping effect at a low temperature of 60 to 70°C, which is the object of the present invention, will be poor. When (C) exceeds 70, the color change of the dyed product becomes large.

When soaping or washing, the soaping agent of the present invention may be used in combination with other compounding agents, such as other soap pinking agents (alkylphenol oxide adducts, ethylene oxide adducts of higher alcohols, ethylene oxide adducts of higher fatty acids, higher fatty acids and alkanols). (Amides with amines, ethylene oxide adducts of higher amines, polyvinylpyrrolidone, etc.) can be used in combination.

The amount of other soaping agents used is usually 5% of the total soaping agent.
It is 0% by weight or less. These are soaping baths or washing baths containing aqueous solutions or dispersions.

The soaping agent (I) of the present invention and other soaping agents (II)
), there are no restrictions on how they can be used together. For example, (1) and (n) may be mixed in advance to prepare a soaping agent solution consisting of (I) and (II) in a bath (water bath). Also, CI) and (It) as they are,
Alternatively, there is a method in which both are dissolved in water and added to the bath simultaneously or sequentially.

The concentration of total soaping agent in the bath is usually 0.05-7g/l
, preferably 0.1 to 5 g/l (solid content).

The pu of the soaping bath is usually from IO to less than 12, preferably from IO. 5 to 11.8. p) If I is IO, the effect of shedding and removing undyed dye on the fibers will be poor. Moreover, if it exceeds 12, the dyed product will be greatly discolored and the reproducibility of the hue will be lacking.

The soaping of the present invention is usually carried out at a temperature of 60 to 70 degrees Celsius, but of course it may also be carried out at a temperature of 90 degrees Celsius or higher, which is the conventional method. Needless to say, it can be done.

The soaping agent of the present invention can be used for soaping dyed articles dyed with any jet dyeing machine, Wince and other dyeing machines, but for example, dyed articles dyed with a jet dyeing machine can be used. (Continuous soaping is preferable.)

When soaping is carried out using a jet dyeing machine, usually after dyeing, the dyeing solution containing the dyed product is removed and washed with water to form the soaping bath of the present invention in the dyeing machine, and the dyeing machine is operated for soaping or washing. The conditions in this case are usually as follows.

That is, the cloth speed (m/min) is l1iO-150, the bath rotation speed (
times/min) 1.5 to 3, bath ratio 0 to 20 per batch, heating time (
(minutes) is 15-25, temperature ('C) is 20-70°C (actual soaping temperature is 60-70'C), and total soaping time (minutes) is 25-50. After soaping, the dyed material is washed with water and sterilized.

The soaping agent of the present invention can also be used in conventional dyeing machines (Loco type, Wince, etc.) and open dyeing machines.

Subsequently, wax treatment is performed using a usual dye fixing agent (diethylenetriamine/ammonium chloride polycondensate in dicyandiamide, diallyldimethylammonium chloride polymer, etc.).

[Example] The present invention will be further explained below with reference to Examples and Test Examples, but the present invention is not limited thereto.

Examples 1 to 12, Comparative Examples 1 to 3 The soaping agents of the present invention and comparative amounts are shown in Table-1.

Comparative Example 1 Ethylene oxide adduct of nioleic acid (
14 mol) Comparative Example 2: Sodium Stearate Comparative Example 3:
Sodium polyacrylate (molecular member: 10000) Test Example I (White water staining test) Soaping agents of the present invention (Examples 1 to 12) and comparative amounts (
A soaping bath was prepared using Comparative Examples 1 to 3), and 5 g of each dyed cloth and 5 g of undyed multi-fiber M-test cloth were added to the bath, and each fiber part of the multi-fiber test cloth was soaped under the following conditions. The degree of contamination was determined on a gray scale, and the results are shown in Tables 2-8.

[Test conditions ■] Sample fabric: Cotton knitted (scoured and bleached) multi-fiber test cloth (attached fabric) 2) Dyeing conditions: Dyeing was performed according to the general dyeing recipe for each dye below.

Dyes a, c, 1. Reactlve Red 21
5% oyw, f.

b, c, 1. Reactlve Blue 21
5% o, w, f.

c, c, 1. Reactlye Black 5'
5% o, v, f.

d, G, 1.5ulphur Red 13
15% o, v, f.

e, c, 1.5ulphur Black 1
20% o, w, f.

f, c, IJat Blue 20 6%
oyw, f.

g, c, 1. Yat Green l
6% o, w, f.

3) Soaping bath soaping agent (amount used in Table 1) Bath ratio
1:10 Temperature, time 70°C x 10 minutes, 90°cxxo water washing 20°C x 3 minutes drying 105°C x 30 minutes 4) Testing machine Shaking dyeing machine [Tsuzii Dyeing Machine Wholesale Co. Test example 2 (soaping test) Using the soaping agent of the present invention (Examples 1-12) and comparative amounts (Comparative Examples 1-3), the same soaping bath as in Test Example I was prepared, and 10 g of each dyed cloth was placed in the bath under the same conditions as in Test Example ①. I soaped it with Each soaping cloth was subjected to the following color fastness test and the results are shown in Table 9-15.

l) Washing fastness test JIS LO844A-4 method, contamination of the attached cloth after the test was determined on a gray scale. (Grade) 2) Water fastness test JIS LO84 [i B method (16 hours) Contamination of the attached cloth after the test was determined on a gray scale. (grade)
3) Sweat fastness test JIS LO848A method, acid and alkali tests were conducted to determine the contamination of the attached cloth using a gray scale. (grade) 4)
Abrasion fastness test JIS LO849 Dry and wet abrasion tester (type 2) After 100 reciprocating abrasions under a load of 200 g, the contamination of the attached cloth was determined on a gray scale. (grade) Test Example 3 (Foaming property test) A soaping bath similar to Test Example 1 was prepared using the soaping agent of the present invention (Examples 1-12) and comparative amounts (Comparative Examples! to 3), and a foaming property test was conducted. The amount of foaming (+nm) was measured using a machine, and the results are shown in Table 18.

(Test conditions) Liquid amount: 1.51 Circulating liquid amount: 1.5+/min Nozzle diameter: 1 mm Testing machine: Injection type liquid flow foaming tester [Effects of the invention 10 The soaping agent of the present invention is made of cellulose fibers Soap or wash at a low temperature of 60 to 70°C for dyed textiles containing! ] The same soaping effect as when performed at 0'C or higher can be obtained. In other words, it is possible to obtain a dyed product with less contamination of hot water, clear color, easy to wash, and excellent color fastness against water, sweat, friction, etc.

2. Also, the soaping agent of the present invention has less foaming property than conventional soaping agents such as soda salts of higher fatty acids, ethylene oxide adducts of higher fatty acids, and ethylene oxide adducts of higher alcohols, and is suitable for RAVID jet dyeing. It can also be used on machines.

3. The soaping agent of the present invention, like ordinary soda salts of higher fatty acids, does not combine with calcium and magnesium ions in water to form water-insoluble alkali metal salts, causing stains such as white powder and speck on dyed fabrics. do not have.

Claims (1)

[Claims] 1. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) (In the formula, R_1, R_2 and R_3 have a carbon number of 1 to 9 an alkyl group, an acylaminoalkyl group, an acyloxyalkyl group, an alkoxyalkyl group, an aralkyl group which may be substituted with alkyl, an alkylpolyoxyalkylene group, an alkylarylpolyoxyalkylene group, a hydroxyalkyl group or a polyoxyalkylene group. Yes; R
_4 is an alkyl group having 1 to 4 carbon atoms, a hydroxylalkyl group having 2 to 4 carbon atoms, or an aralkyl group having 7 to 14 carbon atoms; X is an anionic counterion; Y is a cationizing agent having p functional groups; residue, m is 0 or an integer from 1 to 3, n
represents an integer of 2 to 3, and p represents an integer of 2 to 4. However, R_1, R_2, and R_3 in the above formula may be the same or different. ) Cellulose fiber dyeing with a reactive dye, vat dye or sulfur dye consisting of an aliphatic amine quaternary nitrogen atom-containing surfactant (A), or (A) and an alkaline compound (C) Soaping agent for things. 2. Heterocyclic amine quaternary nitrogen atom-containing surfactant (B
), or (B) and an alkaline compound (C). 3. Cellulose-based fibers dyed with reactive dyes, vat dyes, or sulfur dyes are soaped using the soaping agent according to claim 1 or 2 at a pH of 10 to less than 12 in the soaping bath. Processing method for textile dyeing. 4. The treatment method according to claim 3, wherein the soaping is carried out at a temperature of 75°C or lower.