JPS60252787A - Wet fastness enhancer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to wet fastness enhancers.

[Conventional technology]

Conventional enhancers include polycondensates of cyanamide and/or dicyandiamide and polyalkylene polyamines (eg, US Pat. No. 2,649,854).

[Problem that the invention seeks to solve]

The present inventors have arrived at the present invention as a result of intensive studies to obtain a fastness enhancer that exhibits less discoloration after processing and has excellent light fastness, sweat/light fastness, and chlorine fastness. .

[Means for solving problems]

The present invention is a wet fastness enhancer for dyed cellulose fibers, characterized by comprising a polycondensate of an aliphatic diamine (salt) having 6 or more carbon atoms and a guanidine compound (B).

Aliphatic diamine (salt) having 6 or more carbon atoms used in polycondensation (refers to aliphatic diamine and/or its salt. The same description will be used hereinafter.) In (A), the aliphatic diamine is straight-chain aliphatic Diamine (1,6-hexanediamine, 1.7-heptanediamine, 1.8-octanediamine, 1.9-nonanediamine, 110-decanediamine, 1.11-undecanediamine, 1.18-octadecanediamine, etc.) side Chain aliphatic diamine (2,2,
4-)limethylhexamethylene diamine, etc.) and two or more thereof. Preferred among these are 1,6-hexanediamine and 2,2,4-trimethylhexamethylenediamine.

Salts include inorganic acids (hydrochloric acid, nitric acid, carbonic acid, phosphoric acid).

Examples include salts of organic acids (such as sulfuric acid, etc.) and organic acids (such as formic acid, acetic acid, and sulfamic acid), as well as two or more of these. Among these, hydrochloride is preferred.

Examples of the guanidine compound (B) include compounds having a guanidino group and salts thereof. Specifically, dicyandiamide, guanidine, hydrochloric acid-2 carbonic acid-, phosphoric acid-1
Nitric acid-, formic acid-acetic acid-guanidine; alkyl-substituted guanidine (1,1,8,8-tetramethylguanidine, n-
dodecylguanidine, isoamyleneguanidine, etc.);
Aryl-substituted guanidines (such as phenylguanidines);
Aralkyl-substituted guanidines (triphenylguanidine, etc.): Hydroxyalkyl-substituted guanidines (methylolguanidine, dimethylolguanidine, etc.); Amino-substituted or amino group-containing group-substituted guanidines (aminoguanidine, L-arginine, N-alkanoyl-1-alkinine ethyl esters, etc.); cyano-substituted guanidines (
Guanylurea, methylol phosphate guanylurea, etc.):
Biguanide [xylyl biguanide, biguanide hydrochloride.

1-n-butyl biguanide, 1.1'-hexamethylenebis(5-(p-chlorophenyl) biguanide), N,
Examples include N-dimethylbiguanide hydrochloride, N-[β-phenethyl)biguanide, etc.]. Among these, preferred are dicyandiamide, guanidine hydrochloride and guanidine sulfamate.

Other than the above (C) For example, metal salts (group 1 metal salts such as beryllium, magnesium, calcium, strontium, barium, zinc, etc.): aldehydes (
formaldehyde, acetaldehyde, paraformaldehyde, glyoxal, etc.); cellulose-reactive resin (
Dimethylolbihydroxyethyleneurea, dimethylolpropyleneurea.

dimethyloltriazone, dimethyloluron, etc.);
Isocyanates (hexamethylene-1°4-diisocyanate, isophorone diisocyanate, etc.); Epihalohydrins (epichlorohydrin, ebipromohydrin, ebiodohydrin, etc.); Monomeric cyclic amines (ethyleneimine, etc.).

propylene imine, 2-butylene imine, etc.); cationic agents (3-chloro-2-hydroxypropyltrimethylammonium chloride, 2゜3-epoxypropyl-N-)realkylammonium salt, etc.); ureas (
Urea, ethylene urea.

thiourea, etc.); polyoxyalkylene compounds (polyethylene glycol (molecular weight: 20,000), pluronic type nonionic surfactant adhesives may be used to form polycondensates.

In the polycondensate, the equivalent ratio of the guanidino groups of (A) and (B) is usually 1:09 to 1.1, preferably substantially 1°.
It is 1. The molar ratio of (A) and (C) is usually 1:0 to 1.
, preferably 1:0-05.

The polycondensate can be obtained by adding (A), (B) and, if necessary, (C) simultaneously or later and heating. The heating temperature is usually 100 to 300°C, preferably 120 to 250°C, and the heating time is usually 2 to 6 hours, preferably 3 to 5 hours. Ammonia is generated violently by heating.

The resulting polycondensate is a brown solid. Polycondensate is part 2
The intrinsic viscosity [η] of 0INNaC (l) at 5°C is closely related to the wet fastness (washing, water fastness, etc.) of the enhancer.The intrinsic viscosity is usually 0.05 to 2.0. Preferably 01 to 15. If the intrinsic viscosity [η] is less than 0.05, wet fastness (washing, water fastness, etc.) will not be sufficiently improved, and if it is greater than 2.0, wet fastness will improve. Hardening of the texture of things.

Or blistering water is observed.

It is thought that the obtained polycondensate can be obtained by the following reaction when (B) is guanidine.

NHR'R' 111 XH2N CNH2+xHNR
/ represents H1 hydrocarbon group, cyan group, etc., and X is an integer greater than 1. ) In the dyed cellulose fibers to which the enhancer of the present invention is applied, the cellulose fibers include cellulose fibers (hemp, hemp,
cotton, rayon, etc.) or the above fibers and other natural fibers (
Examples include blends and interwoven fabrics with wool, silk, etc.) or synthetic fibers (polyester fibers, acrylic fibers, acetate fibers, nylon fibers, etc.). The fibrous form is cotton. Examples include tow, tape, cheese, cake, and 9-braid yarn for fabrics.

Examples of dyed products include those dyed with direct dyes and/or reactive dyes. Direct dyes and reactive dyes are commonly used and may be used, for example, in the New Edition Dye Handbook [
Examples include the dyes described in pages 315-890 (direct dyes) and pages 881-934 (reactive dyes) of Maruzen, edited by Organic Synthesis Association.

In treating textile dyed products using the enhancer of the present invention, the enhancer can be used in an aqueous solution, a hydrophilic organic solvent (methanol, ethanol, ethylene glycol, propylene glycol,
dioxane, dimethylformamide, etc.) or a mixed solution of water and a hydrophilic organic solvent. The concentration (solid content) of the treatment liquid is generally 0.05 to 10% by weight, preferably 0.1 to 5% by weight. PH of processing solution
can be freely selected within the range of 2 to 11 depending on the purpose of processing, but if the pH is too low, it will be difficult to improve the fastness, and if the pH is too high, the water solubility of the fastness enhancer will be poor.
In addition, since the discoloration of the dyed cloth becomes large, a value of 3 to 10 is preferable, and a value of 4 to 9 is particularly preferable.

The treatment solution can be applied to the dyed article by dipping, spraying, coating, padding, or other methods. In the case of immersion treatment, the temperature of the treatment solution during treatment is usually 20 to 70°C, preferably 4°C.
0-60°C. The valley ratio is usually 1:20.

After treatment, it is washed with water or dried without washing. Drying may be either natural drying or heat drying.

The treatment solution includes metal salts of inorganic acids (e.g. copper sulfate).

Copper acetate) and finishing agents commonly used in dyeing processes.

Resin processing chemicals etc. can be added.

〔Example〕

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

The color fastness test method in the test example is as follows.

(])discoloration Judgment was made using the gray scale for color change and fading of treated fabric (grade).

(2) Washing fastness JIS L 0844 A-4 Method Fastness evaluation was performed by determining the staining of the cotton attached fabric using a gray scale for staining (grade).

(3) Hot water fastness JIS L 0845 Beaker method (No. 8) For fastness evaluation, contamination of the attached cotton fabric was determined using a contamination gray scale (grade).

(4) Water fastness JIS L 0846 B method (16 hours) For fastness evaluation, contamination of the wool-attached fabric was determined using a contamination gray scale (grade).

(5) Light fastness After irradiation at 65°C for 20 hours using a fade meter, the discoloration and fading of the irradiated area of the dyed fabric was determined using a gray scale for color change and fading (grade).

(6) Sweat fastness JIS L 0848A method For evaluation of acid and alkali fastness, contamination of wool-attached cloth was determined using a contamination gray scale (grade).

(7) Chlorine fastness immersion method After dissolving 50 ppm (available chlorine) of sodium hypochlorite in water 1
Rinse with running water for 0 minutes and dry. The discoloration and fading of the treated fabric was evaluated using the Lou Scale for discoloration and fading (grade).

Examples 1-10. and Comparative Examples 1 to 9 Table 1 shows the enhancers of the present invention (Examples 1 to 10) and comparative products (Comparative Examples 1 to 9).

Note 1) HDA is 1,6-hexanediamine.

TMHMDA is 2,2.4=trimethylhexamethylene diamine, G is guanidine, DD is dicyandiamide,
DTA is diethylenetriamine, TTA is triethylenetetramine, EDA is ethylenediamine, PDA is propylenediamine, TMDA is trimethylenediamine, T
EMDA stands for tetramethylene diamine.

Note 2) The numbers in parentheses indicate the number of moles.

Note 8) HDA hydrochloride (■) is a hydrochloride produced by the reaction of HDA (t,o) and ammonium chloride (i,o).

Test Example The direct dye dyed products obtained by dyeing broad #40 cotton with the following direct dyes in a conventional manner were treated with the enhancer of the present invention (Examples 1 to 10) and the known enhancer (
Comparative Examples 1 to 9) and the color fastness test results are shown in Tables 2 to 4.

(Direct dyes used in the test) Dye name Dye concentration Dye manufacturer famous Yarasu Light Trend F5B 2%0・wl Kayarasu Spray Yellow RL 2%0・W −f //Guiyako Soton Fast Scareso) 4B3 2% o-w-f Made by Mitsubishi Kasei Kyou (
Processing conditions) Enhancing agent concentration: 1g7'd (solid content) Bath ratio: 1:20 Temperature x time: 60°C x 15 minutes Immersion water washing 2 Washing with running water, 30 seconds dehydration, drying: Centrifugal dehydration 120°C x 8 minutes discoloration As is clear from Tables 2 to 4, the dye fastness test results for washing, hot water, light and chlorine resistance show that the dye fixing agent of the present invention is better than known dye fixing agents when dyeing cotton knitted fabric with the following reactive dyes. The reactive dye dyed products obtained by dyeing each in a conventional manner were treated with the enhancer of the present invention (Examples 1 to 10) and the known enhancer (Comparative Examples 1 to 9), and the dyeing fastness was evaluated. The results are shown in Tables 5 to 9.

(Reactive dyes used in the test) Dye name Dye concentration Dye manufacturer's name Revafix Red E-4B 2% o-w-f Remazol Black B manufactured by Bayer 3% o -w-f Kayacion Turquoise EA manufactured by Requist 2% o-w4 Nippon Kayaku ■ (processing conditions) Enhancing agent concentration: 0.2 g/l (solid content) Bath ratio: 1
: 20 Temperature x Time: 50°C x 10 minutes Immersion in water Washing: Washing under running water, 30 seconds dehydration, Drying: Centrifugal dehydration 120°C x 5 minutes Color change, water, light, sweat and chlorine resistance test results As is clear from Tables 5 to 9, the enhancers of the present invention had better color fastness than the known enhancers.

〔Effect of the invention〕

Claims (1)

[Claims] 1. A wet fastness enhancer for dyed cellulose fibers, comprising a polycondensate of an aliphatic diamine (salt) having 6 or more carbon atoms (A) and a guanidine compound (B).