JP2000136484A - Processing of cellulose fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for processing cellulose fabric that can give cellulosic fabric having excellent color fastness, wrinkle resistance, shrinkage resistance through the rationalized dyeing and resin treatment simultaneous processing step. SOLUTION: When cellulose fabric is simultaneously dyed and finished with a glyoxal resin, a mixture of (A) an organic amine hydrochloride and (B) a borofluoride compound is used as a catalyst for the glyoxal resin and the concentration ratio of (A)/(B) is adjusted in the range of 95/5-60/40 in the pure base.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a cellulosic fabric, and more particularly, to a method for dyeing and improving the performance of a cellulose fiber cloth such as form stability, anti-wrinkling property, wash and wear property, and the like. And a method of processing a cellulose fabric simultaneously.

[0002]

2. Description of the Related Art Resin processing of cellulose fabric is usually performed after dyeing, but various studies have been made on simultaneous processing of dyed resin for rationalization. For example,
No. 8835 proposes a simultaneous processing of a dyeing resin using a direct dye, a urea formalin precondensate and an organic amine hydrochloride and zinc nitrate as an acidic catalyst. But,
In this method, formalin released from the processed product is generated,
There was a problem with safety.

On the other hand, in recent years, a resin processing method using a glyoxal resin which does not relatively generate formalin and a magnesium chloride or magnesium sulfate as an acidic metal salt catalyst has been adopted for a dyed product of a cellulose fabric. The glyoxal-based resin has an action of improving the shrinkage resistance of the cellulose fabric under an acidic metal salt catalyst, and is usually used in combination with a finishing agent after dyeing in the resin processing of cellulose. However, when dyeing is performed simultaneously with resin processing using a processing agent solution of a glyoxal resin and an acidic metal salt catalyst, the dye tends to precipitate due to the catalyst, and there is a problem that dyeing cannot be performed.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to overcome the above-mentioned problems of the safety of the prior art formalin and the disadvantage that the dye is liable to precipitate when dyeing and resin processing are performed at the same time. In the dyeing resin simultaneous processing process,
It is an object of the present invention to provide a method for processing a cellulose fabric capable of obtaining a cellulose fabric having excellent color fastness, wrinkle resistance and shrink resistance.

[0005]

Means for Solving the Problems As a result of various studies on the above-mentioned problems, the present inventors have found that, in simultaneous processing of a dyeing resin, the use of two specific catalysts in a specific mixing ratio for a glyoxal resin allows the above-mentioned process to be carried out. The inventors have found that the object can be achieved, and have reached the present invention. That is,
The invention claimed in the present application is as follows. (1) When a cellulose fiber fabric is dyed and processed simultaneously with a glyoxal resin using a glyoxal resin, a mixed catalyst of an organic amine hydrochloride (A) and a fluorinated compound (B) is used as a catalyst for the glyoxal resin. Characterized in that the ratio (A) / (B) of the pure component concentration of 95/5 satisfies 95/5 to 60/40.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the present invention, the cellulose fiber fabric is a fabric using natural cellulose fibers such as cotton and hemp, and regenerated cellulose fibers such as rayon, cupra and polynosic, and refers to a fabric containing 30% or more of these cellulose fibers. As the yarn constituting the cellulose fiber cloth, in addition to the filament consisting of 100% of the cellulose fiber and the spun yarn,
Filaments, spun yarns, twisted yarns, and the like made of fibers other than the cellulose fibers can be used. When fibers other than the cellulose fibers are used, the content of the cellulose fibers in the entire fabric is 30% or more. So that its usage is adjusted. The form of the fabric is not particularly limited, and a woven fabric such as taffeta, twill, and georgette, and a knitted fabric such as tricot and circular knit are used. The processing method of the present invention is particularly effective when applied to a cupra fiber fabric. The processing in the present invention is preferably performed after the cellulose fiber cloth has been scoured or scoured and bleached in advance. When fibers other than cellulose fibers are contained, it is also possible to dye the other fibers in advance and then perform the processing in the present invention.

For dyeing cellulose fiber fabrics, direct dyes are usually used. As the direct dye, commercially available products such as polyazo and thiazole azo can be used, for example, products with trademarks such as Serious, Kyalas and Sumilite. Direct dyes are used in a mixture of one or more according to a desired hue.The concentration of the direct dye in the solution is determined by the solubility of the direct dye to be used, the hue, the desired color concentration and the weight of the adhered resin relative to the weight of the fabric, that is,
The squeezing rate [(weight of attached solution / weight of fabric) × 100] is used. For example, in the case of a fabric with a squeezing rate of 100%, if there is no washing step such as soaping after the simultaneous processing of the dyeing resin, the upper limit of the direct dye solution concentration is 2% by weight, Poor color fastness makes it difficult to use.

In the present invention, the kind of the direct dye is not particularly limited, but a dye having a weak acidic property in which the pH of the resin / catalyst aqueous solution is 4 to 6 and which is stable in this pH range and has high dyeability is appropriately selected. It is preferable to use them. Preferred direct dyes include C.I. Direct. Yellow-
86, Yellow-87, Yellow-130, R
ed-83, Red-89, Red-95, Red-2
43, Blue-71, Blue-90, Blue-2
01, Green-59, Black-112 and the like.

In the present invention, as the glyoxal resin, a dimethylol glyoxal urea resin which is generally called a low formalin resin, a dimethyl glyoxal urea resin which is generally called a non-formalin resin, and the like are used. Examples of the former commercially available products include Euramine T-FNS (manufactured by Mitsui Chemicals, Inc.) and Beckamine LFK.
(Manufactured by Dainippon Ink and Chemicals, Inc.) and Uniresin GS-15 (manufactured by Yunika Giken Co., Ltd.), and the latter commercially available products include, for example, Euramine T-NF-210 (manufactured by Mitsui Chemicals, Inc.) and Becamine NF-5 (Manufactured by Dainippon Ink and Chemicals),
Uniresin NF-168N (manufactured by Unica Giken), Sumitec Resin NF-500K (manufactured by Sumitomo Chemical), Alcofix V-3751 (manufactured by Hoechst) and the like. Of these, the use of non-formalin-based resins that do not generate free formalin is preferred.

The concentration of the glyoxal resin used is not particularly limited, but in the case of a cloth with a squeezing rate of 100%, the concentration of the glyoxal resin in the solution is preferably 5 to 20% by weight in apparent resin concentration. Preferably 8 to 15
% By weight. When the apparent resin concentration exceeds 20% by weight, the toughness is improved, but the Martindale abrasion strength and the tear strength may be reduced, and when it is less than 5% by weight, sufficient shrinkage resistance and wrinkle resistance are obtained. May be difficult to obtain.

In the present invention, the catalyst of the glyoxal resin includes an organic amine hydrochloride (A) and a fluorinated product (B) in view of the color developing property, fastness, anti-wrinkling property, and tear strength of the cellulose fiber cloth. ) Is used. As the organic amine hydrochloride, amino alcohol hydrochloride, semicarbazide hydrochloride and the like are used. Examples of the amino alcohol hydrochloride include monoethanolamine hydrochloride, diethanolamine hydrochloride, triethanol hydrochloride, 2-amino and 2-methylpropanol hydrochloride.
Examples of these commercially available products include Euramine Catalyst P (manufactured by Mitsui Chemicals), Sumitex Accelerator ACX (manufactured by Sumitomo Chemical), and Dick Catalyst 376.
(Manufactured by Dainippon Ink and Chemicals, Inc.). As the fluorinated compound, magnesium borofluoride, for example, commercially available Unicatalyst G-35P (manufactured by Dainippon Ink and Chemicals, Inc.), zinc borofluoride, or the like is used. Magnesium borofluoride having little adverse effect on the human body is used. preferable.

The mixing ratio of the mixed catalyst of the organic amine hydrochloride (A) and the fluorinated compound (B) is determined as follows:
/ (B)] is 95/5 to 60/40, preferably 90 /
It is necessary to be 10-70 / 30. If the mixing ratio of the fluorinated compound (B) is less than 5, no improvement in anti-wrinkling property is observed, and if it exceeds 40, the dye precipitates or the solution drops to pH 4 or less, and the dyeing property of the dye decreases. And the color developability decreases. When only the organic amine hydrochloride (A) is used as the catalyst, the anti-wrinkle property is poor, and when only the fluorinated compound (B) is used, the anti-wrinkle property is good, but the dye directly precipitates and the coloring property is low. Low, and insufficient wet rub fastness. In the present invention, the concentration of the catalyst varies depending on the solution concentration of the glyoxal-based resin, but is 1 to the apparent resin concentration of the glyoxal-based resin.
Preferably, the apparent catalyst concentration is 0 to 50% by weight,
More preferably, it is 20 to 40% by weight.

In the present invention, in processing a cellulose fiber fabric, a required amount of a glyoxal resin, a mixed catalyst and a resin / dye aqueous solution containing a direct dye are used, and the resin and the dye are simultaneously applied to the cellulose fiber fabric. A finishing agent used for finishing after dyeing of a general cellulose fabric may be appropriately used in combination with the aqueous resin / dye solution according to the purpose. Examples of the finishing agent include a softening agent, a water repellent, an oil repellent, an antifouling agent, an antistatic agent, a sewability improving agent, an antibacterial deodorant agent, a penetrant, a migration inhibitor, a reduction inhibitor, and the like. Preferably, the ionicity of these processing agents is nonionic. In the case of the cationic type, ionic bonding occurs directly with the dye, the dyeing property of the dye inside the fiber is low, and the fastness tends to be inferior to the nonionic type.

The above resin, dye, and processing agent are applied to the cellulose fiber fabric by a coating method, a spray method, a padding method, a roller printing method, a screen printing method, etc. In view of this, a padding method in which the cellulose fiber cloth is immersed in an aqueous solution of a resin, a dye, and a processing agent and then squeezed with a mangle is preferable.

A specific example in the case of processing by the padding method will be described below. First, the scoured and dried cellulose fiber cloth is immersed in a resin / dye / processing agent liquid, squeezed with a mangle to uniformly apply the resin, the dye and the processing agent, and then wound into a roll. Next, the wound fabric is kept in a state where moisture does not evaporate (first step). Usually, the fabric wound into a roll is wrapped in a vinyl sheet and is heated in a room adjusted to room temperature to 95 ° C. for 1 to 10 hours.
It is left rotating for about an hour. As a result, the dye is directly diffused into the fiber and dyed. The temperature and time at this time are not particularly limited, but from the viewpoint of the fastness, it is preferable to leave at a high temperature. On the other hand, from the viewpoint of leveling properties, the lower the temperature, the slower the adsorption of the dye to the outer surface of the fiber, and the better the leveling properties. When simultaneously obtaining high levelness and high fastness, wrap the rolled-up fabric in a vinyl sheet and leave it for 1-2 hours while rotating at room temperature, then raise the temperature to 70-95 ° C. Two
It is preferable to leave it further for 5 hours.

Next, the glyoxal resin is crosslinked with the cellulose fiber by curing (second step). This curing may be usually performed at a temperature of 140 ° C. to 180 ° C. for 1 to 5 minutes. Curing temperature is 14
If the temperature is lower than 0 ° C, crosslinking of the resin becomes insufficient, and the shrinkage resistance and wrinkle resistance may be insufficient.
In some cases, cellulose is embrittled, resulting in a decrease in tear strength.

The present invention proposes the most streamlined method for simultaneously processing a dyed resin of a cellulose fiber cloth. When the cured cloth is processed, the dyeing fastness is a problem in the deep color processing. After finishing without adding a finishing agent to the resin / dye aqueous solution, after curing, after performing soaping to remove the undyed direct dye, the finishing used for general cellulose fabric By providing the processing agent, it is possible to improve the fastness.

[0018]

The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. In addition,
The evaluation in the examples was performed as follows. (1) Color development: The surface of the work cloth is measured with a spectrophotometer (Macbet).
h2020). The colorimetric conditions are:
C, UV light; included, specular gloss; included, field of view; 2 degrees. The color density is represented by K / S (Kubelka-Munk) at a wavelength at which light absorption in the visible region is maximum. (2) Washing fastness: Evaluated according to JIS L-0844. (3) Friction fastness: Evaluated using a friction tester type II according to JIS L-0849. (4) Wrinkle resistance: Evaluated according to the wire method of JIS L-1059, Method A. (5) Tear strength: Evaluated according to JIS L-1018 pendulum method. (6) Washing shrinkage: Evaluated according to JIS L-1042, G method home washing machine method.

Example 1 A warp density of 131 filaments / inch, a cupra fiber of 50 denier 30 filaments (manufactured by Asahi Chemical Industry Co., Ltd.) and a weft of 54 denier 54 filament cupra fibers,
Using a taffeta greige with a weft density of 83 pieces / inch, in accordance with a conventional method, using a fabric that has been desizing, scouring, dewatering, and drying, immersed in the following resin, dye, and finishing agent solution, and squeezed with a mangle at a pickup rate of 80%. , Rolled up.

<Resin / Dye / Processing Agent Liquid> Resin: Euramine-T-NF-210 15% by weight Catalyst: Organic amine hydrochloride (Euramine Catalyst P) 3.4% by weight Magnesium borofluoride (Unicatalyst G) -35P) 1.1% by weight Catalyst mixing ratio: Organic amine hydrochloride: Magnesium borofluoride 88:12 Direct dye: Kayarus Supra Yello RL (manufactured by Nippon Kayaku) 0.2% by weight Kayarus Supra Red BWS (B) 0 15% by weight Kayarus Supra Blue BRL 200% (〃) 0.15% by weight Finishing agent: Softener Silicone 810M (manufactured by Yokosha Yushi Kogyo Co., Ltd.) 1.0% by weight Water repellent Zebulan F-1 (〃) 2.0% % Zebulan FC-2 (〃) 1.0% by weight Strength enhancer Epol 900 (〃) 1.0% by weight Epol HC-1 (〃) 2.0% by weight

The cloth wound around the roll was wrapped with a vinyl sheet so that moisture did not evaporate. Next, the roll was allowed to stand at room temperature (30 ° C.) for 2 hours while rotating, then moved to a room set at 95 ° C., and left for 3 hours while rotating. After the standing, the vinyl sheet was opened, and curing was performed at 180 ° C. for 1 minute by a heat setter, and the dyeing resin finishing was simultaneously performed. The resulting fabric was brown and had no spots. The evaluation results of this fabric are shown in Table 1, and it was found that the fabric was excellent in dyeing properties, washing fastness, friction fastness, wrinkle resistance, tear strength and washing shrinkage.

Example 2 A dyed resin finishing simultaneous processing was carried out in the same manner as in Example 1 except that the following resin, dye and finishing liquid were used. <Resin / Dye / Processing agent liquid> Resin: Uniresin GS-15 10% by weight Catalyst: Organic amine hydrochloride (Euramine Catalyst P) 2.4% by weight Magnesium borofluoride (Unicatalyst G-35P) 0.6 % By weight Catalyst mixing ratio: Organic amine hydrochloride: Magnesium borofluoride 90:10 Direct dye: Sumilight Supra Gray CGL (manufactured by Sumitomo Chemical Co., Ltd.) 0.5% by weight Finishing agent: Softening agent Siliconcorane 810M (manufactured by Yushi Yushi Kogyo Co., Ltd.) 1.0% by weight Water repellent Zebulan F-1 (〃) 1.0% by weight Zebulan FC-2 (〃) 0.5% by weight Strength improver Epol 900 (〃) 1.0% by weight Epol HC-1 (〃) 2.0% by weight The resulting fabric was brown and had no dyeing spots. The evaluation results of this fabric are shown in Table 1, and it was found that the fabric was excellent in dyeing properties, washing fastness, friction fastness, wrinkle resistance, tear strength and washing shrinkage.

Comparative Example 1 Dyeing was performed in the same manner as in Example 1 except that the catalyst of the resin, dye and processing agent liquid was only 3.3% by weight of the organic amine hydrochloride (Euramine Catalyst P). Simultaneous resin finishing was performed. The evaluation results of the obtained fabric are shown in Table 1, and were found to be inferior in washing fastness, rub fastness and wrinkle resistance.

Comparative Example 2 In Example 1, the catalyst of the resin, dye and processing agent liquid was changed to magnesium borofluoride (Unicatalyst G-35P).
Simultaneous processing of dyeing resin finishing was performed in the same manner as in Example 1 except that only 3.3% by weight was used. The evaluation results of the obtained fabric are shown in Table 1. As a result, the fabric was inferior in color development, washing fastness, rub fastness and tensile strength.

Example 3 In Example 1, the mixing ratio of the organic amine hydrochloride (Euramine Catalyst P) and the magnesium borofluoride (Unicatalyst G-35P) as the catalyst for the resin, dye and processing agent liquids was changed. Simultaneous dyeing resin finishing was carried out in the same manner as in Example 1 except that the total was 4.5% by weight at 95: 5. Table 1 shows the evaluation results of the cloth.
It was excellent in washing fastness, rub fastness, wrinkle resistance, tear strength and washing shrinkage.

Example 4 In Example 1, the mixing ratio of the organic amine hydrochloride (Euramine Catalyst P) and the magnesium borofluoride (Unicatalyst G-35P) as the catalyst of the resin, dye, and processing agent liquid was changed. Simultaneous processing of the dyed resin finishing was performed in the same manner as in Example 1 except that the total was set to 4.5% by weight at 70:30. The evaluation results of this fabric are shown in Table 1, and it was found that the fabric was excellent in dyeing properties, washing fastness, friction fastness, wrinkle resistance, tear strength and washing shrinkage.

Example 5 In Example 1, the pure mixture ratio of the organic amine hydrochloride (Euramine Catalyst P) and the magnesium borofluoride (Unicatalyst G-35P) as the catalyst of the resin, dye, and processing agent liquid was changed. Simultaneous processing of the dyed resin finishing was performed in the same manner as in Example 1 except that the ratio was 60:40 and the total was 4.5% by weight. The evaluation results of this fabric are shown in Table 1, and it was found that the fabric was excellent in dyeing properties, washing fastness, friction fastness, wrinkle resistance, tear strength and washing shrinkage.

Comparative Example 3 In Example 1, the mixing ratio of the organic amine hydrochloride (Euramine Catalyst P) and the magnesium borofluoride (Unicatalyst G-35P) as the catalyst of the resin, dye, and processing agent liquid was determined. Simultaneous processing of dyeing resin finishing was performed in the same manner as in Example 1 except that the total was 97: 3 to 4.5% by weight. The evaluation results of this fabric are shown in Table 1, and it was found that the fabric was inferior in washing fastness, rub fastness and wrinkle resistance.

Comparative Example 4 In Example 1, the mixing ratio of the organic amine hydrochloride (Euramine Catalyst P) and the magnesium borofluoride (Unicatalyst G-35P) as the catalysts of the resin, dye and processing agent liquids was changed. Simultaneous processing of the dyed resin finishing was performed in the same manner as in Example 1 except that the ratio was 50:50 and the total was 4.5% by weight. The evaluation results of this fabric are shown in Table 1, and it was inferior in dyeability, washing fastness, rub fastness and tear strength.

[0030]

[Table 1] * A: organic amine salt, B: fluorinated compound From Table 1, the cellulose fabric obtained by the processing method of the present invention has excellent color developability and dyeing fastness, and has no strength reduction.
It shows that it is excellent in wrinkle resistance and shrink resistance.

[0031]

Industrial Applicability According to the processing method of the present invention, industrially advantageous rationalized dyeing and resin processing can be achieved at the same time, and the color developability and dyeing fastness are excellent, the strength is not reduced, and the process is prevented. It is possible to obtain a cellulose fabric having excellent wrinkle properties and shrink resistance.

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Claims (1)

[Claims] 1. An organic amine hydrochloride (A) as a catalyst for a glyoxal resin when a cellulose fiber fabric is dyed and processed simultaneously with the glyoxal resin using a glyoxal resin.
And a fluorinated compound (B) mixed catalyst, and their pure component concentration ratio (A) / (B) is 95/5 to 60/40.
A method for processing a cellulose fabric, characterized by satisfying the following.