JPH05247851A - Cellulose fiber imparted with shrink resistance and its production - Google Patents

Abstract

PURPOSE:To obtain a fiber having durable shrink resistance and free from generation of formalin by immersing a cellulose fiber in a treating liquid containing a specific polycarboxylic acid and a silicon compound and heat- treating the impregnated fiber. CONSTITUTION:A textile material composed of cellulose fiber is immersed in a treating emulsion liquid containing a polycarboxylic acid (especially butanetetracarboxylic acid) and a silicon compound having at least one aliphatic hydroxyl group and/or amino group in the molecule (preferably polyether- modified silicone, etc.) and adjusted to pH 2-5. The impregnated textile material is squeezed, dried and heat-treated to obtain the objective cellulose fiber imparted with shrink resistance durable to washing and free from the problems of the deterioration of fiber and the generation of formalin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to shrink-proof cellulose fibers and a method for producing the same.

[0002]

2. Description of the Related Art Cellulose typified by cotton is widely used because of its many advantages such as hygroscopicity and texture, but on the other hand, it has a drawback that it tends to shrink. Therefore, various treating agents have been used to overcome such drawbacks. For example, a method has been adopted in which a cellulose fiber is treated with a fibrin-reactive resin containing a urea formalin resin or a glyoxal resin which is a derivative thereof as an active ingredient.

However, the method of treating with such a fibrin reactive resin has the following drawbacks. That is,
When cellulose fibers are treated with a fibrin-reactive resin containing urea formalin resin or its derivative, glyoxal resin, as an active ingredient, it is inevitable that formalin remains in the cellulose fibers even after the treatment. In addition to its peculiar malodor, formalin is known to be a carcinogen, and it not only adversely affects the working environment in the fiber treatment process but also the consumer who uses the final product. In recent years, the safety orientation has been further increasing, and the use of carcinogenic formalin tends to be obliged to tighten regulations and refrain from restraint.

Under the circumstances, therefore, there is a demand for an epoch-making non-form processed cellulose fiber which does not use urea formalin resin or glyoxal resin.

[0005]

In view of the present situation, the inventors of the present invention have conducted extensive studies to provide a cellulose fiber having the above-mentioned drawbacks and having shrink resistance. as a result,
It has been found that by impregnating a polycarboxylic acid and a silicon compound containing at least one aliphatic hydroxyl group and / or amino group in the molecule and heat-treating the cellulose fiber, it is possible to impart excellent durability to shrink resistance. It was The present invention has been completed based on such findings.

That is, according to the present invention, a polycarboxylic acid and a cellulose compound which is impregnated with a silicon compound having at least one aliphatic hydroxyl group and / or amino group in the molecule and is heat-treated to impart shrinkage resistance are provided. Related to fiber.

Cellulose fibers in the present invention include cotton, hemp, rayon and blended fibers containing these fibers, and also products such as woven fabrics, knits and nonwoven fabrics made of these fibers.

As the polycarboxylic acid used in the present invention, conventionally known ones can be widely used. Examples thereof include linear aliphatic polycarboxylic acid, branched aliphatic polycarboxylic acid, alicyclic polycarboxylic acid and aromatic. Examples thereof include polycarboxylic acids, and these acids may have a hydroxyl group, a halogen atom, a carbonyl group, a carbon-carbon double bond, or the like. As such polycarboxylic acid, specifically, oxalic acid, malonic acid,
Succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, etc. and their branched carboxylic acids, maleic acid, unsaturated dibasic acids such as fumaric acid, cyclohexanedicarboxylic acid, tetrahydrophthalic acid, nadic acid, etc. Alicyclic dibasic acid, tricarballylic acid, aconitic acid,
Tribasic acids such as methylcyclohexene tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, tetrahydrofuran tetracarboxylic acid, tetrabasic acids such as ene adducts of methyltetrahydrophthalic acid and maleic acid, malic acid, tartaric acid, citric acid Aromatic polycarboxylic acids such as hydroxy fatty acids such as o-phthalic acid, m-phthalic acid, p-phthalic acid, trimellitic acid, pyromellitic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid and diphenylsulfonetetracarboxylic acid Etc. can be illustrated. Among these polycarboxylic acids, butanetetracarboxylic acid, tricarballylic acid, aconitic acid,
Water-soluble carboxylic acids such as citric acid have good workability,
It is a compound preferably used. In particular, butanetetracarboxylic acid, which is a water-soluble and tetrabasic acid, is the most suitable because it can exert the effect of the present invention that the cellulose fiber can be provided with the shrink-proof property with excellent durability.

At least 1 in the molecule used in the present invention
The silicon compound containing one aliphatic hydroxyl group and / or amino group is a compound having dimethylpolysiloxane as a basic skeleton, and is generally amino-modified silicon or polyether (polyoxyethylene and / or polyoxypropylene) -modified Compounds which are called silicon, alcohol-modified silicone, epoxy-polyether-modified silicone, etc., and which are on the market can be widely used. Specific examples of such silicon compounds include the following. For example, as amino-modified silicon, SF8417, BY16-828, BY manufactured by Toray Dow Corning Silicone Co., Ltd.
16-849, BY16-850, SM8702, SM
8709, BY22-812, BY22-819, BY
22-823 and the like are used as polyether-modified silicone, SH manufactured by Toray Dow Corning Silicone Co., Ltd.
3746, SH3749, SH3771, SH377
2, SH3773, SH3775, SH8400, SF
8410, SH8700 and the like are alcohol-modified silicones such as SF8427 and SF8428 manufactured by Toray Dow Corning Silicone Co., Ltd., and epoxy-polyether-modified silicone is Toray Dow Corning
Examples include SF8421 manufactured by Silicone Co., Ltd. Among the above silicon compounds, polyether modified silicon is particularly preferable. These silicon compounds are available as a raw material or an emulsion solution and can be used as they are in the present invention.

The cellulose fiber of the present invention is produced, for example, by impregnating the above-mentioned polycarboxylic acid and silicon compound into the cellulose fiber and then heat-treating the cellulose fiber.

When the cellulose fiber is impregnated with the polycarboxylic acid and the silicon compound, the cellulose fiber may be dipped in a treatment liquid containing the polycarboxylic acid and the silicon compound, for example. The treatment liquid usually comprises a polycarboxylic acid, a silicon compound and a solvent. Although an organic solvent can be used as the solvent, it is preferable to use water as the solvent in consideration of safety and price. When the polycarboxylic acid or silicon compound does not dissolve in water, it is preferable to prepare a liquid in which the polycarboxylic acid or silicon compound is emulsified or solubilized with a surfactant. Here, as the surfactant, conventionally known ones can be widely used as long as they are active in an acidic aqueous solution, for example, an ethylene oxide adduct of an alkylphenol, an ethylene oxide adduct of a higher alcohol, an alkylbenzene sulfonate, an alkyl sulfate, an alkyl. Examples thereof include betaines, sorbitan fatty acid esters and ethylene oxide adducts thereof, fatty acid monoglycerides and ethylene oxide adducts thereof. In the present invention, an alkylphenol ethylene oxide adduct and a higher alcohol ethylene oxide adduct, which are stable in an acidic aqueous solution for a long period of time and are hardly affected by alkalis for pH adjustment described below, are particularly preferable. The amount of such a surfactant to be used is not particularly limited as long as it can stably disperse the polycarboxylic acid or the silicon compound in water, and is usually 0.1 to 10% by weight in the treatment liquid. Good.

The concentration of the polycarboxylic acid and the concentration of the silicon compound in the treatment liquid may be set to the concentration calculated from the squeezing ratio of the treatment liquid and the required impregnation amount. The amount of the polycarboxylic acid to be impregnated into the cellulose fiber varies depending on the type of the polycarboxylic acid used and the like and cannot be generally specified, but it is usually about 0.1 to 50% by weight, preferably 0% to the cellulose fiber. It is preferable to be about 0.5 to 20% by weight. If the impregnated amount of the polycarboxylic acid is too small, it becomes difficult to exert the effect of the present invention that it is possible to impart the cellulose fiber with the shrink-proof property excellent in durability, while the impregnated amount corresponds to the impregnated amount even if a large amount is impregnated Not effective and not economical. The amount of the silicon compound to be impregnated into the cellulose fiber varies depending on the type of the silicon compound used and cannot be generally specified, but is usually about 0.1 to 100% by weight, preferably 1 to 100% by weight based on the cellulose fiber. It is preferable to set it to about 50% by weight. If the impregnated amount of the silicon compound is too small, it becomes difficult to exert the effect of the present invention that it is possible to impart the cellulose fiber with a shrinkproofing property excellent in durability, and even if impregnated in a large amount, an effect corresponding to the impregnated amount is obtained. Not effective and not economical.

To the aqueous solution in which the polycarboxylic acid and the silicon compound are dissolved, a pH adjusting agent is added in advance to adjust the pH of the solution.
It is desirable to adjust. The pH range is usually 1 to
6, preferably in the range of 2-5. If the pH of the liquid is higher than the above range, the shrink-proofing effect tends to be difficult to be exhibited, while if the pH of the liquid is lower than the above range, a decrease in fiber strength tends to be unavoidable due to hydrolysis of cellulose. , Not preferable. pH
Alkali or a salt thereof is usually used as a regulator. Specific examples of the pH adjusting agent include sodium hydroxide, sodium bicarbonate, sodium borate, sodium metaborate, sodium silicate, sodium metasilicate, sodium phosphate, sodium metaphosphate, sodium polyphosphate, sodium pyrophosphate. , Sodium phosphite, sodium hypophosphite, sodium formate, sodium acetate and the like. Instead of sodium as the pH adjuster, potassium, ammonium or the like, or a salt of a volatile lower amine such as methylamine, dimethylamine, trimethylamine or triethylamine can be used. These may be used alone or in combination of two or more. These p
The amount of the H adjuster used varies depending on the amount and type of the polycarboxylic acid and the silicon compound dissolved and cannot be generally specified, but it is usually preferable to add about 0.1 to 10% by weight to the treatment liquid.

In the present invention, the cellulose fibers to be treated are immersed in the treatment liquid prepared as described above, squeezed according to the required impregnation amount, and then dried.

The permeation rate of the treatment liquid of the present invention into the cellulose fibers is sufficiently high, and the immersion time and bath temperature are not particularly limited. Generally, the immersion time is 0.5 to 300 seconds and the bath temperature is 10
Performed at ~ 40 ° C. The drawing depends on the cellulose fiber product to be processed, and an appropriate drawing method and drawing ratio can be adopted for each. Usually, it is preferable that the drawing rate is 40 to 200%. The temperature during the next drying is 40-
The temperature is preferably about 150 ° C., and the drying time may be set appropriately according to the temperature.

When heat-treating the cellulose fibers impregnated as described above, the heat treatment temperature is usually 100 to 250 ° C., preferably 120 to 200 ° C., and the heat treatment time is about 30 seconds to 1 hour. Is good. If the heat treatment conditions are milder than the above, the shrink-proofing effect of the cellulose fibers tends to be difficult to be exhibited, while on the other hand, if the conditions are too strict than the above, the cellulose fibers tend to deteriorate and the strength decreases and the fiber yellows. Either of them is not preferable.

In the present invention, it is not necessary to impregnate the cellulose fiber with the polycarboxylic acid and the silicon compound in the same bath as described above. For example, it is possible to first impregnate the cellulose fibers with the polycarboxylic acid, heat-treat it, impregnate the cellulose fibers with a silicon compound, and heat-treat again. However, from the viewpoint of productivity, it is preferable to employ a method of impregnating the cellulose fibers with a treatment liquid obtained by dissolving, solubilizing or emulsifying the polycarboxylic acid and the silicon compound in the same bath.

The cellulose fiber processed as described above is further subjected to conventional means such as washing with water, soaping, and application of a fiber softening agent to obtain a desired product.

[0019]

EFFECTS OF THE INVENTION According to the present invention, there is provided a cellulose fiber having excellent durability and shrink resistance.

[0020]

EXAMPLES The present invention will be further clarified with reference to Examples and Comparative Examples below. In the following, "%" simply means "% by weight".

Example 1 As a test cloth, a cotton knit cloth (Kanoko) (30 cm × 30 c) on which marking of 20 cm × 20 cm is preliminarily marked.
m) was used.

1,2,3,4-butanetetracarboxylic acid 4%, polyether modified silicone [SH3771C,
5% of Toray Dow Corning Silicone Co., Ltd.] and 4% of sodium phosphate monobasic were dissolved to prepare an aqueous solution. The test cloth was immersed in the aqueous solution at 25 ° C. for 5 minutes and squeezed at a drawing rate of 80%. After drying at 100 ° C. for 10 minutes, heat treatment was performed at 180 ° C. for 3 minutes to obtain a heat-treated test cloth.

Example 2 An aqueous solution was prepared by dissolving 4% of 1,2,3,4-butanetetracarboxylic acid and 4% of sodium phosphate monobasic. The test cloth of Example 1 was added to the aqueous solution at 25 ° C. for 5 hours.
It was soaked for a minute and squeezed at a squeezing ratio of 80%. After drying at 100 ° C. for 10 minutes, heat treatment was performed at 180 ° C. for 3 minutes. Next, the test cloth after the heat treatment was treated with amino-modified silicone [SM87
02C, manufactured by Toray Dow Corning Silicone Co., Ltd.]
Was immersed in an aqueous dispersion liquid in which 12% was emulsified at 25 ° C. for 5 minutes and squeezed at a squeezing ratio of 80%. After drying at 80 ° C for 10 minutes, heat treatment was performed at 100 ° C for 30 minutes to obtain a heat-treated test cloth.

Comparative Example 1 The same procedure as in Example 1 was repeated except that an aqueous solution containing 4% 1,2,3,4-butanetetracarboxylic acid and 4% sodium monobasic phosphate was used. A heat-treated test cloth was obtained.

Comparative Example 2 Heating was carried out in the same manner as in Example 1 except that an aqueous dispersion prepared by emulsifying polyether modified silicone [SH3771C, manufactured by Toray Dow Corning Silicone Co., Ltd.] at a ratio of 5% was used. A treated test cloth was obtained.

Comparative Example 3 A dry-treated test cloth was obtained in the same manner as in Example 1 except that the heat treatment was not performed.

Comparative Example 4 1,2,3,4-butanetetracarboxylic acid 4%, polyether modified silicone [SH3771C, Toray Dow Corning Silicone Co., Ltd.] 5% and monosodium phosphate. A heat-treated test cloth was obtained in the same manner as in Example 1 except that soft water was used instead of the 4% dissolved aqueous solution.

Each of the treated test cloths obtained in Examples 1 to 2 and Comparative Examples 1 to 4 was washed and dried with a tumbler dryer, which was repeated 10 times, 20 times and 30 times. The marking distance of the test cloth after the above operation was measured, and the ratio to the distance immediately after the heating or drying treatment was determined to be the shrinkage rate. The results are shown in Table 1.

[0029]

[Table 1]

Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI technical display location // D06M 101: 06 (72) Inventor Koichi Murai 4-6-6 Tenjin, Nagaokakyo-shi, Kyoto (72) Inventor Miaki Sakai 1-23-6, Shirakashi-cho, Kashihara-shi, Nara (72) Inventor Hiroyuki Miura 175 Shinkai, Gohihobo-cho, Konan-shi, Aichi (72) Inventor Hiroshi Tsujimoto 1-1, Takasu-cho, Nishinomiya-shi, Hyogo Mukogawa housing complex Building No. 2, Building 918

Claims (2)

[Claims] 1. Cellulose fibers having shrink resistance, which are obtained by impregnating a polycarboxylic acid and a silicon compound having at least one aliphatic hydroxyl group and / or amino group in the molecule and heat-treating the same. 2. A cellulose fiber is impregnated with a polycarboxylic acid and a silicon compound containing at least one aliphatic hydroxyl group and / or amino group in the molecule, and the cellulose fiber is then heat treated. The method for producing a cellulose fiber according to claim 1.