JP3225009B2 - Method for producing anti-wrinkle protein fiber structure - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wrinkle-resistant protein fiber structure having improved wrinkle resistance in a protein fiber structure composed of protein fibers such as wool and silk, and a method for producing the same.

[0002]

2. Description of the Related Art Hitherto, studies have been conducted on protein fibers, mainly wool and silk, and products thereof to improve the wrinkle resistance.

[0003] Here, as a wrinkle-preventing method for imparting wrinkle-preventing properties to a protein fiber structure composed of the above-mentioned protein fiber and its product, a physical method and a chemical method described below have been conventionally used. Methods have been developed.

[0004] As a physical method, a property inherent in protein fibers such as wool, that is, aging and annealing phenomena are used. A protein fiber structure is formed using high-pressure decatizing, vacuum autoclave, or the like. In general, a method of setting and thereby imparting wrinkle resistance to a protein fiber structure is used.

However, when the wrinkle resistance is imparted by such a physical method, the wrinkle resistance is easily lost when the protein fiber structure is steam-pressed or put in water. It was not possible to impart a long-lasting sufficient wrinkle resistance to the protein fiber structure.

On the other hand, as a chemical method, there are a method of introducing a bulky compound into a protein fiber structure, a method of subjecting the protein fiber structure to resin processing and the like, and stabilizing the structure of the protein fiber structure with a resin or the like. Is generally known.

Here, bulky compounds to be introduced into the protein fiber structure include ninhydrin, benzoquinone,
Phenylisocyanate, tannic acid, Mittin FF and the like are used, and when these compounds impart wrinkle resistance to a protein fiber structure, a longer lasting wrinkle resistance is imparted as compared with a physical method. It has been pointed out that the introduction of such bulky compounds causes problems such as a decrease in hygroscopicity and an increase in the weight of the protein fiber structure at high humidity of 80% RH or more (J.
D. Leeder, J .; A. Ass; Text. Che
m. Color. , 3, 193 (1971-8), Textile processing, 24, 343 (1972)).

Further, as such a bulky compound,
When mercuric acetate and potassium dichromate are used, excellent wrinkle resistance is imparted to the protein fiber structure. However, when these compounds are used, there is a problem in safety or the protein fiber structure Are colored, and neither of them has been put to practical use.

On the other hand, as a processing agent for performing resin processing on the protein fiber structure, toluene diisocyanate, pyrogallol / formaldehyde resin and the like are generally used, and these processing agents are used to prevent wrinkles on the protein fiber structure. When the property is imparted, an effective wrinkle resistance is imparted to the protein fiber structure. However, due to such resin processing, the texture of the protein fiber structure is impaired, and the weight of the protein fiber structure increases. Problems have been pointed out.

[0010] In recent years, there have been reports of research attempts to impart wrinkle resistance to protein fiber structures using a crosslinkable processing agent such as formaldehyde or glyoxal. Does not provide sufficient wrinkle resistance to protein fiber structures (JD.
Leeder, J .; A. Ass; Text. Chem.
Color. , 3, 193 (1971-8), Textile processing, 24, 343 (1972)).

Also, studies have been reported on a wrinkle-preventing method for a protein fiber structure in which a physical method is combined with a chemical method. In order to stabilize the annealing effect, the protein fiber structure is treated with resorcinol, melamine, and monoamine. It has been proposed to pre-treat with methylolmelamine and then anneal in the presence of paraformaldehyde to impart wrinkle resistance to the protein fiber structure.

When the wrinkle resistance is imparted to the protein fiber structure in this way, the protein fiber structure is provided with an effective wrinkle resistance. However, the tensile strength and the frictional strength of the protein fiber structure are reduced. It has been pointed out that the texture is deteriorated and the texture is impaired (Kaimori Michinobu; Dyeing, 4
1 (No. 6), 289-303 (1993)).

Further, as a method of imparting wrinkle resistance to the protein fiber structure, a method of graft-polymerizing the protein fiber structure using a vinyl monomer, a methyl-substituted styrene derivative or the like, or a method of impregnating an epoxy compound with an alkali metal catalyst. A microwave irradiation method or a method of adsorbing derivatives of wool keratin, silk fibroin, collagen, etc. have also been proposed, but the effect of improving wrinkle resistance without impairing the intrinsic properties of protein fibers has been proposed. Is currently not available.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to solve the various problems as described above in the case where wrinkle resistance is imparted to a protein fiber structure composed of protein fibers such as wool and silk. It is assumed that.

That is, in the present invention, in imparting wrinkle resistance to a protein structure, without changing the original properties of the protein fiber, specifically, without changing the texture or hue of the protein fiber, Weight increase, 8
In order to impart excellent wrinkling resistance to the protein fiber structure without lowering the hygroscopicity under high humidity conditions of 0% RH or more, and without impairing the safety. The task is to do so.

[0016]

SUMMARY OF THE INVENTION In the present invention, the wrinkle-preventing protein fiber structure and the method for producing the same are intended to solve the above-mentioned problems by providing a thiol group to the protein fiber structure via a crosslinkable spacer. Then, the protein fiber structure is oxidized to introduce a cross-link having a disulfide bond between and / or in the molecules of the protein fiber structure.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The invention disclosed in the present invention will be described in detail below. Here, the protein fiber structure in the present invention may be animal wool fibers such as wool, mohair, cashmere, and alpaca; silk fibers such as silkworms and wild silkworms; or wool, silk, or fibers or yarns obtained from these fibers. Woven fabric, knitted fabric, non-woven fabric, etc., and other fibers,
For example, polyester fiber, nylon fiber, acrylic fiber, cellulose fiber, blended or woven with hemp fiber, etc.,
The meaning includes a twisted product and the like.

In the method of introducing a thiol group into a protein fiber structure via a spacer or the like, a bivalent cross-linking chemical or the like is used as the spacer.

The divalent cross-linking chemicals include homobivalent chemicals having the same reactive group in the molecule and heterodivalent chemicals having a different reactive group in the molecule. Among them, amino groups are cross-linked. Preferably, a cross-linking chemical is used.

Examples of the cross-linking chemicals for cross-linking between amino groups include alkyl diimidates such as dimethyl succinimidate and dimethyl adipimidate, acyl azides such as diazide tartrate, disuccinimidyl sperate, and disuccin. N-hydroxysuccinimide esters such as imidyl tartrate and dithiobis (succinimidyl propionate); isocyanates such as xylene-m-diisocyanate; 1,5-difluoro-
Aryl dihalides such as 2,4-dinitrobenzene,
Examples include dialdehydes such as glutaraldehyde.

Using these divalent cross-linking chemicals, a spacer is introduced into an amino group in the protein fiber.
If necessary, the unreacted thiol group introduction reagent is removed by washing with water or the like, followed by drying.

Next, a compound having a thiol group in the molecule is introduced. As the compound having a thiol group, L-cysteine or the like is preferable when a cross-linking chemical that cross-links between amino groups is used, depending on the divalent cross-linking chemical used. Then, an oxidizing agent such as hydrogen peroxide is sprayed or applied to the above-mentioned protein fiber structure or steamed to oxidize the same, and then the protein fiber structure is air-dried or forced-dried. .

In this manner, most of the thiol groups introduced into the protein fiber structure form disulfide bonds, and finally, a large number of three-dimensional intermolecular crosslinks are introduced into the protein fiber structure. The wrinkle resistance of the protein fiber structure is improved.

[0024]

EXAMPLES Next, examples of the present invention will be specifically described, and it will be apparent that the examples of the present invention are superior in terms of wrinkle resistance as compared with those of comparative examples. To However, the present invention is not limited to the embodiments described below, and can be implemented with appropriate modifications without departing from the spirit of the present invention.

[0025]

Example 1 In this example, a fabric composed of wool fibers was used as a protein fiber structure, and the fabric of the wool fibers was mixed with a 0.1 M phosphate buffer solution containing 1% by weight of glutaraldehyde ( pH 7) (containing 0.1% Triton X100) at a bath ratio of 54 times, and while shaking, the wool fiber fabric was reacted at 50 ° C. for 2 hours to form a spacer on the wool fiber. After the introduction of the wool fiber, the wool fiber fabric was washed with water to remove unreacted reagents.

Thereafter, this wool fiber cloth is immersed in a 0.4% L-cysteine aqueous solution (containing 0.1% Triton X100) and reacted at room temperature for 30 minutes to introduce SH groups into the wool fibers. At the same time, the disulfide bond existing in the wool fiber was cleaved. Next, a pickup (drawing ratio) was prepared, the wool fiber cloth was held in a flat shape using a steam iron, and in this state, the wool fiber cloth was oxidized by steaming to obtain a processed cloth of Example 1. I got

[0027]

Comparative Example 1 In this comparative example, the same wool fiber fabric as in Example 1 was used as the protein fiber structure.
This wool fiber cloth was treated with a glutaraldehyde-free 0.1 M phosphate buffer solution (pH 7) (0.1%
Triton X100) at a bath ratio of 54 times, and the wool fiber fabric was reacted at 50 ° C. for 2 hours while shaking in the same manner as in Example 1 above. This was washed with water, a pickup (diaphragm ratio) was prepared, the wool fiber fabric was held in a flat shape using a steam iron, and in this state, the wool fiber fabric was oxidized by steaming to obtain a comparative example. 1 work cloth was obtained.

Next, the wrinkle resistance of each work cloth obtained as described above was evaluated.

In evaluating the wrinkle resistance of each work cloth, a size of 15 mm × 4 in the warp yarn direction was used.
A test piece of 0 mm was collected from each work cloth, and each test piece was stored in advance at a temperature of 20 ° C. and a humidity of 65% RH for about 24 hours, and then the test pieces were further heated to a temperature of 30 ° C. using a thermo-hygrostat. ,
Stored under 90% RH for 24 hours, adjusted the sample,
Then, each test piece was folded, and each test piece was subjected to a temperature of 2
At a temperature of 0 ° C. and a humidity of 65% RH, an 800 g load was applied for 90 minutes to perform wrinkling. After that, the opening angle after 30 minutes was measured using a Monsanto type tester, and the wrinkle recovery rate was determined. The results are shown in Table 1.

[0030]

[Table 1]

As a result, after introducing a thiol group into the wool fiber via a spacer using glutaraldehyde, the fabric of the wool fiber was oxidized by steaming to form a disulfide bond, thereby increasing cross-linking by the disulfide bond. The work cloth of Example 1 had a larger opening angle and an improved wrinkle recovery rate than the work cloth of Comparative Example 1 in which no thiol group was introduced.

[0032]

As described in detail above, when the wrinkle resistance is imparted to the protein fiber structure as shown in the present invention, the texture and hue of the protein fiber are not changed as in the prior art.
In addition, the weight does not increase, the hygroscopicity under high humidity conditions of 80% RH or more does not decrease, and further, safety is not hindered.
Excellent wrinkle resistance has been imparted to protein fiber structures.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) D06M 13/00-13/535

Claims (1)

(57) [Claims] After introducing a thiol group into a protein fiber structure via a crosslinkable spacer, the protein fiber structure is oxidized to form disulfides between and / or within the molecule of the protein fiber structure. A method for producing a wrinkle-resistant protein fiber structure, characterized in that a crosslink having a bond is introduced.