JPH09268470A - Set processed product of protein fiber structure and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable the impartment of excellent setting performances to a protein fiber structure by preventing a touch feeling or a color tone of a protein fiber from changing and a button, etc., from rusting. SOLUTION: Disulfide bonds are introduced among and/or into molecules of a protein fiber structure to thereby increase the number of cross-linkages among and/or in the molecules thereof in a set processed product of the protein fiber structure prepared by setting the protein fiber structure into a desired shape. Furthermore, thiol groups are introduced into the protein fiber structure, which is then held in a desired shape. The protein fiber structure in this state is treated by oxidation and disulfide bonds are introduced among and/or into the molecules of the protein fiber structure to thereby increase the number of the cross-linkages among and/or in the molecules thereof.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a set product of a protein fiber structure in which a protein fiber structure composed of protein fibers such as wool and silk is set in a desired shape and a method for producing the same. It is characterized in that it imparts a set performance with excellent morphological stability to a structure.

[0002]

2. Description of the Related Art Conventionally, a set process such as a flat process, a pleated process and a crease process has been performed on a protein fiber structure composed of a protein fiber such as wool.

Here, when the protein fiber structure is subjected to set processing such as crease processing as described above, conventionally, lanthionine, lysinoalanine and disulfide bonds are generated by setting while heating with steam. It was made to process such as a crease.

However, in order to carry out processing with sufficient durability by this method, it is necessary to set using steam of high temperature and high pressure, and the protein fiber structure turns yellow and becomes brittle. Then, there was a problem such as impairing the texture.

Further, conventionally, when a protein fiber structure is subjected to crease processing or the like, Japanese Patent Publication No. 37-309
As disclosed in Japanese Patent Publication No. 9, a thiol compound typified by ammonium thioglycolate is used as a reducing agent to cleave a disulfide bond in a protein fiber structure, and then the protein fiber structure is provided with folds or the like. , A method of recombining this in this state has been proposed, and a method called syroset processing using monoethanolamine bisulfite or monoethanolamine sulfite instead of ammonium thioglycolate is also proposed. Has been done.

[0006] Here, ammonium thioglycolate effectively acts on disulfide bonds in wool fibers, but has a great effect on dyes, and changes the hue, texture, and residue of protein fiber structures. It has been pointed out that there is a strong odor.

Also, when monoethanolamine bisulfite or monoethanolamine sulfite is used, the hue of the protein fiber structure is changed to impair the texture or remain as in the case of ammonium thioglycolate. It has been pointed out that it has a strong odor and that buttons and other parts rust.

Further, in the study of permanent wave agents for human hair, a method has been proposed in which cysteine, which has a lower reducing power than ammonium thioglycolate, is used instead of ammonium thioglycolate, and cysteine is in a solution state. In order to make up for the drawback of being easily oxidized by cysteine, a method using a cysteine derivative such as N-acetyl cysteine, cysteine ester, N-carbamoyl cysteine or a mixture of these cysteine derivatives with cysteine is used instead of cysteine. Methods etc. have been proposed.

It is considered that the technique for the permanent waving agent for human hair is used for set processing in a protein fiber structure such as wool fiber. In Japanese Patent Publication No. 5-61386, a wool fiber product is used. It has been proposed to make durable folds using cysteine or cysteine derivatives.

However, as described above, the reducing power of cysteine is weaker than that of ammonium thioglycolate, monoethanolamine bisulfite or monoethanolamine sulfite, and discoloration or the like in the protein fiber structure is less likely to occur. However, it is difficult to obtain sufficient settability, and it is necessary to strictly adjust the settling conditions, and further, in order to obtain sufficient settability, a large amount of such reducing agent must be used. Therefore, the reducing agent is likely to remain in the processed product, and when the reducing agent remains in the processed product like this, if it gets wet in the rain, wrinkles formed during wearing will not return, There was a problem that sometimes a sulfur odor was generated.

Further, in recent years, in order to improve alkali resistance, mechanical properties and the like without impairing the setting property, a processing method in which a crosslinking agent having a disulfide bond is used to crosslink between amino groups in a wool fiber. Has been reported (Sakamoto M; Proc 7th
Int Wool Text Res Conf,
4,382 (1985)).

However, when the reduction treatment is carried out in this method, the settability is rather deteriorated and the desired effect is not obtained.

[0013]

SUMMARY OF THE INVENTION It is an object of the present invention to solve various problems as described above in setting a protein fiber structure composed of protein fibers such as wool and silk into a desired shape. To do.

That is, an object of the present invention is to set a protein fiber structure in a desired shape by using a conventional processing method using ammonium thioglycolate, monoethanolamine bisulfite, monoethanolamine sulfite or the like. In addition, it does not change the original properties of the protein fiber, specifically, the texture and hue of the protein fiber do not change, and the buttons etc. do not get rusted. Unlike conventional processing methods using cysteine derivatives, the reducing power is weak and there is no need to strictly control the setting conditions, and there is no drawback that the reducing agent easily remains in the product, and excellent setting performance is achieved. It is intended to provide a set processed product of an imparted protein fiber structure and a method for producing the same.

[0015]

In order to solve the above problems, a set processed product of a protein fiber structure according to the present invention is a set of protein fiber structure in which the protein fiber structure is set in a desired shape. In the processed product, intermolecular and / or intramolecular disulfide bonds were introduced into the protein fiber structure to increase the number of intermolecular and / or intramolecular crosslinks in the protein fiber structure.

In the method for producing a set processed product of protein fiber structure according to the present invention, in order to solve the above problems, after introducing a thiol group into the protein fiber structure, the protein fiber structure is treated with the thiol group. The protein fiber structure is retained in the desired shape, and in this state, the protein fiber structure is subjected to an oxidation treatment to introduce a disulfide bond between the molecules of the protein fiber structure and / or in the molecule, thereby maintaining the protein fiber structure in the desired shape. The number of crosslinks between and / or within the molecule of the product is increased.

Here, the protein fiber structure in the present invention includes animal hair fibers such as wool, mohair, cashmere, alpaca, silk fibers such as domestic silkworms and wild silkworms, or yarns or silk yarns obtained from these fibers, or these fibers. Woven fabrics, knitted fabrics, non-woven fabrics and the like obtained from fibers or yarns, and other fibers, for example,
It is also meant to include mixed-spun products with polyester fibers, nylon fibers, acrylic fibers, cellulose fibers, hemp fibers, mixed knitted fabrics, and twisted products.

When a disulfide bond is introduced into such a protein fiber structure to increase the number of intermolecular and / or intramolecular crosslinks, when a thiol group is introduced into the protein fiber structure as described above, Usually, a thiol group is directly introduced into the protein fiber structure by using a chemical agent or the like for introducing the thiol group.

Here, examples of the chemical agent for introducing a thiol group include 3-mercaptopropionimidate, methyl 4-mercaptobutyrimidate, 2-iminothiolane, N-acetylhomocysteine thiol lactone and 2-thiol group. Succinimidyl 3- (2-pyridyldithio) propionate protected with pyridyl disulfide group, S in which thiol group is protected with acetyl group
-Acetyl mercaptosuccinic anhydride, succinimidyl S-acetyl thioacetate, etc. can be used. These protective groups can be easily removed by reacting with the protein fiber structure and then treating with a reducing agent such as dithiothreitol or by treating with hydroxylamine.

When the thiol group is introduced into the protein fiber structure using the thiol group-introducing chemical agent, the thiol group-introducing chemical agent is contained in an amount of 1 × 10 ^-6 M to 1 M. Buffer (pH 5-1
0) The protein fiber structure is immersed in a bath ratio of 2 to 400 times, and the mixture is reacted at a temperature of 0 to 100 ° C. for 1 minute to 24 hours while adding stirring, shaking and the like as necessary. ,
Introduce a thiol group into the protein fiber structure. Then, if necessary, the above-mentioned unreacted chemicals are removed by washing with water or the like and dried.

After introducing the thiol group into the protein fiber structure in this manner, the pickup (drawing ratio) is adjusted at the 2 dip nip, and the steam iron,
The protein fiber structure is held in a desired shape by using a press machine, a vacuum autoclave, or the like.

Next, in the oxidation treatment of the protein fiber structure thus held in the desired shape, the above protein fiber structure is steamed, or a peroxide agent such as hydrogen peroxide is sprayed or It is applied so that it is oxidized, and then the protein fiber structure is naturally dried or forced to be dried.

By doing so, most of the thiol groups introduced into the protein fiber structure form disulfide bonds, and finally many three-dimensional intermolecular crosslinks are introduced into the protein fiber structure, As described above, the protein fiber structure held in the desired shape is sufficiently set.

When the above-mentioned protein fiber structure has a disulfide bond like wool fiber, a thiol group is introduced as described above, and this is washed with water, and then this protein fiber structure is reduced with a reducing agent. Is immersed in an aqueous solution containing, to cleave the disulfide bond originally possessed by this protein fiber structure by reduction, and then subjected to an oxidation treatment while maintaining this protein fiber structure in the desired shape as described above. It is preferable to form a disulfide bond, and when this is done, the protein fiber structure is provided with superior setting performance.

Here, as the above-mentioned reducing agent, for example,
Ammonium thioglycolate, mercaptoethanol, L-cysteine, N-acetyl-L-cysteine and the like can be used, but the reducing agent is not particularly limited thereto.

[0026]

EXAMPLES Next, the examples of the present invention will be specifically described, and it will be clarified that the examples of the present invention are excellent in settability in comparison with those of the comparative examples. However, the present invention is not limited to the embodiments described below, and can be implemented with appropriate modifications within the scope of the invention.

(Example 1) In this example, a fabric composed of wool fibers was used as the protein fiber structure, and 0.05 containing 2-iminothiolane at 2.9 mM.
The wool fiber fabric is dipped in a M phosphate buffer solution (pH 8) at a bath ratio of 67 times, and the wool fiber fabric is reacted at 25 ° C. for 2 hours while shaking to obtain a wool fiber. After introducing a thiol group into the, the wool fiber cloth was washed with water to remove unreacted reagents.

Then, 0.4% L of the wool fiber cloth is used.
-Dip in an aqueous cysteine solution for reduction to cleave the disulfide bonds present in the wool fiber, then adjust the pickup (squeeze ratio), make a crease on the fabric of this wool fiber using a steam iron, and in this state Then, the wool fiber cloth was steamed twice each on the left and right sides, whereby the wool fiber cloth was oxidized to obtain the processed cloth of Example 1.

(Example 2) Also in this example, as the protein fiber structure, the same wool fiber cloth as in Example 1 was used, and 0.05 M phosphoric acid containing 2.9 mM N-acetylhomocysteine thiol lactone was used. Buffer solution (pH
In 8), the wool fiber cloth was dipped in a bath ratio of 67 times, and the wool fiber cloth was reacted at 25 ° C. for 2 hours while shaking to introduce a thiol group into the wool fiber. Thereafter, the wool fiber cloth was washed with water to remove unreacted reagents.

Then, 0.4% L of this wool fiber cloth is used.
-Dip in an aqueous cysteine solution for reduction to cleave the disulfide bonds present in the wool fiber, then adjust the pickup (squeeze ratio), make a crease on the fabric of this wool fiber using a steam iron, and in this state Then, this wool fiber cloth was steamed two times each on the left and right sides, whereby the wool fiber cloth was oxidized to obtain the processed cloth of Example 2.

(Comparative Example 1) In this comparative example, the same wool fiber cloth as in Example 1 was used as the protein fiber structure, and this wool fiber cloth was placed in a 0.05M phosphate buffer solution (pH 8). After soaking in a bath ratio of 67 times and reacting this wool fiber fabric for 2 hours at 25 ° C with shaking, wash this with water, adjust the pickup (drawing ratio), and steam iron This wool fiber fabric was used to make creases, and in this state, the wool fiber fabric was steamed twice each to the left and right to obtain a processed fabric of Comparative Example 1.

(Comparative Example 2) In this comparative example, the same wool fiber cloth as in Example 1 was used as the protein fiber structure, and this wool fiber cloth was placed in a 0.05 M phosphate buffer solution (pH 8). The wool fiber fabric was soaked at a bath ratio of 67 times, reacted with shaking at 25 ° C. for 2 hours, and then washed with water.

Then, 0.4% L of this wool fiber cloth is used.
-Dip in an aqueous cysteine solution for reduction to cleave the disulfide bonds present in the wool fiber, then adjust the pickup (squeeze ratio), make a crease on the fabric of this wool fiber using a steam iron, and in this state Then, this wool fiber cloth was steamed twice each on the left and right, whereby the wool fiber cloth was oxidized to obtain a processed cloth of Comparative Example 2.

Next, the set performance of each work cloth obtained as described above was evaluated.

Here, in evaluating the setting performance of each of the above-mentioned work cloths, a test yarn measuring 2 cm on the left and right (4 cm in total length) around the pleated line of each work cloth is taken,
These test yarns were dipped in a 0.1 W / V% Triton X100 aqueous solution, and the open angle of each test yarn after 2 minutes was measured. The results are shown in Table 1 below.

[0036]

[Table 1]

As a result, after introducing a thiol group into the wool fiber using 2-iminothiolane or N-acetylhomocysteine thiol lactone, the wool fiber fabric is reduced to cleave the disulfide bond existing in the wool fiber,
After that, with the creases in this wool fiber fabric,
Each of the processed fabrics of Examples 1 and 2 in which the wool fiber fabric was oxidized by steaming to form a disulfide bond and the number of crosslinks by the disulfide bond was increased, was present in the wool fiber without introducing a thiol group. The open angle was much smaller than that of the processed cloth of Comparative Example 1 in which the disulfide bond was not cleaved and rebonded, and the set performance was remarkably improved.

Further, compared to the processed cloth of Comparative Example 2 in which the disulfide bond existing in the wool fiber was only cleaved and re-bonded without introducing the thiol group, the processed cloths of Examples 1 and 2 were obtained. The opening angle was significantly smaller, and the settability was significantly improved over that of Comparative Example 2.

[0039]

As described in detail above, when the protein fiber structure is provided with the settability as shown in the present invention, the texture and hue of the protein fiber are changed as in the conventional case, and the original property of the protein fiber is obtained. And the buttons and the like did not rust, and excellent setting performance was given to the protein fiber structure.

Claims (2)

[Claims] 1. In a set processed product of a protein fiber structure in which the protein fiber structure is set in a desired shape, a disulfide bond is introduced between the molecules of the protein fiber structure and / or in the molecule to form a protein fiber structure. Between molecules and /
Alternatively, a set processed product of a protein fiber structure, characterized in that the number of crosslinks in the molecule is increased. 2. After introducing a thiol group into the protein fiber structure, the protein fiber structure is held in a desired shape, and in this state, the protein fiber structure is subjected to an oxidation treatment to obtain the protein fiber structure. A set of protein fiber structures characterized by increasing the number of intermolecular and / or intramolecular crosslinks of a protein fiber structure retained in a desired shape by introducing a disulfide bond between the molecules and / or in the molecule. Processed product manufacturing method.