JP2855189B2 - Process for producing modified protein fiber and modified protein fiber product and product thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a modified protein fiber having water repellency and abrasion resistance, a method for producing a modified protein fiber product, and a modified protein having water repellency and abrasion resistance obtained by the method. The present invention relates to fibers and modified protein fiber products.

[0002]

2. Description of the Related Art Wool, mohair or other animal hair fibers or silk fibers, which are natural protein fibers, have excellent dyeing properties, moisture absorption / desorption properties, and feeling (feel) and are not found in synthetic fibers. have. Since protein fibers such as wool and silk have a high affinity for water and show hydrophilicity, muddy water and water-soluble dirt usually adhere once to the material surface when used in formal clothing materials such as kimono. It is extremely difficult to remove this only by washing. If a permanent water-repellent function can be imparted by modifying the surface of the protein fiber by a chemical reaction, it can be expected that the material can be used in the fields of Japanese clothing and Western clothing. In addition, an effective guideline for chemically modifying the surface of the protein fiber to use it as various industrial materials should be obtained.

[0003] Since the protein fiber body such as silk or wool has a fibril structure based on microfibrils, physical force is applied, and when the fiber surface is subjected to excessive wear, the fibrils are peeled off and the fiber functions and products are reduced. The value is significantly reduced. Animal hair fibers such as wool have excellent properties such as crimp shape, elasticity, hygroscopicity, and dyeability, but the material surface has developed a dense scale-like structure called scale. Since the structure prevents the penetration of processing chemicals, it is difficult to control the water repellency and hydrophilicity of the animal hair surface by chemical modification in a usual manner. Therefore, there has been a strong demand for the development of a technology capable of controlling the degree of hydrophilicity and water repellency or the degree of abrasion resistance of protein fibers and protein fiber products by relatively simple chemical modification processing. On the other hand, technology is being developed to give protein fibers such as silk or wool a new functional property in addition to the inherent properties of the fiber by grafting. However, it is extremely difficult to impart practical properties such as a water-repellent function and abrasion resistance to protein fibers and protein fiber products even if the grafting rate is increased in order to achieve the above. That is, when the graft polymerization reaction proceeds and the grafting rate increases, the functional properties such as water repellency and abrasion resistance of natural protein fibers such as silk threads decrease, and have a direct relationship with the mechanical properties of the fibers. It has been pointed out that there are adverse effects such as breakage of the fine structure (molecular orientation, crystallinity, etc.) of the fiber. Therefore, there is a demand for the development of a processing technique in which the texture of the protein fiber is not lost even after the grafting or the chemical modification processing and the degree of destruction of the microstructure is minimal.

In Japanese Patent Publication No. 47-6076, N, N
Disclosed is a method in which a silk fabric or a silk thread is treated with lauroyl chloride at 65 ° C. in a solvent such as dimethylformamide to promote an acylation reaction to improve the anti-wrinkling property of the silk fabric. However, in this conventional technique, when the number of carbon atoms of the carboxylic acid chloride is 10 or more, processing efficiency is reduced, and it is difficult to improve wrinkle resistance.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides an excellent repellency for protein fibers and protein fiber products at a low temperature of 60 ° C. or less without adversely affecting the fine structure of the fibers. An object of the present invention is to provide a method for imparting water resistance and abrasion resistance, and a protein fiber and a protein fiber product having excellent water repellency and abrasion resistance.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted research on the elucidation of the physical properties of silk protein fibers and animal hair fibers such as wool, and on the development of functions imparting technology through chemical modification processing as the central issues. The reforming method by processing has also been studied diligently. As a result, when a carboxylic acid chloride having a long-chain aliphatic hydrocarbon group is reacted with a protein fiber or a protein fiber product in an organic solvent in the presence of a base, the acylation is smoothly performed at a low temperature of 60 ° C. or less. The reaction has progressed, and it has been found that the protein fiber and the protein fiber product are imparted with good water repellency and abrasion resistance without impairing the advantageous properties inherent in the protein fiber. Reached. That is, according to the present invention, a protein fiber or a protein fiber product is represented by the following general formula (1) CH ₃ (CH ₂ ) nCOCl (1) (where n represents an even number from 10 to 16). The present invention provides a modified protein fiber having water repellency and abrasion resistance and a method for producing a modified protein fiber product, wherein the long-chain acylating agent is reacted at a temperature of 60 ° C. or lower in the presence of a base. . Further, according to the present invention, the following general formula (2) CH ₃ (CH ₂ ) nCO- (2) is added to a protein fiber via a free amino group and / or a hydroxyl group contained in the fiber. , N represents an even number of 10 to 16). A modified protein fiber having improved water repellency and abrasion resistance and a modified protein fiber product obtained by introducing a long-chain acyl group represented by the following formula:

The long-chain acylating agent used in the present invention is represented by the general formula (1). Specific examples of the long-chain acylating agent include lauroyl chloride, myristoyl chloride, palmitoyl chloride, stearoyl chloride and the like.

The protein fibers of the present invention include, in addition to silk fibers, animal hair fibers such as wool and mohair, and modified fibers obtained by modifying these fibers. In this case, the modification process means a process for imparting new functional characteristics to the fiber without impairing the feeling of texture originally possessed by the protein fiber, and examples thereof include a graph polymerization process and a chemical modification process.

[0009] The protein fiber product in the present invention means a fiber product containing the protein fiber in at least one part thereof, and includes yarn, woven fabric, knitted fabric, clothing and the like.

In order to carry out the method for producing the modified protein fiber and the modified protein fiber product of the present invention (hereinafter simply referred to as fiber), the fiber is treated with an organic solvent containing the long-chain acylating agent and a base. Immerse in the solution and heat-treat. Any organic solvent can be used as long as it can dissolve the long-chain acylating agent and the base. Examples of such a substance include N, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, pyridine and the like. In the present invention, it is preferable to use an organic solvent that swells the protein fiber, for example, N, N-dimethylformamide, dimethylsulfoxide and the like. The bath ratio of the organic solvent is from 1:20 to 1:40.

The amount of the long-chain acylating agent added to the organic solvent is 0.5 to 1 part by weight, preferably 0.7 to 0.9 part by weight, per part by weight of the fiber. The amount of the base added to the organic solvent is 0.5 to 1 mol of the long-chain acylating agent.
It is at least 1 mol, preferably at least 1 mol, and the upper limit is not particularly limited. When a basic organic solvent such as pyridine is used as the organic solvent, the organic solvent itself acts as a base. When using a non-basic organic solvent,
Add the base. As the base in this case, pyridine,
Examples thereof include alkylamines and the like, and the amount of addition is 0.5 mol or more, preferably 1 to 1.5 mol, per 1 mol of the long-chain acylating agent.

The treatment temperature is 60 ° C. or less, preferably 55 ° C.
° C or lower, and the lower limit temperature is 20 ° C, usually room temperature. In the case of animal hair fiber, the temperature is 25 to 60 ° C, preferably 30 to 55 ° C.
0 ° C, preferably 40-55 ° C. The treatment time is the time during which the desired long-chain acylating agent reacts with the fiber, and is usually 30 minutes or more. When the organic solvent is one that swells the fiber such as dimethyl sulfoxide, the acylation reaction on the fiber can be easily performed, and the acylation reaction can be performed in a short time at a low processing temperature. .

After completion of the acylation reaction, the acylated fiber (modified fiber) is separated from the organic solvent solution, drained, washed with an organic solvent, and then dissolved in an aqueous solution which acts as a good solvent for the long-chain acylating agent. Wash with a neutral organic solvent and finally with water and dry. In this case, examples of the organic solvent include the various solvents described above, and examples of the water-soluble organic solvent include lower alcohols such as methanol, ethanol, and propanol, acetone, and methyl ethyl ketone.

The acylation reaction on the fiber occurs between the active hydrogen contained in the fiber and the long-chain acylating agent. That is, an amino acid side chain containing a free amino group such as lysine or arginine contained in a protein fiber or an amino acid side chain containing a free hydroxyl group such as serine or tyrosine serves as a base of the acylation reaction.
The hydrogen bonded to these free amino groups and hydroxyl groups acts as active hydrogen and reacts with the long-chain acylating agent. In this acylation reaction, hydrogen chloride (HCl) is by-produced, and this by-produced hydrogen chloride reacts with a base present in the reaction system to form a salt, and the concentration of hydrogen chloride in the reaction system decreases. And
Thereby, the acylation reaction is promoted and proceeds smoothly.
When a long-chain acylating agent having more than 12 carbon atoms in the aliphatic hydrocarbon group is used, the reactivity to the fiber becomes poor, and the acylation reaction does not proceed smoothly at a low temperature of 60 ° C. or lower. In the presence of a base, even such a low-reactivity long-chain acylating agent reacts efficiently.

As described above, the acylation reaction in the present invention proceeds smoothly even at a low temperature of 60 ° C. or less, and the introduction of this long-chain acyl group to the fiber imparts water repellency to the fiber. The wear resistance of the fiber is improved.
In the case of the present invention, the introduction temperature of the acyl group is 60 ° C.
Since the temperature is as low as the following, the following advantages can be obtained. (1) Even if the introduction ratio of the acyl group is increased, the degree of destruction of the fine structure such as the degree of molecular orientation and the degree of crystallinity of the protein fiber becomes small, so that the texture and mechanical properties of the protein before processing are reduced. Is not impaired. (2) Since the chemical reaction can be performed in a low temperature range, the present invention can provide an energy-saving processing technique.

The introduction ratio of the long-chain acyl group to the fiber is as follows:
It is 1 to 10% by weight, preferably 1 to 5% by weight, more preferably 1 to 3% by weight, based on the fiber weight (dry matter amount). When the introduction ratio of the long-chain acyl group exceeds the above range,
It is not preferable because the texture of the fiber is impaired,
If it is lower than the above range, sufficient water repellency and abrasion resistance cannot be imparted to the fibers.

[0017]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The following methods were used to evaluate the functions of the acylated protein fibers and fiber products. A. Bending Softness JIS L1079 (1966) A cantilever method was used to horizontally send out a sample piece having a size of 2 cm × 15 cm, and the sending length until reaching a 45 ° slope was measured. For the measurement, five samples were sampled in the weft direction from the sample fabric and measured from the front side and the back side, and the average value was indicated in mm. Numerical values indicate that the larger the hardness, the harder the smaller the value. B. Contact angle Using a contact angle measuring device (FACE model CAS, manufactured by Kyowa Interface Chemical Co., Ltd.), water is sprayed on the monofilament of the sample silk thread. The site of the polka dots was photographed with an optical microscope with a magnification of 36 times, the polka dot site was enlarged and printed on photographic paper, and the contact angle was evaluated by drawing. The larger the contact angle, the higher the water repellency. C. Flexural wear strength A- specified in JIS L1096 (1990)
A 2.5 × 20 cm test piece from which a warp and a weft was removed from the cloth was folded in two and attached to a test apparatus so as to sandwich a bar by the two method (bending method). The average value was 5 times in each of the warp direction and the weft direction. The number of times the test piece was cut at a distance of 2.5 cm with a reciprocating friction of 125 times per minute was measured.

EXAMPLE 1 A scoured and bleached silk fluff with 14 momme (hereinafter abbreviated as silk fluff) was placed in a 200 cc eggplant-shaped flask, and 8 g of stearoyl chloride, 200 ml of N, N-dimethylformamide were added.
After addition of 2.1 g of pyridine, the mixture was treated at 50 ° C. for 1 hour with a back-flow condenser. After the reaction treatment, the treated fabric was drained, washed with N, N-dimethylformamide, ethanol and water in this order, further washed with 50 ° C warm water, and air-dried.
Thus, silk feathers chemically modified with stearoyl groups were obtained.

Comparative Example 1 Modification of silk feathers was performed under the same conditions as in Example 1 except that pyridine was not used.

Example 2 A silk feather with 14 momes was modified in the same manner as in Example 1, that is, in a processing solution consisting of 8 g of palmitoyl chloride, 200 cc of N, N-dimethylformamide and 2.4 g of pyridine. The sample was immersed in the sample and treated at 50 ° C. for 1 hour. After completion of the reaction, the reaction solution is drained, washed with N, N-dimethylformamide, benzene, ethanol, and water in this order, and washed with water.
It was washed with warm water of 0 ° C. and air-dried. As a result, silk feathers chemically modified with palmitoyl groups were obtained.

COMPARATIVE EXAMPLE 2 Modification of silk feathers was performed under the same conditions as in Example 2 except that pyridine was not used.

Example 3 A silkworm double with 14 momes was modified using myristoyl chloride. Myristoyl chloride 8 as in Example 1
g, 200 cc of N, N-dimethylformamide and 3.7 g of pyridine at a temperature of 50 ° C. for 1 hour. After completion of the reaction, the mixture was drained, and then N, N-
It was washed in the order of dimethylformamide, benzene, ethanol and water, washed with warm water at 50 ° C., and air-dried. As a result, silk feathers chemically modified with myristoyl groups were obtained.

Comparative Example 3 A silk feather was modified under the same conditions as in Example 3 except that pyridine was not used.

Example 4 A graft polymerization process was performed on silk feathers using methyl methacrylate (MMA). That is, in a sulfuric acid acidic solution having a pH of 2.8, 1.8% by weight of potassium persulfate of a sample weight is added as a polymerization initiator, and 1 g / L of a nonionic surfactant Neugen HC (Daiichi Kogyo Seiyaku Co., Ltd. 3) of the sample weight was added to the graft polymerization processing solution to which
The graft polymerization reaction was advanced in a graft system to which MMA was added so as to be 0%. The bath ratio was 1:15. The temperature of the grafting solution was raised from room temperature to 80 ° C. over 45 minutes, and heat treatment was performed at a constant temperature of 80 ° C. for 60 minutes to advance the graft polymerization reaction. After the completion of the graft polymerization reaction, the sample was treated with a 1 g / L aqueous solution of Neugen HC at 80 ° C. for 30 minutes to remove unreacted chemicals attached to the sample surface. Run the sample thoroughly washed with running water under standard conditions (20 ° C, 65% R
H), left for 1 hour, lightly dried, and dried in a thermostat at 105 ° C for 2 hours to prepare a grafted silk feather double with a graft ratio of 27%. Further, this sample was prepared in Example 1.
In the same manner as described above, a modified silk feather was prepared by treating with stearoyl chloride.

Example 5 A graft polymerization was carried out using 2-hydroxyethyl methacrylate. That is, in the same manner as in Example 4, p
In a sulfuric acid solution adjusted to H3.8, ammonium persulfate was used as a polymerization initiator at a reaction temperature of 80 ° C. to prepare methacrylic acid 2
A graft polymerization reaction with -hydroxyethyl was performed.
Next, the thus-prepared processed silk feathers having a graft ratio of 24% were modified using stearoyl chloride in the same manner as in Example 1.

The functional characteristics of the products obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated. Table 1 shows the results.

[0027]

[Table 1]

As can be seen from Table 1, the modification treatment according to the present invention can impart water repellency and resistance to bending wear to protein fibers and protein fiber products, and affect the feel of the protein fiber products such as the softness. The properties to be performed are not bad. It was also found that the addition of a base acting as a catalyst to the acylation reaction increased the reactivity of the long-chain carboxylic acid chloride with protein fibers.

Example 6 The pigments and fats contained in Merino wool (64'S) were removed by treating with a mixture of benzene-ethanol 50/50 / vol% with a Soxhlet extractor for 2.5 hours. did. The sample was washed with running water for 30 minutes to remove reagents and the like contained on the sample surface, and dried at 105 ° C. for 2 hours to obtain defatted wool fibers. Using this wool fiber, a modification treatment with stearoyl chloride was performed in the same manner as in Example 1,
A wool fiber having excellent water repellency was prepared.

Example 7 Tussah silk thread which had been scoured by immersing a tussah cocoon thread in a 0.1% aqueous sodium peroxide solution 50 times the weight of the cocoon thread and treating it at 98 ° C. for 1 hour to remove sericin Hereinafter, abbreviated as tussah silk thread) was prepared. Using this tussah silk in place of the silk feather in Example 1, modification processing was carried out with stearoyl chloride in the same manner as in Example 1 to prepare a tussah silk having excellent water repellency.

[0031]

According to the method of the present invention, a long-chain aliphatic carboxylic acid chloride used as an acylating agent is reacted with a fiber at a low temperature of 60 ° C. or less and in a relatively short time. Without adversely affecting the microstructure of
Excellent water repellency and abrasion resistance can be imparted to the fiber. Moreover, the long-chain acyl group introduced into the fiber according to the present invention is not easily removed because it is chemically bonded to an amino group or a hydroxyl group in the fiber, and is imparted by introducing the long-chain acyl group. The obtained water repellency and abrasion resistance are excellent in durability.

Claims (5)

(57) [Claims] 1. A protein represented by the following general formula (1): CH ₃ (CH ₂ ) nCOCl (1) (where n is an even number from 10 to 16), for a protein fiber or a protein fiber product. A method for producing a modified protein fiber and a modified protein fiber product having water repellency and abrasion resistance, comprising reacting a chain acylating agent in the presence of a base at a temperature of 60 ° C. or lower. 2. The method according to claim 1, wherein the reaction is carried out in a polar organic solvent that swells the protein fibers. 3. The method according to claim 1, wherein said base is pyridine.
the method of. 4. With respect to a protein fiber, a compound represented by the following general formula (2) CH ₃ (CH ₂ ) nCO- (2) (where n is a number) through a free amino group and / or a hydroxyl group contained in the fiber. A modified protein fiber and a modified protein fiber product having a water-repellent and abrasion-resistant property obtained by introducing a long-chain acyl group represented by the following formula: 5. The modified protein fiber and modified protein fiber product according to claim 4, wherein the introduction ratio of the long-chain acyl group is at least 1% by weight based on the protein fiber.