JPH04100976A - Fibrous structure modified with modified silk fibroin and its production - Google Patents

Abstract

PURPOSE:To obtain the title fibrous structure resistant to washing, having silk touch and gloss by imparting a fibrous structure with a specific quaternary trimethylammonium-modified silk fibroin. CONSTITUTION:The objective fibrous structure can be obtained by imparting (A) a fibrous structure consisting of natural or synthetic fiber with (B) a quaternary trimethylammonium-modified silk fibroin of the formula (R is side chain of the amino acids constituting silk fibroin; (n) is average number of monomer units: 100-1000) prepared by reaction in an alkaline state of (1) 3-chloro-2- hydroxypropyl trimethylammonium chloride with (2) a solution prepared by dissolving spun silk waste as raw material in e.g. calcium chloride. Specifically, said modified silk fibroin solution, i.e., the treating agent, can be prepared through the following process: a 3-20% silk fibroin solution is hydrolyzed, with an acid, alkali or protease into 100-1000 in the mean number of monomer units followed by making the system alkaline and then dripping 3-chloro-2- hydroxypropyl trimethylammonium chloride thereto.

Description

[Detailed description of the invention] (Industrial application) This book is about improving the texture of cod fiber structure. Fiber! #Structures and their li&l
Regarding the manufacturing method.

(Conventional technology) Silk has a quiet and deep luster, an ever-changing waist, soft texture, and graceful drape, which are the goals of other fibers. She is known as a female worker.

Therefore, many spinning and processing methods have been proposed to impart silk properties to fibers other than silk, and some of them have been put into practical use. Processing methods include, for example, alkali treatment of polyester A fibers, enzyme treatment of cellulose 'A' pongee to reduce and soften it, and general-purpose cauterization methods such as urethane, silicone resin, or amino acid resin. While a method of imparting softness and drapability with a single resin treatment has been proposed, for example, Japanese Patent Publication No. 13670/1987 describes a method of modifying fibers with a non-solution of fibcoin.
The disadvantage of silk spun weft is that the so-called stiffness of the yarn is smaller than that of raw silk; in order to improve the inferior drapability and texture, straw consisting of silk fibroin is essentially formed on the surface of the a-fibers. In addition, in Japanese Patent Publication No. 63-8237, at least a portion of the m-vertebral spaces of an acrylic spun yarn (filled with silk fibroin A manufacturing method for silk fibroin-processed acrylic spun yarn has been proposed.3 (Problems to be solved by the invention) However, when looking at these methods, first of all, it is difficult to perform weight loss flexibility processing or surface processing with synthetic resin. , the page change to silk-like am is essentially a process using foreign matter (
This is impossible and is unsatisfactory in terms of effectiveness and durability.

Also, the aforementioned Japanese Patent Publication No. 57-13670 and equity:! B
6! This is the modification process using silk fibroin aqueous solution proposed in Publication No. 8237 (hereinafter referred to as 2nd permit).
What all of these have in common is that the processing target is l
In the case of spun yarn, which has a large amount of stable fibers and voids, a large amount of processing liquid is sucked into the voids by capillary action and is stably retained. On the other hand, in the case of filament yarn, the structure is simple, there are only a few voids, and it is easily deformed, so the amount of machining liquid sucked in is small and it easily falls off due to capillary action, making it impractical. Since the silk fibroin aqueous solution is taken into the inter-row spaces, it is limited to yarn processing. That is, when a fabric is subjected to a fibroin treatment similar to the above-mentioned patent 2 patent 1, the fabric becomes coarse and hard due to the wear between the threads. The above fact is due to strict quality standards and low yarn prices.
In the case of m-tight polyester or nylon, filament,
This means that simple silk fibroin processing is inappropriate for any fabric.

Furthermore, even if it is limited to yarn processing of spun yarn, in the case of the methods of the two patents mentioned above, there is a problem that the degree of processing fluctuates depending on the pick-up amount of the silk fibroin aqueous solution and uneven squeezing, resulting in uneven dyeing. In addition, it is necessary to further improve durability in terms of moisture absorption and other properties.

The purpose of the present invention is to uniformly impart the properties of silk, such as gloss, texture, moisture absorption, etc., to fiber structures such as silk, cotton, wool, polyester, nylon, and acrylic, especially to fabrics made of long fibers. In particular, it is an object of the present invention to provide a fabric having excellent durability with these properties. Another object is to provide a method for manufacturing such fiber structures, especially fabrics, industrially easily and inexpensively.

(Means for Solving the Problems) In view of the problems of the prior art described in the previous section, the present inventors have conducted extensive research into the physical properties of silk fibroin and its conductors, and their practicality mainly in the modification of long-fiber fabrics. It is a completed invention. That is, the present invention is modified with quaternary trimethylammonium-modified silk fibroin consisting of the general formula % (wherein R is the side chain of an amino acid constituting silk fibroin, and n is the average number of molecules of 100 to 1000). The method of the present invention relates to processed fibers, and the method of the present invention has a concentration of 5 to 2.
0% (by weight) silk fibroin aqueous solution was hydrolyzed with acid, alkali, and protease to an average molecular weight of 100 to 1000 (average molecular weight 56 aa to 86,000), and while keeping the reaction system on the alkaline side, 5% -chloro-2=hydroxybrobyltrimethylammonium chloride (hereinafter referred to as CTA
The fibers are immersed in an aqueous solution of quaternary trimethylammonium-modified silk fibroin prepared by dropping a solution of silk fibroin, dehydrated to a predetermined pick-up amount, and subjected to moist heat treatment if necessary.

The problem in processing fiber structures using an aqueous silk fibroin solution is that there is no strong adsorption force between the attached silk fibroin and the target fiber, not only chemically but also statically and atmospherically. Therefore, when processing nylon or polyester threads, the amount of adhesion is small, and if friction or other force is applied to the adhesion, the film-like fibroin can be easily peeled off. In addition, in the case of fabrics, if the drawing is weak, the texture will become rough and hard due to sticking between the threads. It is necessary to remove liquid strongly to prevent sticking between the threads, but in this case, there is no selective adsorption between the silk fibroin and the target fibers, so the silk fibroin aqueous solution in the interfiber spaces is also removed, leaving the silk fibroin virtually unprocessed. It returns to the state of Even in the case of spun yarns such as silk yarns and acrylic yarns, if they have selective adsorption power, they can be strongly removed to prevent uneven processing.

By the way, in general, this fiber has a negative zeta potential in the processing solution. Therefore, if we want to adsorb silk fibroin onto fibers with good durability, it is presumed that this will be possible by modifying silk fibroin and giving it a positive iζ charge (Reference: Chemistry Handbook, Applied Chemical Copper,
P1209. Numata 1961 edition, Maruzen). However, although there are examples of silk peptides, conventional acids and alkalis 1
No method has been found to efficiently cationize unstable silk fibroin in an aqueous solution.

The present inventors prepared an aqueous solution of silk fibroin with a concentration of 3 to 20% (M amount) using acid, alkali, and proteolytic enzyme, with an average number of molecules of 1.
00 to 1000 (average molecular weight 8500 to +15 (to(
When 1) is hydrolyzed and CTA is added dropwise to this while keeping the reaction system alkaline, surprisingly, quaternary trimethylammonium-modified silk fibroin is produced easily and in good yield. Silk fibroin is cationized, and the fibers are immersed in this processing liquid.
When deliquified to a predetermined pick-up amount, subjected to moist heat treatment if necessary, and dried, silk fibroin is efficiently adsorbed to m's and the treated fibers become noticeably silk-like in terms of gloss, texture, bedding S properties, etc. The page has been changed to , and those sexes are also washed? It was found that the durability was significantly lower than that of JJI.

The silk fibroin Kyoto material used in the present invention includes cocoon, raw silk,
Cocoon scraps, raw silk scraps, screws, fried cotton, silk cloth scraps, boulet, etc. are dried in hot water to remove sericin in the presence of a single-tongue agent or in the presence of an enzyme according to a conventional method. Use the one you made.

The solvent for silk buproin used in the present invention is a copper-ethylenediamine aqueous solution, a copper hydroxide-ammonia aqueous solution (Schweisser's reagent), a copper hydroxide-alkali-glycerin aqueous solution (Rohe's reagent), a lithium bromide aqueous solution, calcium, magnesium, or zinc. Examples include aqueous solutions of hydrochloride or nitrate or thiocyanate, and aqueous sodium thiocyanide solution, but calcium or magnesium hydrochloride or nitrate is preferred from the viewpoint of cost and use.

In addition, the concentration of these water g solutions varies depending on the solvent used, temperature, etc., but the concentration of metal salts etc. is generally 10 to 80%.
(by weight), preferably 20 to 40% (by weight). 8
Even if it is 0% (weight) or more, it will dissolve, but there is no substantial difference in the silk fibroin aqueous solution produced, which is a problem from an economic point of view.

The silk raw material after scouring is added to the solvent consisting of the aqueous solution and uniformly dissolved in a device such as a kneader at a temperature of 60 to 95"C, preferably 70 to 85"C, and the liquid ratio is usually 2 to 60"C.
, preferably 3-50.

In order to obtain a highly pure silk fibroin aqueous solution from the obtained silk fibroin solution, dialysis is subsequently performed. Dialysis uses a dialyzer typified by a cellophane membrane or a dialyzer using a hollow i1m to almost completely remove the salts and the like.

In this case, in order to narrow the molecular weight distribution of the target silk fibroin as much as possible, the proportion of α-structure silk fibroin was set at 50%.
In order to make adjustments beyond g measurement, it is necessary to specify the dialysis amount and dialysis membrane area. That is, desalination is performed using a multilayer membrane structure or a hollow fiber structure that satisfies the following formula.

(Here, priming capacity refers to dialysis tube or
(indicates the internal volume of the lock) If the above value is less than 10m, the threshold will be longer during retention in the transparent Fr container because the filtration process will not be carried out quickly, and the obtained fibroin aqueous solution will have already been putrefied. There are many things that happen. In this case, the fibroin protein becomes waterless (β structure) due to denaturation due to putrefaction, and it is difficult to make it easily soluble in cold water again.

In particular, in order to carry out the present invention smoothly and economically, the above numerical value is preferably 30 or more, particularly preferably 50 or more. In order to satisfy this condition, for example, in the case of a hollow fiber convergence structure, the diameter of the hollow fibers must be 4 mm or less.The dialysate obtained by the method of the present invention has a residual salt concentration of 0.
The membrane surface area (cm
, :! This can be achieved with a priming capacity of 200 and a residence time of 10 minutes in the dialyzer.
From this, an extremely high quality silk fibroin aqueous solution can be obtained.

Although the concentration of silk fibroin in the present invention is not critical, it is preferably 3 to 20% (by weight), and concentrated if necessary. If it is less than 3% (weight), it is uneconomical in terms of work efficiency as it requires concentration before the reaction with the cationizing agent, and if it is more than 20% (N amount), the viscosity becomes high and it is difficult to react or operate. There is.

In the present invention, silk fibroin has a natural molecular weight of 30 to increase the number of reactive groups (terminal amino groups) with the cationizing agent.
~400,000 (reference, structure of continuous silk thread P121, 1980 edition, published by the Faculty of Textile Science, Shinshu University) is preferably hydrolyzed to a molecular weight of 100 to 1000 (molecular weight 8500 to asooo). When the molecular number is less than 100, the reactivity with CTA is good, but the strength of the film of silk fibroin adsorbed on the fibers is poor and lacks luster. If it exceeds 1000, the number of terminal amino groups is insufficient and the film tends to come off when washed.

Examples of the acid used for hydrolysis include inorganic acids such as hydrochloric acid and sulfuric acid, but these are not essential. As the alkali, inorganic alkalis such as sodium hydroxide, potassium hydroxide, lithium hydroxide, aqueous ammonia and the like can be used, but sodium hydroxide and potassium hydroxide are preferred from the viewpoints of reactivity, economy and stability.

The conditions for hydrolysis with acid or alkali vary depending on the type of acid or alkali used, the average degree of polymerization and distribution of the degree of polymerization of the target silk fibroin, but are usually 1001 to 0.
．． IN, preferably at a concentration below 0.05N and at a temperature of 2
0 to 110°C, preferably 30 to 100°C, 0.
The reaction is carried out for 5 to 41 hours, preferably 1 to 24 hours, and then neutralized by adding an alkali or acid.

Hydrolytic enzymes applicable to the present invention include ordinary proteases, such as pronase obtained from actinomycetes, prolase obtained from Hapaia, an enzyme group considered to be a mixture of several proteases, bromelin, etc. They can be used alone or in combination of two or more. The amount of enzyme used depends on the type of enzyme, purity 1 reaction conditions,
Or, although it varies depending on the average degree of polymerization of the target silk fibroin, etc., it is usually 001 to 1.0 for silk fibroin.
% (weight), preferably 102 to 0.5% (N amount). In this case, the conditions for hydrolysis include the type of enzyme used,
Although it varies depending on the concentration etc., the normal pH is 5 to 9, preferably 6 to 8.5, and the greenhouse temperature is 20 to 70'C, preferably! O~
0.1-72 hours at 45"C, preferably 0.6-12 hours
Do time.

In the present invention, silk fibroin prepared to have an average molecular number of 100 to 1000 is reacted with CTA to be induced into quaternary trimethylammonium-modified silk fibroin. C
TA is commercially available at a concentration of about 60% by weight and can be obtained at low cost, but by dropping it into an aqueous silk fibroin solution prepared in logarithm, the cationic modification of the fibroin can be easily carried out in an aqueous solution with a high yield. Well done.

At that time, the reaction system is PHII to 12, preferably 9 to 11.
Therefore, during the reaction, an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide is added dropwise.
This is because the reaction does not proceed selectively under acidic conditions that require neutralization of hydrochloric acid generated during cationic modification of silk fibroin. Also, if PEI exceeds 12, CT
Hydrolysis of A and silk fibroin occurs.

The reaction temperature is room temperature to 80°C, preferably 40 to 60°C.
It is. The higher the temperature, the faster the reaction, but because of the reaction on the alkaline side, the temperature at which 80'Cr melts is undesirable because hydrolysis of CTA and silk fibroin progresses.

The reaction time was 30 minutes to 1 hour for the dropwise addition of CTA, then continued stirring for an additional 3 to 4 hours, and finally stirring at 80°C for 30 minutes to complete the reaction. After the reaction is completed, the reaction solution is neutralized with an acid, and alkali ions are removed using a weakly acidic ion exchange resin to obtain a fiber processing solution.

In the present invention, although it varies depending on the target fiber, approximately 50
Since the appropriate pick-up amount is ~200% (1/2 to 2 times the weight of the untreated a-fiber structure), the concentration of cation-modified silk fibroin in the processing solution is usually 0.5 to 20%, especially 1.0 to 200%. A preferable amount is 10.0%, which controls the amount of adsorption onto the fiber structure between 0.5 and 20%.

If it is less than 0.05%, the modification to silk touch will be insufficient, and if it exceeds 20%, the fiber will become coarse and hard.

In the method of the present invention, the liA of modified silk fibroin aqueous solution
The method of applying it to the fiber structure is not particularly limited, but a dipping method, a spray method, a roller method, etc. can be applied.

In addition, in order to develop good adhesion and uniform film-forming properties of modified silk fibroin to fiber structures, the fiber structures may be subjected to pretreatment, such as alkali treatment for polyester fibers, acid treatment for nylon fibers, or oxygen, nitrogen, or air treatment. , low-temperature plasma treatment may be performed in a system such as argon.

The fibers provided with modified silk fibroin are dried.

A strong film can be formed by further performing a moist heat treatment. The moist heat treatment is carried out at a temperature of 90°C or higher, preferably 110''C or higher.

The modified silk fibroin processed fiber structure of the present invention has a uniform thin film surrounding the fibers, and this modified silk fibroin film is no longer soluble in water and has washing resistance.

The modified silk fibroin aqueous solution applied to the present invention contains foreign volatile proteins such as atelocollagen, hydrolyzed collagen, gelatin, casein, etc. before or after the reaction with CTA to stabilize the silk fibroin solution, that is, to prevent gum-up. It may be included. The amount of Iran protein used is at most 30% of that of silk fibroin. If it exceeds 30%, film forming properties are poor and the texture becomes rough and hard.

Furthermore, the silk fibroin aqueous solution applied to the present invention may contain a softener, an antistatic agent, a preservative, a toning agent, a stabilizer, a reaction catalyst, etc. as necessary. The present invention will be specifically explained by way of examples.

In addition, in the examples, all parts indicate parts by weight.

In addition, the increase rate in the examples is It is.

Further, the molecular weight of silk fibroin was determined by high performance liquid chromatography (fiPLC) using a gel filter column. The HPLC conditions are described below.

Column: Asahipak G3-820 soluble JiIF
! i: 0.2M phosphorus warm buffer solution (pHr, o) Elution conditions Two flow rates t Oml/min.

As standard materials, Cytochromec, Ova
lbumin.

Transferrin was used.

Detection was performed by absorbance measurement at 280 nm.

Example 1 Using silk spinning waste as a raw material for fibroin, one of these
00 parts with a solution of 30 parts of Marcel soap and 3000 parts of water at 96-98°C for 5 hours. ! The mixture was stirred and refined to reduce the residual glue to 0.1 micron or less, washed with water, and dried with hot air at 80°C.

Calcium chloride (CaC1ff1・2H!O) 10
0 parts and 100 parts of water were mixed to prepare 200 parts of a 58% by weight calcium chloride aqueous solution and heated to 110"C. To this was added 4a parts of refined silk waste using a kneader while stirring for 5 minutes. After the addition, the mixture was further stirred for 30 minutes to ensure complete dissolution.

Next, 2,000 regenerated cellulose-based hollow fibers with an inner diameter of 200μ, a membrane thickness of 20μ, and a length of 500mm were bundled together, and a hollow fiber type dialysis device was used in which both ends of the fibers were bundled and fixed (sealed) without blocking the hollow holes. , the solution was added to 0.
The mixture was flowed in at a rate of 21 parts per hour and dialyzed against deionized water to obtain an aqueous fibroin solution. The fibroin concentration of the aqueous fibroin solution was 12% by weight, and the residual calcium chloride was a, acx% by weight.

The molecular weight of the obtained silk fibroin was approximately 150,000 as determined by HPLC. Mix 10 parts of an aqueous solution of 0.5 parts of sodium hydroxide with 1000 parts of this, and heat to 85°C.
Silk fibroin was hydrolyzed by heating and stirring for 5 hours.

The molecular weight of silk fibroin after hydrolysis was approximately 18,000. While stirring, 25 g of a 5% CTA aqueous solution was added dropwise at room temperature over 30 minutes. During this time, 001N sodium hydroxide was added dropwise to maintain the pH of the reaction system at 10.

After the dropwise addition of CTA was completed, stirring was continued for another 2 hours while maintaining the pH at 10, and the mixture was left as it was overnight.

Furthermore, this is mixed with a weakly acidic ion exchange resin (Amberlite I).
RC-50 (trade name) was added to neutralize the mixture to pH 6.8 and remove sodium ions and trace amounts of unreacted CTA from the reaction system. The ion exchange resin was filtered out to obtain a fiber treatment solution 1 of cation-modified silk fibroin with a purity concentration of 11.5%.
050 copies were obtained. Measurement of amino nitrogen before and after the reaction with CTA revealed that more than 90% of the amino nitrogen had reacted.

Nylon multifilament γ0d15 as target delicate
4f, warp 106/1nch, weft 84/1n
After scouring, bleaching, and heat-setting the nylon taffeta fabric using a commonly known method, it was immersed in a 5-weight aqueous solution of the cationically modified silk fibroin prepared previously, and picked up with a mangle for 100 minutes. After dehydration to 1
Dry at 20°C for 5 minutes, followed by drying at 110°C for 20 minutes.
Wanseki moist heat treatment was performed.

The obtained nylon taffeta had a weight increase of 12.94%, and the slimy appearance peculiar to nylon disappeared, giving it a silky touch with a silky feel.Also, the metallic luster disappeared and a quiet, deep silk-like luster was exhibited. was modified to be silk-like.

Next, soak the modified nylon taffeta fabric in household detergent.
Washed 0 times. The weight increase rate after washing was 280 mm, and the retention rate of modified silk fibroin was 95 mm. Moreover, there was no change in texture or gloss.

Comparative Example 1 A nylon taffeta fabric was modified in the same manner as in Example 1, except that an aqueous silk solution having a molecular weight of 15,000, which was obtained by simply hydrolyzing silk fibroin without cationically modifying it, was used.

The weight increase rate after soaking, dehydration, drying, and moist heat treatment is over 2.90, and the sliminess peculiar to nylon disappears, giving it a silky touch with a silky feel.Also, the metallic luster disappears, giving it a quiet and deep silk-like feel. The nylon taffeta exhibited luster and was modified to be silk-like.

However, when the modified nylon taffeta fabric was washed 10 times with a household detergent, the weight increase rate was 8.30% and the retention rate was 10%. In addition, the fabric after washing had a slight amount of remaining silk fibroin attached to it in rows, lacked luster, and was of poor quality.

Example 2 Silk fibroin was hydrolyzed in the same manner as in Example 1, and CTA-modified silk fibroin aqueous solutions having the molecular weights shown in Table 1 were obtained by varying the time. In both cases, 90 of amino nitrogen
More than a whisper was responding.

This was diluted to a silk fibroin concentration of 3% by weight, and polyester multifilament 76d156f was used as the target fiber.
A polyester taffeta fabric with 106 warp threads/1 nch and 87 weft threads/1 nch was used and subjected to delicate treatment in accordance with Example 1. The results are shown in Table 1.

The quality of silk-like modification was evaluated by silk-like gloss and texture.

(Hereafter referred to as 1st white) As mentioned above, when the molecular weight of silk fibroin is less than 8,500 (the number of molecules is 100), the silk fibroin film becomes brittle and adheres to the fiber surface in powder form, which reduces the quality of silk-like modification. is inferior. Moreover, if it exceeds +50,000 (without hydrolysis), the number of adsorption points per molecular weight decreases, resulting in poor washing durability.

Example 3 According to Example 1, the concentration and pick-up amount of the treatment liquid were changed to determine the degree of processing, the quality of silk-like modification, and the above-mentioned sea urchin weight increase rate Q. Therefore, silk-like modification is insufficient. Also, if you use 20 whispers, the processed am will become hard and coarse.

Example 4 Target fiber: 60 count single yarn spun cotton, 90 warps/+
%-type 88 pieces/1nci] was used, and was subjected to hair burning, desizing, liquidation, dressing, silk processing,
Performed fix processing. Two sheets of this were prepared and modified with a 200% pick-up using a 3x aqueous solution of CT membrane modified xm fibroin with a molecular weight of 15,000 prepared according to Example 1, while (5) was treated with a 110%
"C" was subjected to 511I moist heat treatment for 20 minutes, and the other case (Tada) was not subjected to moist heat treatment. The results are shown in Table 3.

As described above, the washing resistance of adsorbed silk fibroin is slightly low when not subjected to moist heat treatment.

(Effects of the invention) Moreover, since it is not simply adhering but adsorbed by electrostatic force, it is possible to strongly deliquify treated fiber structures, especially fabrics. Processing is possible. Also, for the same reason, the washing resistance is remarkably good.

Applicant: Kanebo Co., Ltd. Company: Kanebo Silkyo Bijin Co., Ltd. Table 3

Claims (1)

[Claims] 1) General formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ A fiber structure modified with quaternary trimethylammonium-modified silk fibroin. 2) Silk fibroin aqueous solution with a concentration of 3 to 20% (weight) is digested with acid, alkali, and protease to an average number of molecules of 100 to 1.
000 (average molecular weight 8,500 to 85,000), and 3-chloro-2-hydroxypropyltrimethylammonium chloride was added dropwise to this while keeping the reaction system on the alkaline side. A method for producing a fibrous structure modified with quaternary trimethylammonium-modified silk fibroin, which comprises immersing the fibrous structure in an aqueous solution, deliquifying it to a predetermined pick-up amount, and subjecting it to moist heat treatment if necessary.