JPS64506B2 - - Google Patents

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides raw silk to which sericin is attached,
This invention relates to a method for producing shape memory raw silk that has a built-in crimp shape memory obtained through unique processing.

[Prior Art] It is well known that silk, unlike synthetic fibers, cannot be permanently crimped simply by twisting and heat treating it. Silk is treated with a hydrophobic resin to give it crimpability, and its twisted state is fixed against heat.
Although this method is already known (Japanese Patent Publication No. 37-16853), since the surface of the silk is coated with resin, it is not possible to fully utilize the original quality of the silk, and it also requires larger equipment and a more complicated manufacturing process. There are some drawbacks.

Next, at the stage of scouring raw silk, there is a method for producing crimped silk thread by a scouring method using Glauber's salt (Na ₂ SO ₄ 10H ₂ O) as a base (Japanese Patent Publication No. 47-14043); The raw silk is refined using soap and mirabilite, and 10% of the sericin that coats the raw silk is removed.
The effect of the residual sericin imparts crimp properties; however, since glauber's salt has the effect of inhibiting scouring, scouring spots are likely to occur. , autumn silkworm,
Alkali (soap,
Because the solubility of sericin (soda, etc.) and scouring chemicals differs, scouring that leaves a certain amount of sericin is difficult for one type of sericin, as there are many variations in crimpability in reality, making it difficult to produce a uniform product. be.

In addition, because a certain amount of sericin remains in the raw silk, the raw silk cannot fully exhibit the luster, texture, and feel of kneaded silk, and the residual sericin is unevenly deposited, which inevitably causes variations in crimpability. Furthermore, since animal fibers are sensitive to high temperatures and high pressures, the temperature is 148 to 153℃ and the pressure is 3.9℃, as in the above-mentioned Japanese Patent Publication No. 47-14043.
Under processing conditions of ~4.5 Kg/cm ² , silk has many drawbacks such as considerable loss of strength and durability.

By the way, raw silk is made from hibroin and sericin. This hybroin is composed of more than 16 types of amino acids, of which the two main amino acids are hydrophobic glycine and alanine.
Glycine accounts for over 40% and alanine accounts for over 30%, and both account for over three-quarters of the total. These many types of amino acids are long connected by peptide bonds and form a chain, but while glycine and alanine are arranged in an orderly alternating manner in some parts, glycine and alanine are also arranged in other parts. All types of amino acids are arranged irregularly in no particular order. The arrangement of glycine and alanine, which makes up three-quarters of the total, is arranged in an orderly manner, so
This is called the crystalline part, and the remaining one-fourth is a part in which many kinds of amino acids are connected in an irregular and complex manner, and the molecules are arranged in disorder, and is called the amorphous part. and collagen protein derivative {molecular structure RCONH
(R″CHCONHCHR″)nCOOX X=Sodium,
Potassium, ammonium and other organic amines,
By treating the raw silk with a solution of alcohol (R= _C12 - _C18 saturated or unsaturated fatty acids), this is absorbed into the hybroin in the amorphous portion, and the result is a twisting,
It was found that the amorphous portion was stabilized by applying pressure and heat, and permanent crimpability was imparted by utilizing the stress of twisting.

Patent No. 1218009 (Japanese Patent Publication No. 58-39934), filed by the same inventor as the present inventor and the patent applicant, was invented from this perspective. The invention involves scouring raw silk to completely remove sericin, adsorbing collagen protein derivatives to it, and polishing it in the S or Z direction by 2000 ~
Twisted at 2800T/M to absorb moisture until saturated,
10 under the conditions of temperature 130-140℃ and pressure 3-3.5 atm.
It is characterized in that it is set for ~20 minutes, and then untwisted in the direction opposite to the previous twisting direction (Z or S direction) to form combs and impart crimpability with saturated steam. (See Figure 3) According to this method, it is possible to impart fixed form and stretchability to silk without impairing its quality, luster, and texture.

However, if it is possible to crimp the highly durable raw silk that has sericin attached to it, it would be very difficult to weave and knit without damaging the hibroin because this elastic raw silk is covered with sericin. To obtain suitable fabrics and knitted fabrics which have good elasticity, and which have excellent elasticity by scouring after weaving and knitting, and which do not change in any way even after washing and dyeing. However, the problem of how to absorb collagen protein derivatives or collagen protein derivatives into which a hebroin protein derivative has been introduced into hisbroin through a sericin membrane is a problem that has been awaited for resolution. If it were possible to crimp raw silk with sericin attached,
As mentioned above, it is possible to obtain raw silk with excellent properties, but it is also possible to obtain a crimp-like (wavy) silk that has excellent elasticity, texture, and gloss. If it could be obtained, it would be possible to provide raw silk of even better quality, and it would also expand the range of uses, and a solution to the above-mentioned problems was awaited.

There is already a method of producing crimped raw silk by processing unscoured raw silk with resin, but this method is difficult because the synthetic resin remains in the molecules even after scouring.
It has the fatal disadvantage of destroying silk's original texture and being prone to uneven dyeing, and the equipment required to do so must be complicated and large-scale.Also, water-twisted yarn (Haccho-twisted yarn) is required for strong twisting. ), which had many problems such as the extremely high cost.

[Problems to be Solved by the Invention] The present invention provides collagen protein derivatives, or collagen protein derivatives mixed with silk hebroin, through a sericin membrane, by applying a unique process to raw silk to which sericin is attached. By absorbing derivatives, it is possible to produce shape-memory raw silk that has excellent properties of built-in elasticity, and even further, it has the same elasticity but is rich in elasticity, has strong elasticity, and has a stable shape. It is an object of the present invention to provide a manufacturing method that can obtain crimp-like shape memory raw silk with even better properties, texture, and gloss by a rational means.

[Means for solving the problem] The above-mentioned problem can be solved by knitting (tube knitting) after adsorbing collagen protein derivatives or collagen protein derivatives including hybroin protein derivatives to raw silk to which sericin is attached. A collagen protein derivative or a collagen protein derivative including a hebroin protein derivative is adsorbed onto raw silk that has been knitted in advance and has sericin attached to it, and then heated in boiling water (95 to 100℃) for 15 to 30 minutes. Boil for a minute, quickly cool down, then reduce the pressure to 3 to 3.5 atm.
The material is steam-set for 10 to 15 minutes under conditions of 130 to 140°C, and then denited and rolled into a skein or cone shape and dried to obtain a shape memory raw silk that remembers the crimp shape. This is achieved by a method for producing shape memory raw silk.

[Example] Next, one embodiment of the present invention will be described.

First, a collagen protein derivative or a mixture of a collagen protein derivative and a hybroin protein derivative in any proportion may be dissolved in water in an amount 5 to 10 times the weight of raw silk, and a mixture of 3 to 8
Make a solution with a weight concentration of %. The concentration of the solution is appropriately selected depending on the degree of crimp, the type of silkworm, and the breeding period.

The molecular structural formula of the hybroin protein derivative is as follows.

X = Na, H Y = 1/2 (SO ₄ ) R'', R = C ₁ to _{C 10} unsaturated and saturated hydrocarbons Next, two of the 21 raw silks are combined and 100%
The yarn is twisted once per m, then skeined and placed in a solution of the collagen protein derivative etc. at 20~30°C for 20~30°C.
The raw silk is soaked for 30 minutes to impregnate the raw silk with a solution of 30% of the weight of the raw silk, then dehydrated and dried at below 60°C until the moisture content is approximately 11%.

This dried raw silk is knitted with inch 40 gauge, wrapped in cloth and boiled at 95-100℃ for 15 minutes.
Steam set at 3 atm and 130°C for 10 minutes, soaked in water, denited, shaped into strands and dried.
As shown in the figure, raw silk with built-in crimps is obtained.

When this is refined and sericin is removed, crimp-shaped raw silk is obtained which is rich in elasticity and has even better texture and gloss as shown in FIG.

Next, other embodiments will be described.

Two out of 21 raw silks are combined and knitted into a knitted fabric using a 40-inch circular knitting machine, and a collagen protein derivative solution or a hisbroin protein derivative solution with a concentration of 3 to 8% or any mixture of a collagen protein derivative and a hisbroin protein derivative is added. A solution prepared at a certain ratio may be used, but this solution should be heated to 20 to 30°C, the knitted fabric should be immersed in it for 20 to 30 minutes, and the raw silk should be impregnated with a solution of 30% of the weight of the raw silk. After that, dehydrate and dry at 60℃ or less until the moisture content is about 11%, then wrap it in cloth and boil it at 95-100℃ for 15 minutes, and set it in 3 atmospheres of steam at 130℃ for 10 minutes. and
When it was then refined and sewn (if washed without this process, knitted fabrics usually stretch and have no resilience), the resilience was close to 100%, and it was extremely stretchy and knitted. A stable fabric was obtained that had elasticity in the warp and weft directions (normal knit fabrics have elasticity only in the weft direction and no elasticity in the warp direction).

That is, according to the present invention, focusing on the fact that sericin is a water-soluble protein, a sudden change in temperature causes cracks on the surface of the sericin protein, and collagen protein derivatives and hisbroin protein derivatives are transferred through the cracks to silk hebroin. As a result, the arrangement of the hybroin protein in silk becomes ``dense'' like that of synthetic fibers, giving it thermoplasticity.

Since the thermoplasticity of the hybroin is built into the sericin membrane, it is possible to obtain stretchable threads that appear on the surface to be almost the same as raw silk.

However, if this thread is soaked in hot water or an alkaline solution to remove the sericin, the built-in elasticity will immediately appear, and in other words, shape-memory raw silk will be obtained.

Furthermore, the present invention goes one step further by incorporating a unique process in which the solution of the collagen protein derivative described above is absorbed into raw silk and then knitted. A yarn with even better gloss and memorized crimp shape can be obtained. Further, by scouring this, it is possible to easily obtain shape-memory raw silk that immediately exhibits a crimp shape with excellent properties.

[Effect] According to the present invention, the elastic raw silk is covered with sericin, so it does not damage the hibroin, and is very suitable for weaving and knitting. This results in fabrics and knitted fabrics with extremely high elasticity, which can be easily used in crepe manufacturing, etc., and stable fabrics and knitted fabrics that do not change in any way even when washed or dyed. It is something that can be done. Furthermore, it is almost resistant to wrinkles, and the degree of stretch of the raw silk with built-in stretch can be freely adjusted from 10 to 40% depending on the number of gauges to be knitted, and many other useful effects can be exhibited. In addition to the above-mentioned properties, it is possible to efficiently obtain crimp-shaped shape memory raw silk, which has high elasticity and strong stretching force, and therefore can stabilize the shape and has a good texture. It is possible to provide raw silk with even better quality in terms of both gloss and gloss, and which can be used for a further wide range of purposes.

[Brief explanation of drawings]

Figure 1 is a photographic image of the shape-memory raw silk of the present invention, which has a built-in crimp whose surface is covered with sericin, taken under a microscope (13x magnification), and Figure 2 is the crimped shape-memory raw silk shown in Figure 1. Photographic image of the refined state taken under a microscope (13x magnification), 3rd
The figure is a photographic image showing silk thread with a collagen protein derivative adsorbed on it, compared with the conventional method where raw silk is refined to completely remove sericin, and is magnified with an electron microscope at 12,500 times.

Claims (1)

[Claims] 1. Raw silk to which sericin is attached, adsorbed with collagen protein derivatives or collagen protein derivatives including hybroin protein derivatives and then knitted (tubular knitting), or raw silk that has been knitted in advance and has sericin attached to it. to which collagen protein derivatives including collagen protein derivatives or hybroin protein derivatives have been adsorbed, are added to boiling water (95%
Boil for 15 to 30 minutes at a temperature of ~100°C), immediately rapidly cool, then steam set for 10 to 15 minutes at a pressure of 3 to 3.5 atm and a temperature of 130 to 140°C, and then denit to form a skein. Or, a method for producing shape memory raw silk, which is characterized by obtaining shape memory raw silk having a memorized crimp shape by winding it into a cone shape and drying it.