JP2700976B2 - Improved silk spinning raw material and method for scouring organic solvent such as silk spinning - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to scouring of silk spinning materials and silk spinning, and more particularly to scouring of organic solvents for removing residual organic solvent-soluble components.

[0002]

2. Description of the Related Art Silk is called a queen of fibers, and has a noble dignity, such as its elegant texture, luster, smooth drape, and vivid dyeability, which cannot be matched by other fibers. Silk fiber is naturally a cocoon thread and is the only long fiber of natural fiber. This is so-called raw silk, which is produced by unwinding and winding (filing) a cocoon from a cocoon swollen by simmering in warm water. The silkworm cocoon has a two-layer structure, with a fibroin layer, the main body of the cocoon, at the center, and a sericin layer covering the outside. Sericin belongs to the hard protein,
Generally, scouring is performed at the stage of yarn or woven or knitted fabric in order to reduce the luster of the silk yarn, the quality of the hand, and the dyeability, and is almost completely removed. About 75% of the silk fiber before scouring is a fibroin layer,
25% is the sericin layer.

[0003] On the other hand, cocoon thread is cut into short fibers and spun therefrom is a silk spun, which is generally made of waste (sub-silkworm) used in the production of raw silk, which is refined into cotton, After spinning, it is spun to a specified thickness and manufactured.

[0004] A feature of the silk spinning production process is that a scouring treatment for the purpose of removing sericin is required as a very important pre-process. In other words, if the sub-silk silk is left as sericin at the same ratio as the raw silk, the fiber is extremely coarse and hard, so that it is difficult to even produce cotton, and it is even more difficult to produce and spin. Therefore, in the production of silk spinning, it is necessary to first remove most of the sericin of the sub-silk as a raw material (the sericin content is 5% or less).

[0005] Refining methods of silk spinning materials are roughly classified into saponification refining and chemical refining (enzyme-containing refining). This internal scouring scouring is a function of bacteria in the nature to ferment and decompose sericin, oils and fats, and other constituents of the pupal body. 3)), there is a problem such as low productivity, and recently various studies have been mainly made on chemical scouring.

By the way, in the case of chemical scouring, unlike the saponification scouring, the oil, which is a constituent of the pupal body, and the waxes contained in the silk main body (generally referred to as pupal oil in the silk spinning industry) It is difficult to carry out the removal at the same time in a scouring step for removing sericin, and it is carried out in a separate step.

The refining of silk spinning and the like (including woven knitted fabrics) is performed in order to secure the yield and operability of the spinning process and the quality of the silk spinning. It is carried out for the purpose of removing activators and dirt in the production process.

As methods for removing pupal oil, 1) washing with a surfactant, 2) decomposing and removing with a lipolytic enzyme, and 3) extracting and removing with an organic solvent have been conventionally performed. 1), 2)
Method requires a long processing time (8 to 10 hours),
In addition, because of the large amount of enzymes and surfactants used, the cost of chemicals is high and the cost is low, so the extraction with an organic solvent in 3) is currently becoming the mainstream of pupa oil removal methods (reference) Material, JP-B-53-43211).

[0009] The organic solvent treatment of the silk spinning material is performed by immersing a dry cotton (purified cotton) having passed through a chemical scouring process for removing sericin or, in rare cases, a raw material before the scouring process in an organic solvent heated from room temperature to a heated temperature. After stirring for a few minutes to several tens of minutes, the liquid is drained and dried. With this simple treatment, the cotton pupa oil content is almost completely removed although it is related to the bath ratio, but it is very efficient Is a typical method.

[0010] Further, as a measure against the quality of the silk spinning raw material and the silk spinning made from the raw material, a step of removing contaminant polyolefin is employed as necessary. In general, solvent scouring is effective as this method. That is, the polyolefin mixed in the raw material and the polyolefin fiber in the silk spun generated by using the raw material as the raw material can be easily removed by the heated solvent scouring because the polyolefin is rapidly dissolved in the hot organic solvent.

In general, in the production of spun yarn, it is necessary to always add a surfactant for spinning (commonly referred to as an oil agent) to cotton from the viewpoints of operability and quality of the cotton production and spinning process and yield. Is done. Usually, an anionic surfactant or a nonionic surfactant is used as a spinning oil, but if this is not applied to cotton, the yield and quality of the cotton manufacturing / spinning process will be remarkable due to generation of static electricity and poor smoothness. And in extreme cases, may become inoperable.

[0012] In silk spinning, an appropriate amount of the above-mentioned pupal oil remaining as the spinning oil agent shows very favorable behavior as a result. In other words, when the residual pupa oil of the reclaimed cotton is completely removed, it is cotton production and spinning without the use of a spinning oil, and there is no doubt that the operation will become inoperable. Even if an ordinary spinning oil (mainly a surfactant) is applied in an appropriate amount as the amount of residual fats and oils by the immersion method, the operation can be performed, but the quality and yield of the produced cotton and spun yarn can be improved. Adjust the conditions for removing pupal oils and leave an appropriate amount,
This is significantly inferior to the case where a normal spinning oil is supplemented. To date, many researchers have tried various types of oils and methods of applying them, but have not yet obtained the same quality and yield as those obtained when an appropriate amount of pupal oil was left. . Also, regarding the produced silk spinning, it is an essential condition for the operation of the subsequent weaving and knitting process that an appropriate amount of pupal oil still remains. Even hoisting on a class may become impossible.

[0013] Solvent scouring now substantially and completely removes the pupal oil content of cotton and thread as described above. To be precise, if the bath ratio between cotton and thread and the solvent is 10, and the amount of solvent picked up by the cotton and thread after draining is 100%, the residual pupal oil content is 1/10. That is, in the case of the solvent scouring, unlike the surfactant scouring and the enzyme scouring, the pupal oil in the fiber is easily extracted up to the pupal oil content in the fiber, and the pupal oil in the fiber and the bath have the same concentration by the solvent treatment for several minutes to several tens of minutes. . Therefore, the pupa oil content of the silk fiber is diluted to the ratio of the bath ratio, and the pick-up amount when the solvent is suitably drained is approximately 100%. The amount of oil remaining at the ratio of the bath ratio remains in dried silk cotton or silk spun yarn. In this sense, it can be said that it is a scouring method in which the adjustment of residual fat is easy.

However, in general, the solvent ratio of the solvent treatment is generally about 20 to 30 due to the regulation of the liquid stirring. On the other hand, the so-called pupal oil content of the silk cotton before the treatment is large, about 5 to 6%, and small, about 1%. Therefore, the pupa oil content of the refined cotton after solvent treatment is at most 0.25 to 0.3%, and the low one is 0.03 to 0.0%.
5%. In the case of silk spinning, the appropriate amount of spun pupa oil is 1%
Since it is inside and outside, the solvent-treated cotton cannot be subjected to the cotton production and spinning processes as it is. In the case of refining using a surfactant or an enzyme, there is a problem that it takes a long time and the cost of chemicals is high.
Since it can be adjusted to 1.0%, if these are blended and a small amount of spinning oil is applied, a high quality spun yarn can be obtained at a good yield.

On the other hand, in the case of solvent scouring, since the removal of so-called pupal oils is so complete, even if a spinning oil is applied in a later step, the quality and yield as in the case of defatting scouring with a surfactant or an enzyme are reduced. I can't get it. Various studies have been made on the type and method of applying an oil agent to completely defatted silk cotton such as solvent scouring, and as described above, satisfactory results have not yet been obtained. Although the details of the reason are unknown, the solvent extracts the pupal oil inside the fiber, but the spinning oil applied by spraying or dipping in the subsequent process does not penetrate the inside of the fiber, but simply adheres to the surface. This is presumed to be due to the fact that the oil agent easily falls off in the subsequent cotton production process. In the case of spinning a fine and long silk thread with a single fiber, the behavior is considerably different and very delicate as compared with the case of spinning a thick and short cotton thread or wool.

[0016] The result is the same when silk spinning or the like is subjected to solvent scouring to remove polyolefin fibers. The feeling becomes rough due to excessive degreasing, and an oil agent treatment is required again for the subsequent process. Leads to an increase in steps such as immersion and drying.
In addition, in the case of a silk woven or knitted fabric, there is a danger that the texture of the fiber becomes coarse and hard due to excessive degreasing due to solvent scouring, and in this case, the oil treatment is required again.

[0017]

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies on a method of refining a solvent for silk raw materials and silk spinning, and a method of adjusting the amount of residual pupa oils and applied fats and oils, and have completed the present invention. It is. An object of the present invention is a solvent scouring for removing organic solvent-soluble components (collectively so-called pupal oil) such as pupal body constituent oil and silk constituent wax contained in silk spinning raw materials and silk spinning. The purpose of the present invention is to provide an industrially easy and inexpensive method for carrying out this at a liquid ratio required for a uniform treatment, and not causing excessive degreasing, and leaving an appropriate amount of pupa oil and oil and fat on cotton. . Further, in the present invention, in solvent refining for the purpose of removing polyolefin contaminating silk raw materials and silk spinning, etc., this is carried out at a sufficient liquid ratio necessary for uniform treatment, and furthermore, excessive degreasing is performed. Rather, it is an object of the present invention to provide a method for eliminating an aqueous oil treatment step as a post-treatment by employing an industrially easy and inexpensive method for allowing appropriate amounts of pupal oil and oil and fat to remain in cotton.

[0018]

SUMMARY OF THE INVENTION The present invention relates to an organic solvent refining method for removing a residual organic solvent-soluble component after chemically refining a silk spinning material and a silk spun yarn. 0.1 to 3.0% (by weight) of a fat or oil or a mixture of a fat and a surfactant is mixed in a solution concentration as a residual fat or oil content regulator.
And the ratio of organic solvent to silk spinning raw materials and silk spinning (liquid
Ratio) of 10 or more and less than 50 .

The raw material of the silk spinning of the present invention is not particularly limited, and all the ordinary sub-silkworms are applicable. It exhibits a great effect which is more excellent than the conventional method.

The silk spinning and the like of the present invention are not limited to pure silk spinning made of 100% silk fiber, but also blended yarns with natural fibers such as wool, cotton and hemp, and synthetic fibers such as polyester and nylon, and woven and knitted fabrics made of these. Is done.

The organic solvent used in the present invention includes n
-Hydrocarbons such as hexane, benzene, industrial gasoline, and halogenated hydrocarbons such as trichloroethylene, perchlorethylene, and trichloroethane;
Above all, n-hexane, industrial gasoline, and benzene are trichlorethylene, perchlorethylene,
Trichloroethane and the like are preferred in terms of yield.

The fats and oils applicable to the present invention include animal and vegetable oils,
Waxes, higher aliphatic hydrocarbons, higher fatty acids, higher alcohols, silicone oils or combinations thereof, for example, animal and vegetable oils such as olive oil, castor oil, pupa oil, waxes such as ceresin, liquid paraffin, squalane, etc. Higher aliphatic hydrocarbons, higher fatty acids such as linolenic acid and myristic acid, higher alcohols such as oleyl alcohol, and silicone oils such as amino-modified silicone oil, but are not limited thereto, and include hydrocarbons and halogens. All fats and oils that can be dissolved in a chlorinated hydrocarbon solvent can be used.

As the surfactant (commonly referred to as an oil agent) of the present invention, those having an anionic surfactant or a nonionic surfactant as an essential component are effective. Ester salt (eg, trade name Monogen, manufactured by Daiichi Kogyo Seiyaku), liquid fatty oil sulfate ester salt (eg, trade name, roto oil, manufactured by Daiichi Kogyo Seiyaku, etc.), higher alcohol phosphate ester salt (eg, trade name) Ellenon, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), alkyl allyl sulfonate (eg, trade name Raipon, manufactured by Lion Yushi Co., Ltd.), particularly preferably a higher alcohol processed emulsified oil (eg, trade name Pansofter, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) , An emulsion of higher alcohol sulfates and fats and oils). In the case of nonionic surfactants, most types can be used, but preferred are polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ester, polyoxyethylene polypropylene glycol ether, glycerin fatty acid ester, sorbitan fatty acid ester and the like. And particularly preferred are polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenols, polyoxyethylene alkyl esters and the like. Specific examples include polyoxyethylene oleyl ether, lauryl ether, nonylphenyl ether, octylphenyl ether, and polyoxyethylene oleate and stearic ester.

In the method of the present invention, a fat or oil or a mixture of fat or oil or a mixture of a surfactant and a fat is dissolved or emulsified and dissolved in the above-mentioned organic solvent, and sericin is removed to a predetermined amount by chemical scouring (enzyme-containing scouring). The method can be carried out by immersing a silk spinning raw material or silk spinning and the like, removing the organic solvent-soluble matter by stirring, and then deliquoring and drying.

The concentration of the fat or oil solution in the method of the present invention is 0.1
To 3.0% (weight), preferably 0.2 to 2.0% (weight). If it is less than 0.1%, the effect on the subsequent step of mixing fats and oils is negligible, and if it exceeds 3.0%, after the solvent is removed and dried, the fats and oils adhering to the fibers become sticky. In the post-process, the fiber is wound around the machine, or the feeling is poor when silk is spun.

The solution concentration of the surfactant in the method of the present invention is 0.1 to 3.0% (weight), preferably 0.2 to 2.0% (weight) for the same reason as for fats and oils. Also, when using a mixture of fats and oils and a surfactant, the total concentration is 0.1 to 3.0% (weight), preferably 0.2 to 3.0% for the same reason.
2.0% (weight).

The ratio (liquid ratio or bath ratio) of the organic solvent to the silk spinning raw material, silk spinning, or the like is required to be at least 10 for stirring, and preferably 20 to 30. Liquid ratios above 50 are excessive and not economical.

The solvent refining temperature of the present invention is from normal temperature to a high temperature lower than the boiling point of the organic solvent. The higher the temperature, the shorter the processing time, but the more difficult it is to manage due to work environment measures. or,
60 when the purpose is to remove contaminating polyolefin
Requires treatment at a high temperature of 80 ° C to 80 ° C or higher (Reference materials, 1) Chemical Handbook Application, p708, August 2, 1968
2nd edition, published on the 2nd, 2) Introduction to textiles (Kyoritsu Shuppan), p17
8, issued on July 10, 1970.)

The processing equipment for carrying out the present invention is operated in a closed vessel because of handling organic solvents. In addition, when performing solvent scouring at a high temperature, a solvent heating facility is required. Specifically, a dry creasing machine with a heating facility or a solvent-resistant cheese dyeing machine can be applied. In addition, it can be easily implemented by changing a normal thread or cloth processing machine to an organic solvent specification.

The solvent-purified silk spinning raw materials and silk spinning solution are drained so that the solvent pick-up amount is about 100%.
Then, it is dried with hot air or the like.

[0031]

The present invention will be specifically described below with reference to examples.

Example 1 200 parts of domestic screws were used as raw materials,
The resulting mixture was immersed in a treating solution obtained by mixing and dissolving 10 parts of soda ash and 20 parts of Marcel soap in 00 parts, and the mixture was scoured and stirred at 90 ° C. for 1 hour.
This was repeated twice and then washed with water and dried. Residual sericin of the obtained dried cotton was 1.3% and residual fat was 6.0%. Next, 30 parts of the cotton wool was mixed with 600 parts of trichloroethylene.
The mixture was mixed and stirred with 6.0 parts of pupa oil obtained by pressing silkworm pupae into a part, and a solvent was scoured for 5 minutes using a dry cleaning machine (processing temperature: room temperature). Then, the pick-up amount of trichlorethylene was squeezed to about 100% by a centrifugal dehydrator. Subsequently, this was dried with hot air to obtain defatted cotton wool. The defatted cotton wool was applied to a cocoon opener and a cotton cutter according to a conventional method, and turned into silk cotton using a circular carding machine. The yield of silk cotton (vs. defatted and dried cotton) obtained in the above cotton-making process was 42%, which was a very high yield as a raw material for bis, excellent grade of cotton, and good operability. . Also, the residual sericin of cotton was 1.2% and the residual fat was 1.2%.

Comparative Example 1 Cotton was produced by scouring the solvent according to Example 1, except that the pupal oil was not mixed with the solvent, using the cotton wool obtained in Example 1. The yield of the obtained silk cotton (vs. defatted cotton) was very low at 21%. The quality of the cotton was coarse and the parallelism of the fibers was disturbed, and the operability was almost inoperable due to severe static electricity generation and poor cotton smoothness. The residual sericin of the cotton was 1.2% and the residual fat was 0.2%.

Comparative Example 2 Solvent scouring was performed under the same processing conditions as in Comparative Example 1, and the obtained defatted cotton wool was emulsified with a 1% emulsified aqueous solution of Pansofter SG (liquid temperature 40
C.) and gently circulating the solution for 1 hour, followed by squeezing with a centrifugal dehydrator to pick up about 100% of the surfactant aqueous solution. After drying with hot air, this was subjected to a cotton-making process according to Example 1. The yield of the obtained silk cotton (vs. defatted cotton) is 3
At 0%, the parallelism of the fibers was somewhat disturbed. Although the quality of cotton was slightly coarse and hard, the operability of the process was better than that of Comparative Example 1, but was poorer than that of Example 1 due to the slight generation of static electricity and lack of smoothness. . The residual sericin of the cotton was 1.1% and the residual fat was 1.2%.

In the case where no pupa oil was mixed during solvent scouring, the cotton-making performance was remarkably lower than that in Example 1 and Comparative Examples 1 and 2. In addition, when the defatted cotton wool was treated with a surfactant in an aqueous system, the solvent was not added during solvent scouring. It can be seen that the cotton production performance is considerably lower than when pupal oil is mixed.

As described above, the effect of mixing oils and fats as an agent for adjusting residual oils and fats with an organic solvent during the solvent scouring of the present invention is remarkable.

Example 2 Approximately 5 mg of a thread-shaped colored polypropylene stretched tape was twisted into 10 places of a 65 g skein of a silk spun (EC 140/2) in which the residual sericin was reduced to 0.5% by chemical scouring according to a conventional method. This was mixed with 10 g of liquid paraffin (70 seconds) and polyethylene glycol oleyl ether of HLB12 (trade name Neugen ET) in 2000 ml of tetrachloroethylene.
120, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and immersed in a solution in which 10 g was dissolved, and heated. While stirring the solution gently,
Solvent scouring was performed for 0 minutes, and the solution was drained to about 100% of the pickup without cooling, and dried with hot air. No twisted polypropylene was found in the dried silk spinning, and it was confirmed that these were completely dissolved in hot tetrachloroethylene.

The texture of the silk spun yarn from which contaminating polypropylene was removed by the solvent scouring of the above-mentioned method was a so-called silk touch-like and elegant and soft. Also, the winding from the skein to the cone was smooth and no thread breakage occurred. Residual oil was 1.2%.

Comparative Example 3 A silk spun was subjected to solvent scouring according to Example 2, except that the liquid paraffin and the nonionic surfactant were not dissolved.

In this case also, the polypropylene was completely dissolved, but the feeling of the silk spinning obtained was coarse and hard, and the yarns did not slide smoothly, so that it was impossible to wind up the skein from the skein to the cone. Residual fat was 0.2%.

Comparative Example 4 Solvent scouring was performed under the same processing conditions as in Comparative Example 3. The obtained silk spinning was dissolved in warm water (50 g) in which 20 g of Neugen ET120 was dissolved.
C.) and immersed in 2000 ml, and the solution was gently stirred and treated for 1 hour. This was drained to a pickup amount of about 100% and dried with hot air. The feeling of the obtained silk spun yarn was also somewhat coarse and hard, and also in this case, it was difficult to wind up the skein from the skein to the cone due to frequent thread breakage.

As described above, even in the case of solvent scouring as a measure against contamination of polypropylene in silk spinning, the effect of dissolving fats and oils and surfactants in the solvent has a remarkable effect.

Example 3 In accordance with Example 1 and Comparative Example 2, when benzene was used as the solvent and the silk spinning material was Kiki (Kiki), the solvent was used during the scouring of A.
The effect of adding various fats and oils in the subsequent aqueous treatment was compared and studied. The result is the oil concentration and cotton production yield (vs. dry cotton).
The relationship is shown in Table 1.

In this case, in both treatments A and B, polyethylene glycol nonylphenyl ether of HLB6 was mixed at a concentration of 0.1% as a surfactant, and in the case of aqueous treatment, treatment was carried out in an emulsified bath.

[0045]

[Table 1]

As described above, the effect of mixing oils and fats during solvent scouring has a remarkable effect as compared with the case where oils and fats are applied to defatted and dried cotton wool as a post-process. In the case where oils and fats were applied in an aqueous system as post-processing, in all cases, the cotton-making operability was not good due to generation of static electricity and poor smoothness when the application was small, and entanglement of cotton with the machine when the application was large. When mixing fats and oils during solvent refining, the fat and oil concentration is 0.1 to 3.0.
% (Weight), especially in the range of 0.2 to 2.0% (weight), was satisfactory in all respects.

Example 4 According to Example 1 and Comparative Example 2, using tetrachloroethylene as a solvent and bis as a raw material, the effect of adding castor oil and various nonionic surfactants was compared with cotton production yield. did. Castor oil and various nonionic surfactants are 0.5% each
(Weight) were mixed. Table 2 shows the results.

[0048]

[Table 2]

As described above, the effect of mixing the oil and fat and the nonionic surfactant during the solvent scouring is remarkable in the cotton production yield. In addition, the operability of cotton production was much better in terms of antistatic properties and smoothness as compared with the case where oils and fats and a surfactant were added in a post-processing aqueous system.

Example 5 According to Example 4, liquid paraffin and various anionic surfactants were mixed by 0.5% (by weight). Table 3 shows the results.

[0051]

[Table 3]

As described above, the effect of mixing the fat and oil and the anionic surfactant during the solvent scouring is remarkable.

Example 6 The solvent was 1,1,1-trichloroethane and the treatment temperature was 10
Except at 0 ° C. (pressurized state), the contaminating polypropylene in the silk spinning was removed by solvent scouring according to Example 2. In this case, no surfactant was mixed. No twisted polypropylene was observed in the dried silk spinning yarn, and the texture of the yarn was silky touch and elegant and soft. Also, the winding from the skein to the cone was smooth and no thread breakage occurred.

As described above, even in the case of solvent scouring using trichloroethane as a measure against contamination of polypropylene in silk spinning, the effect of dissolving fats and oils in the solvent is remarkable.

[0055]

As described above, the present invention relates to solvent scouring for removing organic solvent-soluble components such as pupal oils and silk constituent waxes possessed by silk spinning materials and silk spinning. By adding a fat or oil or a mixture of a fat and a surfactant to the mixture, it is not excessively defatted even if this is carried out at a sufficient liquid ratio necessary for uniform treatment, and an appropriate amount of pupa oil and applied This makes it possible for oils and fats to remain in the fiber, and in the case of silk spinning raw materials, high-quality cotton and silk spinning can be produced with good yield and good operability in the subsequent cotton production and spinning. In the case of silk spinning, the subsequent weaving and knitting process can be performed with high efficiency. Completely degreases without adding fats or oils or a mixture of fats and surfactants during solvent scouring, and gives apparently the same amount of fats and oils and surfactants in the aqueous process in the subsequent process, and has the same function It is impossible to get In the case of the water-based treatment, it is considered that the treatment is merely mere surface adhesion of fats and oils and surfactants.

The same applies to the case of solvent scouring which is carried out for the purpose of removing polyolefins contaminating silk raw materials and silk yarns. For example, when contaminating polypropylene is dissolved and removed with trichloroethylene or tetrachloroethylene, the system It is an essential condition to add and dissolve fats or oils or a mixture of fats and surfactants therein.

Claims (1)

(57) [Claims] 1. An organic solvent refining method for removing residual organic solvent-soluble components after chemically refining a silk spinning raw material and a silk spun yarn. Or a mixture of fats and oils and surfactants in solution concentration
0.1-3.0% (weight) mixed, silk spinning raw material and silk spinning
The ratio (liquid ratio) of the organic solvent with respect to
A method for refining an organic solvent, such as a silk spinning raw material and a silk spinning, which is carried out in full .