JP2007154395A - Modified silk fiber and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve problems that a whitening phenomenon or pilling is caused in silk fibers when a winch dyeing machine or a jet dyeing machine is used in a silk textile product and home washing cannot be carried out, etc. <P>SOLUTION: The silk fibers can be converted into cationized modified silk fibers to thereby solve the whitening phenomenon or pilling caused during dyeing. The dyeing can be carried out by using the winch dyeing machine or jet dyeing machine. Absorbency and binding force of an acid dye, a reactive dye, a metal complex dye, a chrome dye, a direct dye, a vegetable dye, etc., used for dyeing the silk fibers can be increased to improve color fastness to dyeing. A product made of the modified silk fibers is the modified silk fibers and a modified silk product without causing the whitening phenomenon or pilling by home washing or even when rubbed in a water wetted state. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a modified silk fiber that prevents whitening due to washing and wet friction in a silk fiber product, and provides anti-pilling, enhanced dyeing fastness, and form stability, and a method for producing the silk product.

Even if the silk fibers become fibrillated, that is, light friction such as contact between cloths, it is a problem to prevent fuzz and dyeing from becoming white and deteriorating as a product. Many attempts have been made. It is considered that a crosslinking reaction using a chlortriazine compound, a dialdehyde, a diepoxy compound or the like is effective. Among them, epoxy compounds have recently attracted attention from the viewpoint of safety and environmental conservation. (For example, refer to Patent Documents 1, 2, and 3.) However, all of them have drawbacks that the process is complicated and takes a long time, special techniques and know-how are required, and processing machines are limited.

  Patent Publication No. Hei 7-292571   Patent Publication 8-158256   Patent Publication 11-323735

It is an object of the present invention to simplify such a plurality of processing steps, and to free the selection from the restrictions of the machine used for processing so that it can be freely selected.

A modified silk fiber characterized by cationizing silk fiber and a method for producing the same.

The modified silk fiber according to claim 1, which is cationized by using a quaternary ammonium compound having a reactive group capable of reacting with the silk fiber.

The method for producing a modified silk fiber according to claim 1, wherein the cationization is performed using a quaternary ammonium compound having a reactive group capable of reacting with the silk fiber.

A modified silk product comprising 5% to 100% of the modified silk fiber according to claim 1.

By using the processing method of the present invention, there is no restriction on the processing machine for the modified processing itself, and not only can the fibrillation prevention processing be performed in one bath, but also in the dyeing processing performed after the main processing. This frees you from using special dyeing machines and makes dyeing easier.

The apparel product using the modified silk fiber of the present invention does not cause fibrillation peculiar to silk fiber such as fluff and whitening even if it is washed in a household washing machine.

The modified silk fiber of the present invention has good dye absorption. Particularly in the case of dark colors, dyes can be saved and the load of drainage is reduced. Further, since the binding force with the dye is strong, color fading due to washing or the like is reduced.

Apparel products using the modified silk fiber of the present invention have good shape stability even when washed in a home washing machine.

The present invention can also be applied to silk fibers that have already been dyed, preventing fluff and whitening, and improving dyeing fastness and form stability by washing.

By applying the present invention to silk fibers having fluff and whitening, the fluff and whitened portions can be dyed thereafter, and there is an effect of improving dyeing fastness and form stability.

The silk fiber to be modified can be processed in any form of cotton, sliver, thread, fabric, and apparel.

As a processing machine to be applied, a dyeing processing machine suitable for each of the above forms can be used as it is.

It can also be similarly processed to silk fibers obtained by graft-copolymerizing silk fibers with vinyl compounds such as methacrylamide, 2.hydroxyethyl methacrylate, polyethylene glycol methacrylate, and the like.

On the other hand, it is possible to carry out a process of graft copolymerizing a vinyl compound such as methacrylamide, 2-hydroxyethyl methacrylate, polyethylene glycol methacrylate or the like on the modified silk fiber by cationization.

As the cationization processing agent, a quaternary ammonium compound having a reactive group capable of chemically reacting with silk fiber is used.

The cationization process can be performed in a commonly used alkaline aqueous solution, a concentrated neutral salt, or a neutral salt and alkali combined aqueous solution. A caustic alkali is preferably used as the alkali agent, and a rhodan salt (thiocyanate) is preferably used as the neutral salt. A smaller bath ratio (ratio of silk fiber to solution) is economically advantageous. Usually, it is processed at 1: 5 to 1:30, preferably 1: 5 to 1:15. The higher the bath concentration of the cationizing agent, the higher the degree of cationization, but there is a limit and it is economically disadvantageous. On the other hand, if it is too low, the degree of cationization is lowered and the purpose of the effect cannot be achieved. Usually 3% to 50%. The treatment is preferably carried out in a bath ranging from 4% to 35%. The hydrogen ion concentration index of the treatment liquid is around 12 when caustic is used, around 7 for the neutral salt, and around 8.5 for the combined method. The treatment temperature is from room temperature to around 100 ° C., and the treatment time is from 12 to 24 hours at room temperature and from 30 minutes to 1 hour at around 100 ° C. In the case of padding or printing, drying can be performed at 80 to 120 ° C.

700 g of smelted sliver sliver was treated with a high-temperature pressurization type overmeyer 1 kg dyeing machine as a 5 liter aqueous solution of 22 g / L of Kathionon UK (On the other hand, Yushi Kogyo Co., Ltd.) and 130 g of caustic soda (24% solution). The temperature was raised from room temperature at 1 ° C. for 1 minute and treated at 60 ° C. for 40 minutes, and then the chemicals adhering to the fibers were washed away using water, followed by dehydration and drying.

The cationized sliver of Example 1 was dyed black with a reactive dye. In Comparative Example 1, raw rabbit sliver was dyed with the same formulation.

About the whitening generation | occurrence | production determination The whitening generation | occurrence | production degree used the type of JIS-L0849 friction tester II, and determined the state of the silk fiber surface by the load of 200gx100 times by a wet friction test. The gray scale for fading color (produced by Japan Color Research Institute) was used for the judgment. Those having no discoloration due to whitening after wet friction are judged as grade 5, and those whitened by whitening are judged as grade 1.

The same cationization treatment as in Example 1 was performed using a scoured sliver sliver and dyed black. In Comparative Example 2, the scoured sliver sliver was dyed black.

Table 1 is a test of the rabbit sliver, and Table 2 is a test of whitening occurrence and dyeing performance of the rabbit sliver. Rabbit sliver and sliver sliver that are cationized at the end of dyeing completely absorb the dye. In the whitening occurrence test after dyeing, both cationized slivers have no whitening phenomenon on the fiber surface.

Silk spinning (MC2 / 120) 500g (5 pieces of 100g casserole) after scouring was treated with 275g of Cationone UK and 130g of caustic soda (24% solution) in a 5 liter aqueous solution with a high-temperature pressure-type overmeyer 1kg dyeing machine. The temperature was raised from normal temperature at 1 ° C. for 1 minute, treated at 60 ° C. for 40 minutes, and then the chemical adhering to the fiber was washed away using water, followed by dehydration and drying.

As the cationized silk spinning of Example 3 and Comparative Example 3, a cylindrical knitting of raw silk spinning was prepared, dyed black with a metal-containing dye, and a laundry test was performed.

The washing test uses a two-tank washing machine according to 103 method based on JIS-L0217, puts the sample in a washing net, sets the number of washing times to 5 minutes, and continuously wash for 25 minutes. Subsequently, the test is performed with running water and set to 1 minute for 2 minutes, and the continuous test for 10 minutes is set to 5 times, and the test is repeated 30 times, 50 times, and 100 times.

Table 3 is a test table for dyeing performance, whitening occurrence, and washing durability. The cationized silk spinning completely absorbed the dye and was dyed black. There is no whitening phenomenon even in wet friction, and no pilling or whitening phenomenon occurs after 100 washings.

[FIG. 1] is an enlarged view of the fiber surface after wet-rubbing after black dyeing the cationized silk spinning of Example 3, and [FIG. 2] black-dyed raw silk spinning of Comparative Example 3. Cationic silk spinning does not show whitening. Unprocessed silk spun fiber is fibrillated and can be judged to be the cause of whitening.

Silk spinning (MC2 / 120) 500g (5 pieces of 100g casserole) subjected to test scouring by changing the cationizing agent was added to 300 liters of Wytex E100 (Nagase ChemteX Corp.) and 130 g of caustic soda (24% solution) in 5 liters. Treated as an aqueous solution with a high-temperature pressure-type overmeyer 1 kg dyeing machine. The temperature was raised from room temperature in 1 ° C for 1 minute and treated at 60 ° C for 40 minutes. Then, the chemical | medical agent adhering to the fiber was washed away using water, and it spin-dry | dehydrated and dried.

A tube test of the cationized silk spun by changing the cationizing agent of Example 4 and the raw silk spun of Comparative Example 4 was dyed black with a metal-containing dye, and a laundry test was performed.

Table 4 shows results similar to Table 3. In tests of dyeing performance, degree of whitening, and durability to washing, the cationized silk spinning completely absorbed the dye and became completely black even when the cationizing agent was changed. There is no whitening phenomenon even in wet friction, and no pilling or whitening phenomenon occurs after 100 washings.

For silk spinning (MC2 / 120) treated in advance at 85 ° C for 30 minutes in a bath of methacrylamide 52 g / L, sulfuric acid (62.5%) 1.5 g / L, potassium persulfate 1.2 g / L Cationization was carried out under the same conditions as in Example 3.

After graft copolymerization in Example 5, the knitted silk yarn of the cationized silk yarn and the unprocessed silk yarn of Comparative Example 5 were dyed black with a metal-containing dye and subjected to a laundry test.

Table 5 shows changes in the shape of the knitted fabric during washing. After graft copolymerization in Example 5, the cationized silk spinning tube knitting stretches by 8% in the transverse direction and shrinks by 10.7% in the length direction due to relaxation shrinkage. Almost no dimensional change is seen. There is no size change with respect to washing, and it is excellent in form stability. The raw silk spinning cylinder knitting of Comparative Example 5 expands in the horizontal direction and contracts in the length direction every time the number of washing increases 10 times, 20 times, and 50 times. Further, in the occurrence of the whitening phenomenon of Table 5, Example 5 has no whitening phenomenon. In the tubular knitting of Comparative Example 5, the whitening phenomenon occurs every time the number of washing increases from 10 to 50 times.

A test was conducted in which a vinyl compound was copolymerized on a cationized silk yarn. The cationization treatment was the same as in Example 3, and the copolymerization treatment was the same as in Example 5.

The silk spinning obtained by copolymerizing the cationization treatment + vinyl compound according to Example 6 and the comparative example 6 are obtained by dyeing black knitting of raw silk spinning with a metal-containing dye, dyeing performance, degree of whitening, and durability to washing. The test was conducted.

Table 6 shows the same results as Table 4. In tests of dyeing performance, degree of whitening, and durability to washing, the cationized silk spinning completely absorbed the dye and became completely black even when the cationizing agent was changed. There is no whitening phenomenon even in wet friction, and no pilling or whitening phenomenon occurs after 100 washings.

Cationization treatment was applied to the smooth knitted fabric that had already been dyed and finished. The material used was a black dyed smooth knitted fabric that was knitted with 6 pieces of dynamic silk (raw yarn 42 denier polyurethane 18d) and raw silk 21 denier from Doko Shoji Co., Ltd. (Kyoto City). In the cationization treatment, 32 g (30 cm square) of the knitted fabric was washed with hot water, then 18 g of Cathionone UK and 8 g of caustic soda (24% solution) were used to make a 500 cc aqueous solution and processed with a color pet dyeing machine. Heated from room temperature in 1 ° C for 1 minute and treated at 60 ° C for 30 minutes. Then, the chemical | medical agent adhering to the fiber was washed away using water, and it spin-dry | dehydrated and dried.

A whitening degree test was performed on the cationized knitted fabric of Example 7 and the uncationized knitted fabric of Comparative Example 7.

Table 7 is a whitening evaluation table of dynamic silk (urethane mixed yarn) knitting material using raw silk. In Example 7, cationization treatment was performed, and the expression of whitening of the silk surface when wet was able to be eliminated.

Table 8 is a washing fastness evaluation table of dynamic silk (urethane mixed yarn) knitting material using raw silk. In Example 7, since the cationization treatment was performed, there was no loss of dye or change in hue in 30 subsequent washings.

The scoured silk yarn was subjected to a cationization treatment by a padding method. Cylinder knitting is made using silk spinning (MC2 / 120), soaked in a solution of cathionon UK (pure content 40%) using caustic soda to a hydrogen ion concentration of 11.5, and picked up with a squeeze roller. Dry at 65 ° C at 120 ° C for 10 minutes. Then, the chemical | medical agent adhering to the fiber was washed away using water, and it spin-dry | dehydrated and dried.

Cationized silk spun tube knitting and unprocessed silk spun tube knitting were dyed black with reactive dye, and the cationized knitted fabric was designated as Example 8, and the untreated knitted fabric was designated as Comparative Example 8. .

表９と表１０はパディング処理である。一般的な処理とされる浴中処理と同様な結果が得られた。

Tables 9 and 10 are padding processes. The same results as those obtained in the general treatment were obtained.

Cylindrical knitting was made using amber silk spinning (MC2 / 140) to give Comparative Example 9, and Example 9 was a cationized treatment under the same conditions as Example 7.

Table 11 is a test of the degree of whitening due to wet friction. Example 9 shows that whitening due to wet friction was improved in a cationized product after dyeing. At 30 washings in Table 12, Example 9 resulted in increased dyeing fastness. There is no color loss after washing, and the whitening phenomenon is improved by cationization treatment.

6 double feathers were washed 10 times, dyed black, and stained spots due to the occurrence of whitening were confirmed and used as Comparative Example 10. Example 10 was prepared by performing cationization under the same conditions as in Example 7 and dyeing black on 6 double feathers that were washed 10 times.

表１３における白化が発生した羽二重はカチオン化を行うことで、斑なく染まる。比較例１０は斑染めが発生した。表１４の洗濯３０回テストでは、実施例１０は洗濯による変退色は少なく、白化の発生もない。比較例１０の未カチオン化の羽二重は洗濯を繰り返す事で、白化が進行し、黒色の染色堅牢度も悪く、グレー色となった。Example 10 and Comparative Example 10 were performed 30 times in a washing machine, and dyeing fastness and occurrence of whitening were confirmed.

The feather double in which whitening occurs in Table 13 is dyed without spots by cationization. In Comparative Example 10, spot dyeing occurred. In the washing 30 times test of Table 14, in Example 10, there is little discoloration due to washing and no whitening occurs. The non-cationized feather double of Comparative Example 10 was whitened by repeating washing, and the black dyeing fastness was poor and became gray.

Surface enlargement (100x) after wet friction of cationized silk yarn dyed in black Surface enlargement (100x) after wet friction of raw silk yarn dyed in black

Claims (4)

A modified silk fiber characterized by cationizing silk fiber and a method for producing the same. The modified silk fiber according to claim 1, which is cationized using a quaternary ammonium salt having a reactive group capable of reacting with the silk fiber. The method for producing a modified silk fiber according to claim 1, wherein the cationization is performed using a quaternary ammonium salt having a reactive group capable of reacting with the silk fiber. A modified silk product comprising 5% to 100% of the modified silk fiber according to claim 1.

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