JPS648117B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a treatment method for imparting water absorbency and antifouling properties to hydrophobic synthetic fibers, and for improving knitting yarn breakage during sewing. Originally, hydrophobic synthetic fibers have excellent advantages such as bulkiness and heat retention, but they are difficult to absorb sweat and tend to become sticky, become re-contaminated and darken after repeated washing, and fibers are damaged and knitted by sewing thread friction caused by high-speed sewing machines. There are disadvantages such as thread breakage,
Various improvement measures have been proposed. For example, hydrophilic compounds with water absorption and stain resistance such as block copolymers of polyoxyethylene and caprolactam, copolymers of polyester oligomers and polyethylene glycol, and carboxylic acid derivatives are used to provide water absorption and stain resistance. Post-processing is known. On the other hand, as a measure to improve knitted fabric yarn breakage caused by high-speed sewing machines, silicone-based softeners or paraffin-based smoothing agents are generally used for the purpose of lowering the coefficient of friction on the fiber surface. However, water-absorbing agents and softening and smoothing agents have contradictory properties, and if they are used together, one of the properties will be sacrificed or only half-baked properties will be obtained. The present inventors have arrived at the present invention as a result of intensive research to achieve both water absorption/stain resistance and sewability. That is, the main points of the present invention are as follows. This treatment method is characterized by treating hydrophobic synthetic fibers with a water-absorbing agent, a softening and smoothing agent, and a water-soluble silicone. This means that in any treatment liquid, the weight ratio of softening and smoothing agent to water-soluble silicone in the treatment liquid is 20-2:80-98. The present invention will be explained in detail below. The water-soluble silicone compound referred to in the present invention includes, for example, 2 to 2 repeating units of methylsiloxane.
100, preferably 5 to 80 methylsiloxane or methylhydrodienesiloxane, copolymerized with a compound having an ethylene oxide repeating unit of 2 to 40, preferably 12 to 25 polyoxyethylene segments, etc., but limited to these. It is not something that will be done. On the other hand, water-absorbing agents that provide water-absorbing and antifouling properties include copolymers mainly composed of polyalkylene glycol acrylates or polyalkylene glycol methacrylates and acrylonitrile, and water-soluble polyalkylene glycol-terephthalic acid-ethylene glycol block copolymers. Examples include, but are not limited to, polymers, polyamide-polyalkylene oxide copolymers, and methoxymethylated polyamides. In the present invention, the softening and smoothing agent refers to one or more of polyhydric alcohol fatty acid esters, aliphatic polyamide derivatives, polyethylene glycol fatty acid esters, polyalkylene oxides, polyalkylene oxide surfactants, or a paraffin smoothing agent. The main component is a mixture of The treatment with the above composition simultaneously dyes the treated object in the form of fibers, threads, or fabrics at 80 to 120°C for 10 to 90°C.
After soaking for minutes, dry normally, but after dyeing
Drying may be performed after immersion at 80°C for 1 to 20 minutes. In addition, in the state of fabric, it may be applied by a pad-dry method or a pad-steam method like usual resin processing. In addition, the above-mentioned water-absorbing agent is blended during polymerization in the fiber production stage, or fibers, threads, or fabrics in the form of fibers, threads, or fabrics that are attached to the raw fibers in the aqua gel state after spinning and washing with water are mixed with the above-mentioned softening and smoothing agent and water-soluble silicone. Similar post-processing may also be performed. The fibers obtained by such treatment are knitted as they are in the case of long fibers or spun yarns,
Short fiber fields are spun and then knitted. Also,
When processed in the form of spun yarn, it is knitted as is, and these knitted fabrics exhibit excellent water absorbency, stain resistance, and sewability with excellent washing durability. Of course, it is also effective even if this process is performed after organization. In the present invention, rather than sequentially treating with a water-absorbing agent, a softening and smoothing agent, and a water-soluble silicone, it is preferable to treat the three together in the same bath. In terms of effectiveness, it is preferable that at least the softening and smoothing agent and the water-soluble silicone be treated in the same bath. In the present invention, it is important to process in a system in which there is a large amount of softening and smoothing agent relative to water-soluble silicone in the treatment liquid in terms of weight ratio. In the examples, Example 1 is 1.0g/:5.5g/, Example 2 is 0.5g/:20g/, and Example 3 is 0.5g/:
8g/, Example 4 is 0.3g/: 7g/, Example 5
is 1.0g/:20g/, Example 6 is 0.5g/, and Example 7 is 1.0g/:4.5g/, all of which have a large amount of flexible and smooth material, and a weight mixing ratio of about 4 times or more is adopted. This is what we are doing. The hydrophobic synthetic fiber of the present invention refers to acrylic, polyester, and polyamide synthetic fibers. For example, acrylic fibers contain acrylonitrile as a main component and copolymerized components such as methyl acrylate, methyl methacrylate, sodium styrene sulfonate, sodium allyl sulfonate, and 2-methyl-5-vinylpyridine for the purpose of imparting dyeability. It refers to fibers in which one or more types are copolymerized, and fibers in which vinylidene chloride or the like is copolymerized or blended for the purpose of imparting flame retardance. Polyester fibers are polymers produced by the condensation reaction of terephthalic acid and ethylene glycol or butylene glycol, and sebacic acid, adipic acid, trimellitic acid, isophthalic acid, paraoxybenzoic acid, etc. and ethylene glycol, It refers to condensation polymers of butylene glycol and polyester polymers containing other polyesters. Polyamide fibers include nylon 4, nylon 6/6, nylon 6/10, nylon 12, modified nylons, and blend fibers of these polyamide compounds and other polymers.
Refers to copolymer fibers, etc. Among the above-mentioned hydrophobic synthetic fibers, acrylic fibers are difficult to impart water absorption, antifouling properties, and sewability, and are therefore fibers that can be particularly effectively utilized in the present invention. Further, the effects of the present invention can still be effectively utilized when hydrophobic synthetic fibers are used alone or in combination, and even if they are in the form of cotton, thread, or fabric. Although water-soluble silicones cannot exhibit significant effects when used alone, they have the unique effect of balancing the two contradictory effects of water absorbing agents and softening and smoothing agents without canceling them out. This effect is exhibited only when the silicone is water-soluble, regardless of the type of water-absorbing agent and softening and smoothing agent. The present invention provides hydrophobic synthetic fibers with excellent water absorption,
It is possible to provide stain resistance and sewability at the same time. Hereinafter, the present invention will be specifically explained with reference to Examples. Example 1 Copolymerized acrylonitrile fiber consisting of 95 mol% acrylonitrile, 4 mol% methyl acrylate, and 1 mol% sodium allylsulfonate, 2.5 denier,
Using fibers with a length of 76 mm, a spun yarn with a hair count of 1/80 was obtained. on the other hand,

A water absorption agent was prepared by polymerizing 80% by weight of the monomer of the formula and 20% by weight of acrylonitrile to form a 20% aqueous solution. After dyeing the 1/80 spun yarn with a package dyeing machine using a conventional method, it was washed once with hot water, and 4.5 g of the previously prepared water absorbing agent and 5.5 g of a softening and smoothing agent made of polyhydric alcohol fatty acid ester were added.
, a water-soluble silicone compound consisting of methylhydrodienesiloxane having 50 repeating units of methylsiloxane and polyoxyethylene having 15 repeating units of ethylene oxide was added to a 50°C aqueous solution containing 1.0g of water-soluble silicone compound at a bath ratio of 1:20. It was immersed for a minute. The treated yarn is dehydrated by suction so that the moisture adhesion rate is 60%.
It was then dried in a cheese dryer at 100°C for 20 minutes. (This sample is referred to as A ₁ ) On the other hand, cheeses were treated in the same manner as in A ₁ using 4.5 g of the water absorbing agent, 5.5 g of the softening and smoothing agent, and 5.0 g of the water-soluble silicone solution used in A ₁ . Let A ₂ , A ₃ , and AD.
In addition, 4.5g of the water absorbing agent used in _A1 and the softening and smoothing agent
55.5g/, water-absorbing agent 4.5g/and water-soluble silicone
Cheeses treated in the same manner in a solution adjusted to 1.8 g/softening agent, 5.5 g/softening and smoothing agent, and 1.0 g/water-soluble silicone are designated as A ₅ , A ₆ , and A _7, respectively. Note that the unprocessed yarn is A ₀ . A smooth knitted fabric with a basis weight of 250 g/m was knitted using the above spun yarns A ₀ to A ₇ . After knitting, the fabric was set at 90°C for 25 seconds using a heat setting machine, and then the following sewing tests and water absorption and stain resistance tests were conducted. In addition, to examine washing durability, washing was repeated 30 times at 40°C for 10 minutes in a bath of 2 g of Kao Soap's detergent "Zabu" using a Toshiba electric washing machine. Sewability test: Using industrial sewing machine JUKI DDL-555 and #14 sewing machine needle, 6 stacked samples were sewn together at a sewing speed of 3000 stitches/minute, with 15 stitches/3cm stitches at 20cm intervals. Sewability is evaluated by the number of cuts in the knitting thread during sewing. A knitting yarn breakage rate of less than 8% is considered a pass. Water absorption test: 0.03 cc/drop of water is dropped onto the horizontally placed sample using a pipette, and the time required for the water drop to be completely absorbed by the knitted fabric is measured. If it is 5 seconds or less, it can be said to be good. Antifouling test: 5 c.c. of the following mixture and 200 c.c. of water as a staining agent.
ESSO Automatic Transmission Fluid 300g Coal tar 3g Portland cement 5g Super “Zabu” 5g Add 4 samples of 5cm x 10cm to the contaminated solution and heat at 60℃.
After processing in a rounder meter for 30 minutes, the sample was taken out and washed in a Toshiba electric washing machine on gentle conditions for 12 minutes using 2 g of Zabu neutral detergent in water. After drying, the sample is judged on a gray scale for contamination. If it is grade 3 or higher, it can be said to be good. Table 1 shows the results of evaluating the sample using the test method described above. This result shows that all performances can be satisfied only by using the three components: water absorbing agent, softening and smoothing agent, and water-soluble silicone.

[Table] Example 2 The same acrylonitrile fiber as in Example 1 was used to make a spun yarn with a wool count of 1/48, and then 400 g/m
A knitted fabric with a Pontiloma structure was obtained. The main knitted fabric was dyed by a conventional method. On the other hand, dimethyl terephthalate
A copolymer dispersion liquid (active ingredient: 20%) consisting of 500 parts of polyethylene glycol, 400 parts of ethylene glycol, and 700 parts of polyethylene glycol having a molecular weight of 3000 was obtained. 10 g of the water absorbing agent, 20 g of the aliphatic polyamide derivative softening and smoothing agent, and 0.5 g of a water-soluble silicone compound consisting of methylsiloxane having 10 repeating units and polyoxyethylene having 10 ethylene oxide repeating units. After immersing the pontiloma knitted fabric in the treatment solution containing the solution, it was squeezed using a centrifugal dehydrator so that the amount of solution adhering to the solution was 70%.
Thereafter, it was dried at 80°C (this sample is designated as _B1 ). On the other hand, _the same knitted fabric was immersed in 20g/aqueous solution of a water-absorbing finishing agent made of a ranogen derivative, squeezed in the same manner as _B1 , and dried.
_B3 is a knitted fabric that is immersed in 20g/aqueous solution, squeezed out in the same manner as _B1 , and dried. The untreated knitted fabric was designated as _B0 , and these samples were subjected to sewing tests and water absorption and stain resistance tests in the same manner as in Example 1. As shown in Table 2, _B1 satisfied all the results.

[Table] Example 3 A product consisting of 95 mol% acrylonitrile, 4 mol% methyl acrylate, and 1 mol% sodium allylsulfonate, to which 0.2% by weight of the water-absorbing agent used in Example 1 was attached after washing with spinning water in the fiber manufacturing stage. A spun yarn with a hair count of 1/60 was obtained using copolymerized acrylonitrile fibers with a denier of 3.0 and a fiber length of 102 mm. After cheese dyeing the 1/60 spun yarn using a package dyeing machine in a conventional manner, the yarn was washed once with hot water, and the same softening and smoothing agent as in Example 1 was prepared in advance.
8g/, and water-soluble silicone compound 0.5g/
The sample was immersed in a 30°C aqueous solution of 1:20 for 15 minutes. The treated yarn was dehydrated by suction so that the moisture adhesion rate was 50%, and then dried in a cheese dryer at 80° C. for 30 minutes (this sample is designated as C ₁ ). On the other hand, 10 g of the softening and smoothing agent and 5.0 g of the water-soluble silicone solution used in C ₁ were dehydrated by suction in the same manner as in C ₁ , and the dried cheese was added to C ₂ , respectively.
Let it be C ₃ . Note that the unprocessed yarn is C ₀ . A knitted fabric with a milled structure having a basis weight of 350 g/m was knitted using the above spun yarn of _C0 to _C3 . After knitting, set at 120°C for 20 seconds using a heat setting machine, Example 1
Sewing tests as well as water absorption and stain resistance tests were conducted in the same manner as above. As shown in Table 3, _C1 satisfied all the performance requirements.

[Table] Example 4 Using the same acrylonitrile fiber as in Example 1, a spun yarn with a wool count of 1/64 was obtained. on the other hand,

75% by weight of the monomer of the formula and 25% by weight of acrylonitrile were polymerized to prepare a 20% aqueous solution of a water absorption finishing agent. The 1/64 spun yarn was subjected to simultaneous dyeing treatment using a package dyeing machine in a conventional manner in a dye bath containing 2.0 g of the water absorbing agent. After that, wash once with water and use the same softening and smoothing agent as in Example 1 prepared in advance.
7.0g/and water-soluble silicone compound 0.3g/
It was treated with a 30°C aqueous solution of for 15 minutes at a bath ratio of 1:20. The treated yarn was dehydrated by suction so that the amount of water attached was 65%, and then dried in a cheese dryer at 100° C. for 30 minutes (this sample is referred to as D ₁ ). On the other hand, cheese that was simultaneously dyed and treated with 2.0 g of the water-absorbing agent used in D ₁ was used as D ₂ , and cheese that was simultaneously dyed and treated with 2.0 g of the water-absorbing agent used in D ₁ , and then treated with the softening and smoothing agent used in D _1. The cheese treated with 7.0 g/ of the water-soluble silicone compound used in D 1 was referred to as D ₂ , and the cheese treated in the same manner with 5.0 g/ of the water-soluble silicone compound used in D ₁ was referred to as D ₄ . In addition, unprocessed yarn is
Let D be ₀ . A punch roman knitted fabric with a basis weight of 400 g/m was knitted using the above spun yarns D ₀ to D ₄ . After knitting, the fabric was set at 120° C. for 25 seconds using a heat setting machine, and then a sewing test and water absorption and stain resistance tests were conducted in the same manner as in Example 1. The results are shown in Table 4. The results show that all performances can be satisfied only by using the three components: water absorbing agent, softening and smoothing agent, and water-soluble silicone.

[Table] Example 5 A Tetron spun knitted fabric with a smooth texture having a basis weight of 250 g/m was dyed in a conventional manner using a high temperature dyeing machine. On the other hand, 10 g of a water absorbing agent (active ingredient 25%) obtained from 400 parts of dimethyl terephthalate, 300 parts of ethylene glycol, and 600 parts of polyethylene glycol with a molecular weight of 2800, the softening and smoothing agent used in Example 1.
A treatment solution containing 20 g/g of the water-soluble silicone compound and 1 g/g of the water-soluble silicone compound was prepared. Next, the dyed smooth knitted fabric was padded in the treatment solution at 80% squeezing, dried at 120°C for 3 minutes, and then heat-treated at 170°C for 30 seconds (this sample is referred to as _E1 ). In addition, the same dyed knitted fabric was immersed in 25 g of an aqueous solution of a water-absorbing finishing agent made of polyamide-polyalkylene oxide copolymer, squeezed in the same manner as E ₁ , and the dried fabric was designated as E ₂ , which was made from methoxymethylated polyamide. Soak in 20g/aqueous solution of water-absorbing agent and squeeze in the same way as E ₁ .
The dried knitted fabric is designated as _E3 . Let the untreated knitted fabric be E ₀ ,
The same tests as in Example 1 were conducted on these samples. As shown in Table 5, E ₁ satisfied all the performances.

[Table] Example 6 A 70-denier 24-filament nylon-6.6 woolly processed yarn was knitted into a double-sided double-sided fabric and dyed by a conventional method. On the other hand, 5.0 g of water absorbing agent, 10.0 g of softening and smoothing agent, and water-soluble silicone compound as in Example 1 were added.
The treatment solution was adjusted to contain 0.5g/. Next, the dyed double-sided knitted fabric was padded in the treatment solution at 90% squeezing, dried at 130°C for 3 minutes, and then heat-treated at 170°C for 30 seconds (this sample is designated as F ₁ ). In addition, 5.0 g of the water absorbing agent, 10.0 g of the softening and smoothing agent, and 5.0 g of the water-soluble silicone compound used in F ₁ were each used alone.
Cheese treated in the same manner as F ₁ was used as F ₂ , F ₃ ,
Set it to F ₄ . Note that the same test as in Example 1 was conducted using the untreated knitted fabric as F ₀ . The results are as shown in Table 6.
It can be seen that all performances are satisfied only when the user uses the product.

[Table] Example 7 Using the same acrylonitrile fiber as in Example 1, a spun yarn with a wool count of 1/64 was obtained. on the other hand,

A water-absorbing agent was prepared by polymerizing 70% by weight of the monomer of the formula and 30% by weight of acrylonitrile to form a 15% aqueous solution. After the above-mentioned 1/64 spun yarn was cheese-dyed using a package dyeing machine in a conventional manner, it was washed once with hot water,
2.0 g of the water absorbing agent prepared in advance and 50 parts by weight of polyethylene glycol with a molecular weight of 25,000;
A softening and smoothing agent consisting of 10 parts of paraffin (C ₂₆ H ₅₄ ), 3 parts of sorbitan ester paraffin, and 37 parts of water.
4.5 g/ and 1.0 g/ of the same water-soluble silicone compound as in Example 1 were added to a 35°C aqueous solution at a bath ratio of 1:15.
It was soaked for 10 minutes. Treated yarn has a moisture adhesion rate of 65%
It was dehydrated by suction until it became dry, and then dried in a cheese dryer at 80°C for 45 minutes. (This sample is designated as _G1 ). On the other hand, the water absorption finishing agent 5.0g/, the softening and smoothing agent 10.0g/ and the water-soluble silicone compound used in G ₁ ,
5.0 g of each cheese was treated individually in the same manner as G ₁ , and these cheeses were designated as G ₂ , G ₃ , and G _{4 ,} respectively. Furthermore, unprocessed yarn is
Let it be G ₀ . A smooth knitted fabric with a basis weight of 350 g/m was knitted using the above spun yarns of G ₀ to G ₄ . After knitting, a heat setting machine was used to set the knitting at 120° C. for 20 seconds, and then the same test as in Example 1 was conducted. As shown in Table 7, G ₁ satisfied all the performances.

[Table] Comparative example As a comparative example, 4.5g/
, 1g/softening and smoothing agent, water-soluble silicone
99g/(Blending ratio of softening and smoothing agent and water-soluble silicone = 1:99), A8
And so. In addition, 4.5g of water absorbing agent and 5.5g of softening and smoothing agent were added.
, 104.5g of water-soluble silicone/(blending ratio of softening and smoothing agent to water-soluble silicone = 1:99) was designated as A9, and the rest were Example 1.
processed in the same way. The results of evaluating the performance were as shown in Table 8. As is clear from the table, the knitting yarn breakage rates were high in all cases, and the objects of the present invention were not satisfied at all.

【table】

Claims (1)

[Scope of Claims] 1 Hydrophobic synthetic fibers are treated with a treatment liquid consisting of a water-absorbing agent, a softening and smoothing agent, and a water-soluble silicone, and in the treatment liquid, the softening and smoothing agent is added to the water-soluble silicone in a weight ratio. A treatment method for imparting water absorbency, antifouling properties, and sewability to hydrophobic synthetic fibers, characterized by treating with a system in which the ratio is 20 to 2:80 to 98. 2 Synthetic fibers produced by adding a water absorbing agent are treated with a treatment liquid consisting of a softening and smoothing agent and a water-soluble silicone, and the weight ratio of the softening and smoothing agent to the water-soluble silicone in the treatment liquid is 20 to 20. A treatment method for imparting water absorbency, antifouling properties, and sewability to hydrophobic synthetic fibers, characterized by treating the fibers with a system having a ratio of 2:80 to 98.