JPH06330461A - Fibrous structure excellent in water absorbing and quick-drying property - Google Patents

Abstract

PURPOSE:To obtain a fibrous structure, excellent in water absorption, quick- drying, lightweight and durability. CONSTITUTION:The fibrous structure is characterized by using hollow fiber, composed of a fiber-forming polymer (A) and having a through groove passing from the fiber surface to a hollow part (B) and the surface (D) of the hollow part to which silk protein sticks in at least a part thereof. Modified silk powder having <=2mum particle diameter is preferred as the silk protein and hollow fiber prepared by dissolving or decomposing the core part from core-sheath type conjugate yarn is preferred as the hollow fiber.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber structure which is highly durable, absorbs water, dries quickly, and is lightweight.

[0002]

2. Description of the Related Art Synthetic fibers such as polyester and polyamide are poor in hydrophilicity, water absorption and quick-drying property, and their improvement is desired. Many processing agents or their processing methods have been proposed to improve hydrophilicity and water absorption. Some of these effects are durable, but they are not sufficient and tend to deteriorate due to washing or the like.

In order to improve water absorption, a hollow fiber made of a fiber-forming polymer and having a through groove penetrating from the fiber surface to the hollow portion is disclosed in JP-A-56-169817 and JP-B-60-37203. Has been proposed to.
These hollow fibers are suitable for use in clothing fabrics because they have water-absorbing properties and are lightweight, but even with these fibers, of course, they have not been improved at all in terms of quick drying, Moreover, the water absorption performance was not sufficient.

[0004]

SUMMARY OF THE INVENTION It is very difficult to improve durable water absorption and quick-drying properties by simply using a processing agent or a processing method thereof. The present inventors have conducted extensive studies to solve the above problems, and as a result of fixing silk protein to a hollow fiber having a through groove that penetrates from the fiber surface to the hollow part, it surprisingly dramatically absorbs water. -The present invention was completed by finding that the quick-drying property and its durability are improved. An object of the present invention is to provide a durable fibrous structure that absorbs water, dries quickly, and is lightweight.

[0005]

That is, the present invention provides at least a hollow fiber comprising a fiber-forming polymer, having a through groove penetrating from the fiber surface to the hollow portion, and having silk protein attached to the hollow surface. A fiber structure characterized by being used for a part thereof.

A representative example of a method for producing a hollow fiber having a through groove used in the present invention is as follows. First, a core-sheath type composite yarn as shown in FIG. 1 is produced, and then a fiber structure is formed, and then the core component is dissolved or decomposed and removed to obtain a hollow fiber as shown in FIG. The hollowness of the obtained hollow fiber and the width of the through groove can be adjusted during the core-sheath composite spinning.

The spinning material used for the core portion in the composite spinning is not particularly limited as long as it is capable of composite spinning and convenient for the subsequent core polymer removing step. Convenient for the removal step, there are polymers that can be dissolved in water, polymers that can be decomposed / dissolved in an alkaline aqueous solution, polymers that can be dissolved in an acid, polymers that can be dissolved in a non-aqueous solvent, and the like.
Those which can be dissolved or decomposed with water or an aqueous alkali solution are particularly advantageous.

[0008] There are many water-soluble polymers, but for example, polyethylene oxide, polyethylene oxide / polypropylene oxide copolymers, their derivatives, segment copolymers of other polymer segments (eg polyester or polyamide), and the like. Examples thereof include alkylene oxide polymers, polyvinyl alcohols, polyvinylpyrrolidones, polyvinyl polymers such as polyacrylic acid salts, and water-soluble polyamides such as polybispropoxyethane adipamide and polybispropoxypiperazine adipamide.

Examples of the polymer which can be decomposed / dissolved in an alkaline aqueous solution include fiber-forming polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene oxybenzoate, and their copolymers and modified products. In particular, 1 to 6 for the above polyester
About 0% (weight), preferably 2 to 30%, most preferably 5 to 20% copolymerized or mixed polyalkylene oxides, or 3 to 10% 5-sulfoisophthalic acid sodium salt. The obtained product is easily decomposed by an alkaline aqueous solution. Similarly, a mixture of an aromatic polyester with a low melting point (200 ° C. or less) aliphatic polyester in an amount of about 5 to 50% is also very suitable as a core component.

Examples of the acid-soluble polymer include polyamides such as 6 nylon, 66 nylon, 610 nylon, 612 nylon, 12 nylon and copolymers thereof.

Examples of the non-aqueous solvent include chlorides such as trichlene and perkylene, aromatic compounds such as toluene and xylene, dimethylformamide and acetone, and examples of the polymer soluble in these include polyethylene, Examples thereof include polypropylene, polystyrene, polyvinyl chloride and polyacrylonitrile-based polymers.

The polymer used for the sheath portion is a known fiber-forming polymer, such as polyester type, polyamide type, polyacrylonitrile type and polyurethane type.

The hollowness of the fiber used in the present invention can be arbitrarily selected according to the purpose of use. For example, the hollowness can be 10 to 60% to obtain normal water absorption, and 40 to 80% to obtain a particularly large water absorption.

The water absorbency of the fiber used in the present invention is obtained by the hollow portion and the through groove. That is, water enters the hollow portion of the fiber from the surface of the fiber through the through groove and is retained therein.
Further, the water retained in the hollow portion can be diffused and evaporated to the outside through the through groove. Further, the water absorption and quick-drying properties of the fiber used in the present invention are remarkably improved and the durability is enhanced by the attachment of the silk protein.

The larger the width of the through groove, the easier the passage of water. However, if the width of the through groove is too large, the distinction between the hollow portion and the outside is lost and the water retaining force is lost. Therefore, the width of the through groove is preferably smaller than the diameter of the hollow portion (in the case of a non-circular cross section, the diameter of a circle having the same area). The width of the through groove is average and is usually 0.5 μm or more, preferably 1 μm or more, and the upper limit is usually about 1/3 of the fiber diameter. If the width of the through groove is too small, the passing speed of the silk protein processing liquid may be low, which is not preferable in some cases.

The cross section of the core-sheath type composite fiber that can be used in the present invention has various shapes. The compound may be concentric or eccentric. The core may be circular or non-circular, and the sheath may be circular or non-circular as well. Moreover, the number of cores may be one or more.

The fiber structure of the present invention uses at least a part of the hollow fibers as described above, and may be a mixture of other synthetic fibers, semi-synthetic fibers, natural fibers and the like, and may be woven. . In order to bring out the characteristics of the hollow fiber, it is preferable to use at least 20%, preferably 30% or more of the hollow fiber in the normal fiber structure. Examples of the fiber structure include woven fabric, knitted fabric, non-woven fabric, and flocked fabric.

For the fixation of silk proteins, the crystallinity is modified to 1/2 or less of that of natural silk, and the volume average particle diameter is 2 μm.
A water or organic solvent dispersion liquid of the following fine powder modified silk powder or a processing liquid obtained by adding a synthetic resin emulsion or a water-soluble polymer to the dispersion liquid is applied to the above-mentioned non-woven fabric and subjected to dry heat or wet heat treatment. The method is preferred (Japanese Patent Laid-Open No.
In addition, known methods such as treatment with an aqueous silk fibroin solution and a method of chemically fixing silk protein can be applied. The amount of silk protein adhered is usually 0.
It is 1 to 5.0% by weight. If it is less than 0.1% by weight, the desired water absorption and quick drying properties are not sufficient, while if it exceeds 7% by weight, the flexibility and feel of the woven or knitted fabric are deteriorated.

Examples of synthetic resin emulsions include acrylic resin emulsions and urethane resin emulsions. As the water-soluble polymer, a polymer having a polyalkylene oxide unit, a urethane polymer obtained by reacting a polyol with a diisocyanate, an epoxy compound obtained by condensing epichlorohydrin and a polyol are preferable, and applied to a cloth. The post-heat treatment shifts to a cured state.

In the method of the present invention, the silk proteins used include eyebrows, raw silk, eyebrows scraps, raw silk scraps, screws, fried cotton, silk cloth scraps, burettes, etc., in the presence of an active agent, if necessary, in the presence of warm water. Sintered silk which has been dried by removing sericin in warm water in the presence of an enzyme, regenerated silk coarse powder produced by a conventional method from silk fibroin aqueous solution, and silk fibroin obtained by heat treatment or salting-out of regenerated silk coarse powder And the fragile silk coarse powder produced by treating silk fiber with acid or alkali. The fine powder modified silk powder having a volume average particle diameter of 2 μm or less is produced by a high-speed shearing machine using the recycled silk coarse powder or the embrittled silk coarse powder with water or an organic solvent as a dispersion medium.

In the present invention, the method of applying the water containing the silk protein such as the fine powder modified silk powder to the water or the organic solvent dispersion liquid or the synthetic resin emulsion is not particularly limited, but the pad method and the spray method are used. , And the roller method can be applied. The cloth to which the silk protein is applied is dried, and further subjected to dry heat or wet heat treatment to form a strong film. And the dry heat treatment is 120 ° C. or higher, preferably 150 to 200 ° C.,
The moist heat treatment is performed at 90 ° C. or higher, preferably 110 ° C. or higher. Then, you may wash with warm water as needed. By washing, a proper rubbing action is added, the adhesion between the fibers is relaxed, and the soft finish is improved.

In the fiber structure of the present invention, it is necessary that the silk protein is attached to the surface of the hollow portion of the hollow fiber having a through groove penetrating from the surface of the fiber constituting the fiber structure to the hollow portion. As a result of earnest research on improvement of durability, the present inventors have found that the silk protein attached to the surface of the hollow portion of the hollow fiber has surprising durability against washing and the like, and arrived at the present invention. . The processed silk protein adheres to the fiber outer surface and the fiber hollow surface, but the antistatic agent on the fiber outer surface is easily removed by washing. In the present invention, the surface of the hollow portion is the portion D shown in FIG. 2, and the outer surface of the fiber is the portion E. The state of attachment of the silk protein varies depending on the processing agent or processing method, but is, for example, in the form of a thin film, particles or water drops.

The water absorption / quick drying property and durability in the present invention are measured and evaluated by the following methods. Water retention rate This is the percentage increase in weight after the scouring and air-dried fiber cloth was immersed in water at room temperature for 60 minutes and dehydrated for 3 minutes in a dehydrator of a domestic washing machine. Water absorption The "high water absorption", which indicates the diffusibility of water, was measured according to the Bayrex method (however, the measured value after 5 minutes is shown). Quick-drying The dehydrated cloth used for measuring the water retention rate was hung in an atmosphere of 22 ° C. and 65% RH for 10 minutes, and then the weight of the cloth was measured. The larger the weight reduction rate is, the better the quick drying property is. Durability Washing was carried out 10 times according to JIS L-0217 103 method, and the water absorption and quick drying properties were measured. In the present invention, it is preferable to have a water retention rate of 65% or more, a water absorption rate of 110 mm or more, and a quick-drying rate of 85% or more, although it depends on the yarn structure, the fabric weight and the design.

[0024]

INDUSTRIAL APPLICABILITY The fiber structure of the present invention has many features that it has excellent durability, absorbs water and dries quickly, and is lightweight and heat-retaining. It is suitable for innerwear, shirts, blouses and sports. Suitable for wear, tights, stockings, pajamas, etc.

[0025]

【Example】

Example 1 A copolymerized polyethylene terephthalate (hereinafter referred to as copolymerized PET) containing 17% of a polyether segment obtained by copolymerizing polyethylene glycol having an average molecular weight of 3000 was used as a core, and polyethylene terephthalate (hereinafter referred to as PE) was used.
(Hereinafter referred to as T) as a sheath, melt composite spinning was performed at a joining ratio (weight) of PET: copolymerized PET = 2: 1, and stretched 3.6 times to obtain a composite yarn F1 of 75 denier / 24 filaments. Then, a plain woven fabric was woven using the composite yarn F1 as a warp yarn and a weft yarn to obtain a woven fabric 1. The obtained woven fabric 1 was treated with an alkaline aqueous solution of sodium hydroxide 4% and 80 ° C. for 60 minutes to remove the copolymerized PET at the core of the composite yarn F1. The cross section of the treated yarn was as shown in FIG.

Further, as Comparative Example 1, 75 denier / 24 filament yarn of PET alone was spun and drawn, and the same was used as a warp and a weft to weave a plain woven fabric to obtain a woven fabric 2 and subjected to a scouring treatment. It was The densities of the woven fabrics 1 and 2 after the treatment were both 105 warps / inch and weft 87 threads / inch.

Using silk spinning waste as a raw material for silk fibroin, 100 gr. Marcel soap 30 gr. ,
Water 3000 gr. The solution was stirred and scoured at 95 to 98 ° C. for 3 hours to reduce the residual glue to 0.1% or less, washed with water and dried at 80 ° C. with hot air. Calcium chloride (CaCl ₂
.2H ₂ O) 100 gr. To 100 gr. And a 38 wt% calcium chloride aqueous solution 200 gr. Was prepared and heated to 110 ° C. 40g of refined silk spinning waste
r. Was added with stirring using a kneader for 5 minutes, and further stirred for 30 minutes to completely dissolve it. Next, inside diameter 20
Using a hollow fiber type dialysis device in which 2000 pieces of regenerated cellulose-based hollow fibers having a thickness of 0 μ, a thickness of 20 μ and a length of 500 mm are bundled and fixed (sealed) at both ends without blocking the hollow holes, At a rate of 0.1 l / hour and dialyzed against deionized water to obtain an aqueous fibroin solution. The fibroin concentration of the aqueous fibroin solution was 6.5%, and the residual calcium chloride content was 0.001%.
Met. The obtained fibroin aqueous solution 500 gr. Was stirred at a high speed with a stirring blade so as to give a shear deformation rate of 100 / sec or more. When stirring is continued for 2 to 3 hours, silk fibroin particles are precipitated next, and finally the whole is aggregated as an aggregate of small gel particles (15% crystallinity, 58% β structure) and separated from water to separate silk fibroin. Almost 100%
Regenerate at a yield of. Continue high speed stirring, then 30
% Concentrated ammonium sulfate aqueous solution at about 40 gr. As a result of mixing and further stirring for 1 hour to subject the silk fibroin crystals to α → β conversion, the gel body was crushed into small particles. Then, the gel was filtered off, washed with water and dried at 105 ° C. for 2 hours.
gr. A recycled silk crushed product was obtained (crystallinity 49
%, Β structure ratio 100%). The coarse powder 30 gr. Of water or organic solvent 270 gr. And wet pulverized with a high-speed shearing machine (rotor about 5000 rpm, shearing force about 45 to 600,000 / sec). The aqueous dispersion of finely powdered modified silk powder obtained by pulverization was a white emulsion and had a very smooth feel. As a result of measurement with a centrifugal sedimentation type particle size distribution measuring device (Shimadzu SA-CP3 type), the particle size distribution was 0.3 to 2.7 μm, and the average particle size was 1.1 μm.
Met. As for this product, this 10% dispersion was placed in a graduated cylinder and allowed to stand for 1 week, but no separation of the water layer and powder layer was observed and the dispersion state was very stable.

10 parts of a 10% aqueous dispersion of the modified silk powder described above, as a urethane resin emulsion, BONDIC 1610 (containing 40% solid content) manufactured by Dainippon Ink and Chemicals, Inc.
Fabrics 1 and 2 were immersed in a treatment liquid prepared by dispersing 2 parts in water so that the total amount was 100 parts, and picking up rate was 80%.
Squeeze to 120 ° C, pre-dry at 120 ° C, and heat at 11 ° C with HT steamer
A treatment was performed at 0 ° C. and a steam amount of 0.5 kg / cm ² for 10 minutes. In addition, the above-mentioned alkali-treated woven fabric 1 which does not adhere to silk protein is referred to as Comparative Example 2.

Example 2 8% polyethylene glycol having an average molecular weight of 4000
And sodium 5-sulfoisophthalate 4.3 mol%
Copolymerized PET obtained by copolymerizing and is used as a core, and the PET of Example 1 is used as a sheath. Coupling ratio copolymerized PET: PET =
Melt spinning was performed at 1: 1 and stretched 3.8 times to obtain a composite yarn of 75 denier / 24 filament. The cross section of the obtained composite yarn is as shown in FIG. 1.
It was set to 2. Thereafter, in the same manner as in Example 1, a plain woven fabric was woven using the composite yarn F2 as the warp and the weft (woven fabric 3), and the composite yarn F was obtained.
The core 2 of the copolymer PET was removed (the density of the woven fabric 3 after the treatment was 107 filaments / inch and weft 86 filaments / inch), and then the modified silk powder was fixed.

Example 3 In the same manner as in Example 1 except that the sheath was changed to nylon 6,
A composite yarn F4 was obtained, and then false twisting was performed while two yarns were combined to form a circular knit (knit 1), the copolymer PET of the core part was removed, and then the modified silk powder was fixed.

Further, as Comparative Example 3, nylon 6 alone 5
A circular knit was knitted using 0 denier / 24 filament yarn (knit 2), and then the modified silk powder was fixed.

[0032]

[Table 1]

[Brief description of drawings]

FIG. 1 is an example of a cross section of a core-sheath type composite fiber that can be used in the present invention, in which part C is a dissolution removal component.

FIG. 2 is an example of a hollow fiber having a through groove used in the present invention, where A is a fiber-forming polymer part, B is a hollow part, and D is a hollow part.
Indicates the surface of the hollow portion, and E indicates the outer surface of the fiber.

Claims (2)

[Claims] 1. A hollow fiber comprising a fiber-forming polymer, having a through groove penetrating from the fiber surface to the hollow portion, and having silk protein attached to the surface of the hollow portion is used at least in part. Fiber structure to do. 2. The fiber structure according to claim 1, wherein the silk protein is a modified silk protein powder having a size of 2 μm or less.