JP4340878B2 - Apparel product using non-woven fabric with high extensibility and high extensibility, and method for producing the same - Google Patents

Description

The present invention, by using a high extensibility and high elongation recovery nonwoven fabric, light and warmth, is excellent in wearing feeling, and the garment and the product which made it possible to significantly reduce the sewing cost It relates to a manufacturing method.

  Synthetic fibers have excellent characteristics such as high strength, fineness, abrasion resistance, softness, gloss characteristics, and clearness of dyeing, so that they can be used for clothing such as legwear such as pantyhose, innerwear, and sportswear. Has been used in favor of. In particular, innerwear is favored by the flexibility and drape of polyamide fibers, the smooth touch of the surface, the cool feeling when worn, and is often used as a lingerie or foundation for women.

  However, although synthetic fibers such as polyamide fibers and polyester fibers have excellent properties such as strength and dyeing fastness, they are inferior in hygroscopicity compared to natural fibers. For this reason, the water vapor generated at the time of wearing is not sufficiently absorbed, so that it is not released out of the clothes. Further, although the polyamide fiber has a higher equilibrium moisture content (hygroscopicity in the standard state) than that of the polyester fiber, it is still insufficient from the viewpoint of comfortable wearing (Patent Document 1: Japanese Patent Laid-Open No. 9-188917). Publication).

  In addition, natural fibers such as cotton and wool are preferred because of their texture and comfort. In particular, cotton having an appropriate hygroscopic property is often used for innerwear that directly hits the skin. However, cotton innerwear lacks aesthetics such as suppleness, drape, and gloss, and also has a poor smooth touch on the surface and a cool feeling when worn, especially for women's innerwear. Was unsuitable.

  By the way, generally used non-woven fabrics have little stretchability, especially when used for underwear, the fit is poor, the comfort is lowered, fraying of fibers and fraying from the non-woven fabric surface, sweating However, these non-woven fabrics are not necessarily preferred as materials for clothing products, and this is a factor that hinders the practical use of clothing products made of non-woven fabrics. It was one.

  Conventionally, for example, elastic rubber and thigh parts such as the waist and thighs of a disposable diaper have a natural rubber or polyurethane elastomer thread or tape to prevent wearing and preventing leakage. It has been used. However, these inevitably caused local strains, and were uncomfortable because they were gathered, and there were inconveniences such as leaving a red clamp mark when the diaper was removed. Furthermore, in a pants-type disposable diaper, attempts have been made to attach a highly elastic nonwoven fabric to the tightening portions on both sides, but there is still a complaint that it lacks a tight force.

  In addition, a cup is provided in the bust portion of the women's apparel to shape the breast into an ideal shape and to shape the entire bust beautifully. Nonwoven fabric or polyurethane foam is used as the constituent material of such a breast cup portion. Recently, mold cups molded into a predetermined shape have attracted attention, but mold cups made of polyurethane fibers have the disadvantage of changing to yellow over time, although they are excellent in terms of volume and elasticity. In addition, the touch is not always smooth, and it has a drawback that it gives a harsh feel when worn. Moreover, since the air permeability is poor, there is a drawback that it will be steamed if worn for a long time. In addition, a non-woven fabric that has been pressure-molded is easy to mold, but its stability is poor, so when a large force is applied from the outside or the shape of the part to which a large pressure is applied during washing collapses. Disadvantages remain, and dissatisfaction remains.

  Furthermore, in clothing products, not only the material cost but also the sewing cost is required, so even if a non-woven fabric is used, the cost cannot be sufficiently reduced, which impedes practical application. For example, in the case of male briefs, two front cloths are stitched so as to form a front fit, and then the back cloth is stitched to both sides of the front cloth, and further rubberized, end-treated, and inseam stitched together Etc., many processes are necessary. In addition, innerwear such as shorts and girdles are manufactured by sewing knitted fabric with a large tightening force on areas that require a strong tightening force such as the hem and waist, and the hip hem line is displaced due to bending and stretching movements. In order to go up, it cuts into a shape that stretches toward the center of the foot and deepens the wrapping of the hips, or obtains a long and large dart by the cutting method. However, as much as it stretches in the sitting position, it becomes slack in the upright position, and even if the person has the same size around the hip, the shape is ten people and there are few people who just fit the hip, and such clothing The product has a problem that it takes time for the sewing work, and the sewing part gives the wearer an uncomfortable feeling and is not preferable in appearance.

  Furthermore, in women's clothing such as women's bras and baby dolls, when sewing bust cups and side cloths, when joining the ends of body parts that are doubled with thin fabrics, Since the bias tape is placed on the back side of the joint portion and sewn, the thickness of the joint portion increases, and the joint portion presses a part of the woman's skin, so that the feeling of wear is reduced. In addition, in order to enhance the decorativeness of women's clothing, if decoration is applied to the surface side with tape etc., the thickness will be increased by that amount and the rigidity will be increased, so that it will not bend smoothly when attaching or detaching women's clothing, and it will be removable There is also a problem that the image quality decreases (Patent Document 2: JP-A-2002-69708).

  As garment products having stretchability and stretch recovery properties, weft knitted fabrics using polyurethane elastic fibers are widely used. However, when weft knitted fabric mixed with polyurethane elastic fibers is repeatedly stretched, it becomes deformed and becomes uneven knitted fabric, and the yarn is pulled out from the cut part. Problems such as “run, densen” or “pilling”, “snugg”, “curl” in which the knitted fabric is curved, and so-called “slip-in” in which polyurethane elastic fibers come out are likely to occur. As countermeasures against these problems, for example, the end of the cloth is folded, sewn with another cloth or a stretchable tape, or threaded. Such work is a considerable burden in sewing clothes, and when worn, convexities, steps, seams, etc. directly contact the skin and cause skin damage, loss of touch, and loss of comfort. There was a problem.

  On the other hand, various studies have been made on polyurethane elastic fiber nonwoven fabrics, and techniques for improving air permeability, extensibility, strength, and the like have been proposed (Patent Documents 3 to 6: Patent Nos. 2711257 and 2766474, No. 3255615 and No. 3098681). Moreover, as a clothing product using a nonwoven fabric made of thermoplastic elastomer resin fibers such as polyurethane elastic fibers, Japanese Patent Application Laid-Open Nos. 11-43814 and 2003-201614 (Patent Documents 7 and 8) have hair caps. Proposed.

  Recently, there has been a strong demand for a stretchable nonwoven fabric that follows the body's expansion and contraction and fits well to the body, and that effectively exhibits heat retention, and can be used with a portion of the nonwoven fabric cut. The demand for enjoying casual clothes is growing. For example, in Japanese Patent Application Laid-Open No. 2003-147606 (Patent Document 9), a nonwoven fabric made of a thermoplastic resin fiber such as polyester or nylon is cut into a shape such as an undershirt or a brief, and the cut parts are heat-sealed. Clothing products obtained by joining have been proposed. However, these products are not sufficient in terms of lightness, heat retention, wearing feeling, and the like, and further improvements have been desired.

In addition, as a well-known document relevant to this invention, there exist the following.
Japanese Patent Laid-Open No. 9-188917 JP 2002-69708 A Japanese Patent No. 2711257 Japanese Patent No. 2766474 Japanese Patent No. 3255615 Japanese Patent No. 3098681 JP 11-43814 A JP 2003-201614 A JP 2003-147606 A

The present invention has been made in view of the above circumstances, using light and warmth, excellent wearing feeling and high extensibility and high elongation recovery nonwoven fabric made it possible to significantly reduce the sewing cost clothing An object is to provide a product and a method of manufacturing the product.

As a result of intensive studies to achieve the above object, the present inventor is a product in which fabric parts taken according to the shape of the product are joined at the joint, and at least a part of the part is high elongation resistance and high elongation Ru consists recovery nonwoven parts clothing fee product excellent in light weight because the nonwoven fabric is used, that said nonwoven fabric is breathable, breathable, it is also good thermal insulation and the like, this If, by using the stretch-elongation recovery of high Ipoh polyurethane fiber-containing nonwoven fabric, fit, good wearing feel, yet it was found that beautiful in appearance product obtained. In addition, it has been found that it is economical because it can save most of the labor and cost required for sewing by joining predetermined joints between parts by thermal fusion, etc. The present invention has been made.

Accordingly, the present invention provides the following clothing products and methods for producing the same.
(1) a plurality of fabric parts taken form in accordance with the product shape Ri Na are joined at the junction, at least a portion of the part, including the polyurethane fibers is an average filament diameter 0.5~60μm A clothing product composed of non-woven parts with high extensibility and high extensibility ,
The polyurethane fiber is obtained by melt spinning a polymer obtained by reacting polyol, diisocyanate and low molecular weight diol, and contains 30% by mass or more of polyether diol with respect to the total amount of polyol.
The nonwoven fabric part has a three-dimensional shape obtained by spraying the polymer on a three-dimensional object from a position 10 to 50 cm away, or has a sheet shape obtained by spraying on a net, and has a basis weight of 20 to 500 g. / M ² , a clothing product having a thickness of 0.05 to 3 mm .
(2) The polyurethane fiber is obtained by melt spinning a polymer obtained by reacting a both-end isocyanate group prepolymer obtained from polyol and diisocyanate with a both-end hydroxyl group prepolymer obtained from polyol, diisocyanate and low molecular weight diol. The product according to (1) .
(3) The product according to (1) or (2) , wherein the joint is joined by thermal fusion .
(4) The product according to any one of (1) to (3), wherein the content of the isocyanate group contained in the yarn immediately after spinning of the polyurethane fiber is 0.1 to 3.0% by mass .
(5) Product according to any of the preceding Kipo polyurethane textiles is the side-by-side type composite fiber (1) to (4).
( 6 ) The product according to any one of (1) to ( 5 ), wherein the nonwoven fabric has a 50% elongation recovery rate of 60% or more .
(7 ) Any of (1) to (6) which is a brief, panty, shorts, undershirt, camisole, girdle, bra, spats, body suit, sanitary shorts, underwear, swimsuit, sports tights, supporter or leotard The product described in Crab .
(8) A clothing product comprising a single high-stretchability / high-stretch recovery nonwoven fabric containing polyurethane fibers having an average filament diameter of 0.5 to 60 μm,
The polyurethane fiber is obtained by melt spinning a polymer obtained by reacting polyol, diisocyanate and low molecular weight diol,
The nonwoven fabric has a three-dimensional shape obtained by spraying the polymer on a three-dimensional object from a position 10 to 50 cm away, and has a basis weight of 20 to 500 g / m ² and a thickness of 0.05 to 3 mm. And clothing products.
(9) The product according to (8), wherein the content of isocyanate groups contained in the yarn immediately after spinning of the polyurethane fiber is 0.1 to 3.0% by mass .
(10) The product according to (8) or (9), wherein the polyurethane fiber is a side-by-side type composite fiber.
(11) The product according to any one of (8) to (10), wherein the nonwoven fabric has a 50% elongation recovery rate of 60% or more.
(12) Any of (8) to (11) which is a brief, panty, shorts, undershirt, camisole, girdle, bra, spats, body suit, sanitary shorts, underwear, swimsuit, sports tights, supporter or leotard The product described in Crab.
(13) After obtaining a plurality of fabric parts taken shape according to the shape of the product, a process for the preparation of garments you joined at the junction to assemble the parts, at least some of said parts (1 ) to (6) the method of producing apparel product according to any of characterized that you configuration with high extensibility and high elongation recovery nonwoven parts according (1) to (7) to one of the.
(14) A method for producing a clothing product comprising a single nonwoven fabric shaped according to the shape of the product, wherein the nonwoven fabric has high extensibility and high elongation recovery according to any one of (8) to (11) A method for producing a clothing product according to any one of (8) to (12), wherein a non-woven fabric is used.

  The nonwoven fabric of the present invention is excellent in pilling resistance and snag resistance, and is also excellent in fray resistance and curl resistance at the cut end during cutting. In addition, the non-woven fabric product of the present invention uses a high stretch / high stretch recoverable non-woven fabric, so that it has excellent wearing feeling, is light and has high heat retention, and is also visually attractive. Moreover, according to the manufacturing method of the present invention, the sewing cost can be significantly reduced.

  Hereinafter, the present invention will be described in more detail. The product of the present invention is a product in which fabric parts taken according to the shape of the product are joined at a joint, and at least a part of the part is highly stretched. It is a product characterized by being composed of high-strength and highly stretchable nonwoven fabric parts.

  Here, the product according to the present invention is an industrial material such as a clothing product such as underwear or sportswear, a sanitary product such as a disposable diaper, a filter, a protective cover, or a wiper, and has extensibility and stretch recovery. Although it is used in the required field, it is particularly preferably used as a clothing product, especially underwear.

  As the fabric parts constituting the product, parts made of woven or knitted fabric or parts made of high stretchability / high stretch recovery non-woven fabric can be used, but in the present invention, at least some of these parts are high. Parts made of stretchable and highly stretchable nonwoven fabric are used. Examples of such a non-woven part include (1) a non-woven fabric divided into a predetermined shape by cutting or the like, and (2) a non-woven fabric obtained by spraying a molten elastomer of a thermoplastic resin on a three-dimensional object. (3) A non-woven fabric placed in a molding die and three-dimensional molded, (4) a molded product in a heated atmosphere, and the like can be used. One or a plurality of parts made of these nonwoven fabrics can be used depending on the shape of the target product, and the parts (1) to (4) can also be used in combination.

  When using parts made of non-woven fabric obtained by spraying a thermoplastic elastomer on a three-dimensional object, the molten elastomer is ejected from a spray device, and the trickle is continuously ejected onto the surface where the fiber laminate is to be formed. However, the molten elastomer discharged from the nozzle rapidly cools to become a fibrous solid and reaches the surface of the three-dimensional object. In this case, it is preferable to apply the oblique angle from the nozzle to the three-dimensional object since the thickness of the nonwoven fabric can be made uniform. In addition, the accumulation of the three-dimensional object can be stabilized by forcibly exhausting the gas flow from the nozzle from the back or side of the three-dimensional object.

  Further, the distance from the tip of the nozzle to the three-dimensional object and the spraying range are not particularly limited, and are appropriately set depending on the ability of the spray device, etc., but it is preferable to spray from a position away from the three-dimensional object by 10 to 50 cm. In addition, by adjusting the spraying time and the discharge rate, it is possible to obtain non-woven fabrics with different density and different shades, arbitrarily changing the product elongation, stretch recovery, back power, Diversification can be enabled.

  In addition, as equipment for extruding and discharging molten resin (molten elastomer) or resin solution into a fibrous form as a narrow flow from the die, for example, a surface coating apparatus known as curtain spray of hot melt adhesive can be used. Specifically, ITW Dynatech's Dynafiber System, Sun Tool Corporation, Nordson Corporation's Curtain Spray System, and the like can be suitably used.

  For example, in the case of a breast cup for women (for brassiere, body suit, bustier, bra camisole, bra slip, etc.), it is preferable to set the spray amount to 0.1 to 40 g / min, for example, the product mass is 20 g. In this case, the spraying time is preferably about 5 to 60 seconds. Moreover, in the case of shorts or pants, it is preferable to set the spray discharge amount to 0.1 to 30 g / min. For example, when the product mass is 10 g, the spraying time is preferably about 5 to 60 seconds.

  By performing dry heat treatment or wet heat treatment on the nonwoven fabric obtained by spray molding in this way, the fusion and adhesion of fibers in the nonwoven fabric are enhanced, the solid-layer reaction is advanced, or the formability is increased. Can be increased. In addition, for the purpose of facilitating the separation of the three-dimensional object and the nonwoven fabric obtained by spray molding, the three-dimensional object is composed of a highly releasable material, the separation is promoted by changing the surface temperature of the three-dimensional object, A release agent may be applied to the surface of the three-dimensional object. Furthermore, a release agent can be added to the resin constituting the nonwoven fabric, and various nonwoven fabrics obtained by various spray molding methods can be used.

  In this case, as the release agent, for example, a silicone compound can be used, and thermosetting silicone mainly composed of dimethylpolysiloxane (trade names: KS-776, KS-847, both manufactured by Shin-Etsu Chemical Co., Ltd. Name: TPR-6700, manufactured by Toshiba Silicone Co., Ltd.) or silicone containing fine silica particles in dimethylpolysiloxane (trade names: SD-7230, SD-723, etc., manufactured by Toray Silicone Co., Ltd.) Or modified silicones (trade names: X-62-9022, KS-883, KS) in which 1 to 10% by mass of dimethylpolysiloxane having a phenyl group-substituted alkyl group at the polymer terminal is added to a mixture of alkyd resin and melamine resin -881 etc., manufactured by Shin-Etsu Chemical Co., Ltd.), etc., can be selected from known release agents. As a method for applying the release agent, for example, a spin coating method, a spray coating method, a bar coating method, a gravure coating method, a reverse coating method, a comma coating method, or the like can be used. The coating is preferably performed so that the film thickness after drying is 0.05 to 1.0 μm.

  When using nonwoven fabric parts obtained by placing a nonwoven fabric in a molding die (thermal mold) and three-dimensionally molding (thermoforming), high-frequency heating, electrothermal heating or steam heating and vacuum forming, compressed air molding or hot plate molding Parts having a desired shape obtained by a known combination method can be used. Molding conditions such as temperature and pressure when molding these parts are appropriately selected depending on the thickness, shape, etc. of the target part, but the temperature is preferably close to the melting point or softening point of the resin that is usually used. In general, the temperature is preferably set to 80 to 280 ° C. For example, when a polyurethane fiber is used as the fiber constituting the nonwoven fabric, the temperature is preferably set in a range of 120 to 250 ° C. in consideration of deterioration due to thermal decomposition. The molding time is usually preferably 15 to 300 seconds, more preferably 20 to 180 seconds.

  The nonwoven fabric introduced into the heat mold is heated to near the temperature of the heat mold, heat fixed, and molded. In this case, if the molding temperature is too low, the plasticizing effect is not exhibited and the shape may not be maintained. On the other hand, if the temperature is too high, heat fusion of the fibers in the non-woven fabric will progress, and it will become a film, harden due to thermal deterioration, yellowing, stretch power will be lost, etc. There is a fear.

  In addition, by performing dry heat treatment, wet heat treatment, etc. on three-dimensionally formed nonwoven fabrics, it is possible to increase the fusion and adhesion between fibers in the nonwoven fabric, to promote solid layer reaction, or to improve the formability it can. For the purpose of facilitating separation between the thermal mold and the nonwoven fabric, the thermal mold is made of a highly releasable material, the separation is promoted by changing the surface temperature of the thermal mold, or the mold is released on the surface of the thermal mold. An agent can also be applied. Furthermore, a release agent can be added to the resin constituting the nonwoven fabric, and various nonwoven fabrics obtained by various three-dimensional molding methods can be used. In addition, a mold release agent can be selected and used from a well-known thing timely.

  In the present invention, it is also possible to use parts obtained by thermoforming without using a thermal mold. After introducing a nonwoven fabric into a heated atmosphere, it can be heated to a desired shape simply by performing deformation such as folding. Molded parts can be obtained. In this case, the temperature of the atmosphere is preferably close to the melting point or softening point of the resin that is normally used, and is generally set to 80 to 280 ° C. For example, when a polyurethane fiber is used as the fiber constituting the nonwoven fabric, the temperature is more preferably set in a range of 120 to 250 ° C. in consideration of deterioration due to thermal decomposition.

Here, the nonwoven fabric used for the above parts is not particularly limited, but a nonwoven fabric obtained by wet, dry, melt spinning, reactive spinning, or the like can be used.
In addition, the shape of the fibers used in these nonwoven fabrics is not particularly limited, and short fibers, long fibers (filaments), etc. can be used. In the present invention, manufacturing is easy and productivity is high. Nonwoven fabrics composed of long fibers can be preferably used from the viewpoints of less fuzz and resistance to fraying.

  It does not specifically limit as a long-fiber nonwoven fabric, The thing obtained by various formats can be mentioned. For example, (i) non-woven fabric (spun bond method) formed by spinning, opening, collecting and entanglement of thermoplastic elastomer, (ii) opening and opening thermoplastic elastomer together with high-temperature and high-pressure air A non-woven fabric formed by arrangement (melt blow method), (iii) a non-woven fabric (flash spinning method) formed by jetting thermoplastic elastomer from a die and having a unique network fibril, (iv) a long fiber bundle of thermoplastic elastomer Nonwoven fabric formed by stretching and crimping, opening and widening (tow opening method), (v) Foam extrusion of thermoplastic elastomer, foaming bursting, laminating and spreading (burst) The fiber method) can be used. In the present invention, from the viewpoint of easy production and high productivity, among these, a long fiber nonwoven fabric obtained by a melt blow method and a spun bond method can be preferably used.

  In the melt blow method, the stringiness of the thermoplastic elastomer is not so strongly required, so that a fiber nonwoven fabric having an extremely thin fiber diameter can be easily obtained. That is, in the melt-blowing method, the molten polymer is discharged from the spinning nozzle, and the discharged molten polymer is made fine by ejecting the heated gas from the gas outlets arranged on both sides sandwiching the nozzle outlet. The thinned fiber is sprayed onto a net conveyor that moves without substantially converging, and is separated from the gas flow and laminated on the net.

  The laminated fibers are joined at the contact point between the fibers by the heat of their own, and become a so-called web-like product. In this case, that is, pressurizing with a pressure roller before cooling, the joining may be strengthened. it can. Moreover, after a fiber cools, it can also heat-press using a heat-pressure roller, and can also strengthen joining. In any case, the web-like material laminated as described above and bonded between the fibers moves together with the net conveyor, and then is transferred from the net conveyor to another device for scraping, and finally moves. Taken on a roller.

  In the case of a nonwoven fabric obtained by the melt blow method, the adhesion state between filaments greatly affects the properties of the nonwoven fabric such as tensile strength. The adhesive strength between filaments is the extrusion temperature from the nozzle (the temperature of the molten polymer in the discharged state), the temperature of the high-temperature gas flow for thinning and cooling the extruded molten polymer, the wind speed, the air volume, and between the spinning nozzle and the conveyor net. And the exhaust speed of the gas flow from the conveyor net can be adjusted.

  The discharge (spinning) temperature of the molten polymer extruded from the spinning nozzle is preferably set to be equal to or higher than the melting point or softening point of the resin to be used, but usually 10 ° C. or higher is more preferable. For example, in the case of polyurethane, the upper limit is set in consideration of thermal decomposition of urethane bonds, and the upper limit is around 280 ° C. If the discharge (spinning) temperature is too low, the fineness of the laminated filaments will increase, the adhesion between the filaments will be poor, and if it is severe, the polymer will not melt and clogging of the nozzle may occur. If it is too large, the adhesion between the laminated filaments may be too strong, or the filaments may be converged and laminated. In a severe case, the molten polymer extruded from the nozzle may foam due to thermal decomposition and fail to form a filament.

  In this case, the average fiber diameter of the obtained filament is usually preferably from 0.5 to 60 μm. For example, in the case of polyurethane fiber, it is preferably from 3 to 60 μm, more preferably from 5 to 30 μm. The thinner the fiber diameter, the softer the nonwoven fabric, but if the fiber diameter is too thin, the tear strength may decrease. In particular, for inner applications, the finer fineness is preferable in terms of touch and water resistance, and the average filament diameter is preferably 5 to 15 μm.

  Moreover, the uniformity of the web can be ensured by appropriately adjusting the distance between the spinning nozzle and the conveyor net. For example, in the case of polyurethane, it is preferably set to 15 to 40 cm, more preferably 20 to 30 cm. If the distance between the spinning nozzle and the conveyor net is too large, the filaments may adhere to each other (stack) before lamination, and the web uniformity may be reduced. In addition, the adhesion between filaments becomes poor in a laminated state, and the form stability as a nonwoven fabric becomes poor, and various physical properties such as breaking strength may naturally decrease. On the other hand, if the distance between the spinning nozzle and the conveyor net is too short, the filaments may be strongly bonded to each other, or in some cases, the adhesion may be too strong to form a film and impair the good tactile feel of the nonwoven fabric.

The temperature, the wind speed, and the air volume of the high-temperature gas flow for thinning and cooling the extruded molten polymer can be appropriately changed, but the temperature is preferably near the temperature of the discharged molten polymer. If the temperature difference between the spinning nozzle and the high-temperature gas flow is large, control of the nozzle temperature becomes difficult, which is not preferable.
Regarding the air volume, it is advantageous to reduce the amount used from the viewpoint of productivity, but it is increased to such an extent that the molten polymer can be reduced to the desired fineness. Although the wind speed varies depending on the size of the discharge port, generally, it is advantageous to reduce the fineness by decreasing the discharge port area and increasing the wind speed. In addition, there is a case where the air volume and the wind speed are increased within a range that does not hinder the accumulation of filaments for the purpose of changing the texture of the nonwoven fabric.

In addition, the high-temperature gas flow usually flows from the vicinity of the nozzle outlet while accompanying the molten polymer, but the high-temperature gas flow can also be ejected stepwise or from a plurality of locations along the filament accumulation direction. The exhaust speed of the gas flow from the conveyor net is also a factor that determines the state of adhesion between the filaments. Usually, it is preferable to exhaust the same amount or more as the high-temperature gas flow, and an air volume that can stabilize the filament accumulation state is more preferable. .
In the manufacturing stage, a stable non-woven fabric can be obtained by finely adjusting the measured value of the filament accumulation point temperature, especially by the extrusion temperature from the nozzle (the temperature of the molten polymer in the discharged state) and the distance between the spinning nozzle and the conveyor net. Manufacture is possible.
In the manufacturing stage, the temperature at which the filaments are accumulated is measured, and especially when the spinning temperature is kept within the target range, such as the extrusion temperature from the nozzle (resin temperature of the molten polymer in the discharged state) and the distance between the spinning nozzle and the conveyor net. Stable production of the nonwoven fabric becomes possible.

  Although the resin used contains moisture, if the melt blow is performed in a state containing moisture, the resin will be decomposed, and therefore it is necessary to perform a drying process prior to ejection. Although the water content of the resin is desirably low, for example, in the case of a polyurethane resin, the content is preferably 0.2% by mass or less, and more preferably 0.05% by mass or less.

  The nonwoven fabric obtained by the spunbond method is suitable for clothing and is advantageous in terms of cost. In the spunbond method, a thermoplastic polymer is spun by melt spinning, etc., and filaments continuously drawn from the spinning nozzle are randomly accumulated in a mat shape to form a web, which is used to melt or soften the resin used. A nonwoven fabric can be obtained by heating in the vicinity of the point and entanglement treatment. For example, in the case of polyurethane, the nonwoven fabric is preferably obtained by heating to 150 to 280 ° C., more preferably 180 to 250 ° C., and entanglement treatment.

  The feeding device for quantitatively supplying the molten thermoplastic polymer includes a feed pump for quantitatively feeding the molten polymer through a hopper filter that can be continuously melted by an electric heater, and a supply hose for supplying the molten polymer. Composed. The feed pump is not particularly limited as long as it can feed a molten polymer at a constant and constant pressure, such as a gear pump, a piston pump, and a screw pump. Further, it is more desirable that the supply line has a heating device in which the temperature of the molten polymer is heated to a constant temperature and can be controlled within a certain viscosity range. The heating temperature is preferably at least 20 ° C. or higher than the softening point of the thermoplastic polymer, and more preferably 40 to 60 ° C., but it should be adjusted in consideration of the thermal stability of the thermoplastic polymer. Can do.

  Furthermore, the shape of the conveyor net for laminating or accumulating discharged filaments is not limited to a flat surface, regardless of whether it is a melt blow method or a spun bond method. Can be produced continuously. Furthermore, the laminate or the accumulated product may be wound up as it is, or a nonwoven fabric sheet that is continuously and complicatedly shaped while being cut at a predetermined length as necessary can be produced.

  Uses non-woven fabric-containing multi-layer sheets obtained by continuously or discontinuously feeding other sheets, films, knitted fabrics, woven fabrics and non-woven fabrics to a conveyor net for laminating or accumulating discharged filaments, and laminating or accumulating filaments thereon. You can also

  As a nonwoven fabric used by this invention, what processed the nonwoven fabric obtained by the above by the well-known entanglement processing method can be utilized. For example, a nonwoven fabric in which fibers are fused by heat embossing, a nonwoven fabric in which fibers are fused by ultrasonic waves, a nonwoven fabric in which fibers are entangled using a water jet, a nonwoven fabric in which fibers are entangled by hot air through, a needle punch Among them, there are non-woven fabrics in which fibers are entangled, and among these, non-woven fabric subjected to heat embossing treatment, ultrasonic fusion or non-woven fabric that has been heat-sealed can be preferably used.

The basis weight and thickness of the nonwoven fabric used in the present invention are appropriately selected depending on the target product, but in clothing products, for example, products for shorts, the basis weight is preferably about ²⁰ to 500 g / m ² , more preferably. It is about 40 to 300 g / m ² . Moreover, it is preferable that thickness is about 0.05-3 mm, More preferably, it is about 0.1-2 mm.

  In addition, the elongation rate (or elongation) is preferably 40 to 650%, more preferably 50 to 550%, and after 50% elongation from the viewpoint of following the movement of the body and not losing clothes. The recovery rate is preferably 60% or more, more preferably 70% or more. When the 50% elongation recovery rate is less than 60%, the force for mounting and fixing is weak, and a fit that follows the expansion and contraction of the body may not be obtained. The upper limit of the 50% elongation recovery rate is 100%, but the value may be intentionally lowered in order to give a soft fit feeling, and it can be used depending on the purpose and purpose. When the elongation rate is below the above value, the fit to the body may be deteriorated. When the elongation rate is exceeded, the feeling of wear may be deteriorated due to stress reduction during use, or the wear feeling may be deteriorated when repeatedly used. The method for measuring the 50% elongation recovery rate is as described later.

  Moreover, it is preferable that the nonwoven fabric used for this invention has high yellowing resistance. As the nonwoven fabric having yellowing resistance, (1) a nonwoven fabric containing fibers made of a resin composition containing various stabilizers, (2) a nonwoven fabric containing fibers obtained by changing the raw material of the resin, (3 ) Non-woven fabrics containing fibers obtained by combining the blending of various stabilizers and the change in the raw material of the resin can be mentioned, and any of them can be used.

  Here, for example, in the case of polyurethane, heat resistance, oxidation resistance, and light resistance are problems, and particularly deterioration and discoloration occur during molding processing or use of the product. Therefore, antioxidants, light stabilizers, etc. Many stabilizers and combinations thereof have been developed. Among them, it is desirable to add a stabilizer such as a hindered phenol-based antioxidant, a hindered amine-based light stabilizer, a benzotriazole-based ultraviolet absorber, and a semicarbazide-based compound.

  What is necessary is just to mix | blend the quantity which exhibits an effect as the mixture ratio of various stabilizers. There is no restriction | limiting in particular as a method of mix | blending a stabilizer with a polyurethane polymer, It can be mix | blended in the arbitrary steps of a polyurethane polymerization process. For example, it may be added directly to the polyurethane polymer after the polyurethane polymerization and before the molding step. Further, a stabilizer may be added to the raw material of the polyurethane polymer. Furthermore, the stabilizer can be added after being dispersed or dissolved in a solvent.

  Specific examples of the hindered phenol antioxidant include, for example, 3,9-bis (2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy) -1,1. -Dimethylethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid , Pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) ) Propionate] and the like.

  Specific examples of the hindered amine light stabilizer include, for example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4-piperidyl). Sebacate, dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine condensate and the like.

  Specific examples of the benzotriazole ultraviolet absorber include 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole and 2- (3-t-butyl-5-methyl-2-). Hydroxyphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, and the like.

  Specific examples of the semicarbazide compound include 1,6-hexamethylenebis (N, N-dimethylsemicarbazide), 1,1,1 ′, 1′-tetramethyl-4,4 ′-(methylene-di-1, 4-phenylene) disemicarbazide and the like.

  Moreover, high yellowing resistance can be obtained by changing the diisocyanate used when synthesizing the polyurethane to a non-yellowing organic polyisocyanate. A variety of non-yellowing organic polyisocyanates can be used, and those that are liquid at room temperature and do not need to be diluted with a solvent are particularly preferable. Examples include hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate, and their burette, isocyanurate, and carbodiimide modified products. Two or more kinds of these polyisocyanates can be used in combination.

  As will be described later, 4,4′-diphenylmethane diisocyanate is generally used as the diisocyanate usually used for the synthesis of polyurethane because of its reactivity with polyols and physical properties of elastic bodies. Since it has a ring, it is easily discolored and yellowing is prevented by the stabilizer described above. In addition, as a method for improving yellowing resistance while maintaining excellent physical properties of 4,4'-diphenylmethane diisocyanate, a non-yellowing organic polyisocyanate can be used in combination. Furthermore, yellowing resistance can be satisfied by maintaining the excellent physical properties of 4,4'-diphenylmethane diisocyanate by using the additives described above in combination.

  The yellowing resistance of the nonwoven fabric obtained by such a method can be measured by the following method. For example, the NOx yellowing resistance of a polyurethane fiber-containing nonwoven fabric can be obtained by determining the Δb value of the nonwoven fabric before and after being exposed to 650 ppm NOx atmosphere at 25 ° C. for 1 hour. Here, the b value is a measured value of the degree of yellowing change as will be described later, and this value is preferably 12 or less, more preferably 10 or less. When a non-woven fabric having a Δb value exceeding 12 is used for a product that may be exposed to NOx, it may be insufficient in terms of yellowing resistance.

  Chlorine yellowing resistance of a polyurethane fiber-containing nonwoven fabric can be obtained by determining the Δb value of the nonwoven fabric before and after being treated with an aqueous solution having an effective chlorine concentration of 20 ppm for 3 hours. In this case, the Δb value is preferably 25 or less, and more preferably 10 or less. When a nonwoven fabric having a Δb value exceeding 25 is used in a product that may be exposed to chlorine water, it may be insufficient in terms of yellowing resistance.

The light yellowing resistance of the polyurethane fiber-containing non-woven fabric can be obtained by determining the Δb value of the non-woven fabric before and after being irradiated for 32 hours with an ultraviolet fade meter U48S (temperature 46 ° C., humidity 50% RH) manufactured by Suga Test Instruments. In this case, the Δb value is preferably 15 or less, more preferably 10 or less. When a non-woven fabric having a Δb value exceeding 15 is used for a product that may be directly exposed to light, it is insufficient in terms of yellowing resistance.
The lower limit value of the Δb value is not particularly limited, but is usually 0 or more in any method.

When the product of the present invention is used particularly for apparel applications, the temperature retention of the nonwoven fabric used in the present invention is preferably 0.5% or more from the viewpoint of maintaining body temperature. For example, in the case of polyurethane fibers, 1 to 20% is preferred. Moisture permeability is preferably at 600g / m ² · 24HR or more, for example, be the case of using the polyurethane fibers, 1,500~8000g / m ² · 24HR because of high fitness to the skin More preferred. The air permeability is preferably 100 mL / cm ² · sec or more. For example, when polyurethane is used, it is more preferably 1,000 mL / cm ² · sec or more for the same reason as described above. Below these conditions, peeling or the like may occur due to water or sweat, and when exceeding these conditions, excessive performance may be maintained, which may be undesirable. In addition, the measurement method of a heat retention rate, moisture permeability, and air permeability is mentioned later.

  The fabric parts made of woven or knitted fabric used in the present invention are not particularly limited, and natural fibers such as cotton, hemp, wool, silk, rayon, cupra, polynosic, high-strength regenerated cellulose fibers (for example, trade name Tencel), etc. Recycled fiber, Semi-regenerated fiber such as acetate, Nylon, Polyester, Acrylic, Polypropylene, Polyurethane, Polysynthetic fiber, etc. One or two or more types of parts composed of warp knitted fabrics such as circular knitted fabrics such as pearl knitting, other weft knitted fabrics, combed knitted fabrics, denvi knitted fabrics, cord knitted fabrics, and atlas knitted fabrics can be used.

  Here, the fiber used for the yarn constituting the nonwoven fabric used in the present invention is preferably a thermoplastic elastomer fiber, and the type thereof is not particularly limited as long as the object of the present invention can be achieved. Examples thereof include fibers made of thermoplastic elastomers such as elastomers, polyamide elastomers, polystyrene elastomers, and polyolefin elastomers. These thermoplastic elastomer fibers can be used individually by 1 type or in combination of 2 or more types as appropriate. In the present invention, among these, thermoplastic polyurethane fibers can be suitably used from the viewpoints of stretchability and thermoformability.

  The composition of the polyurethane fiber used in the present invention, the production method and the like are not particularly limited. For example, a polyol and an excess molar amount of diisocyanate are reacted to produce a polyurethane intermediate polymer having isocyanate groups at both ends, A polyurethane solution (polymer solution) is produced by reacting a low molecular weight diamine having active hydrogen that can easily react with an isocyanate group of the intermediate polymer or a low molecular weight diol in an inert organic solvent, and then the solvent is removed to remove the yarn. A method of forming into a strip, a method in which a polymer obtained by reacting a polyol, diisocyanate, and a low molecular weight diamine or a low molecular weight diol is solidified and dissolved in a solvent, and then the solvent is removed and formed into a yarn. Chips and pellets), etc.) by heating to yarn without dissolving in solvent, before A method in which a solidified polymer (chip shape, pellet shape, etc.) is melted and then mixed with a polyisocyanate compound to form a yarn. The polyol, diisocyanate and low molecular weight diol are reacted to obtain a polymer. There are a method of forming into a yarn without solidifying, a method of mixing the polymer or polymer solution obtained by each of the above methods, and then removing the solvent from the mixed polymer solution to form into a yarn.

  Among these, (A) both-end isocyanate group prepolymer obtained by reacting polyol and diisocyanate (hereinafter referred to as “both-terminal NCO group prepolymer”), (B) polyol, diisocyanate, and low molecular weight diol, Is a method that can be continuously produced without reacting the polymer obtained by reacting with both-end hydroxyl group prepolymer obtained by reacting (hereinafter referred to as “both-end OH group prepolymer”). In addition, since the heat history of the fiber is reduced, the heat resistance is increased, and a non-woven fabric with a high chemical crosslink density can be continuously produced, which further increases the heat resistance, and in addition, usually tetrahydrofuran, dimethylformamide, dimethylacetamide, etc. Low dissolution even in highly soluble solvents for thermoplastic polyurethane resins Was organic solvent resistance can be imparted, and more preferably in view of such uniformity of fineness of this polyurethane fibers one by one is raised, also a small process economical and environmental burden because it does not contain a solvent recovery. Also, a method of melt spinning using a polyurethane polymer chip or pellet obtained by solidifying a polymer obtained by reacting both terminal NCO group prepolymers and both terminal OH group prepolymers can be suitably employed. .

  In this case, the polyols constituting the prepolymers of the components (A) and (B) may be the same or different, but it is preferable to use a polyol having a number average molecular weight of about 400 to 5,000.

  As such a polyol, polyether glycol, polyester glycol, polycarbonate glycol or the like can be used.

Examples of the polyether glycol include linear polymers having a hydroxyl group at the terminal and a number average molecular weight of 400 to 5,000. For example, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxy Pentamethylene glycol, modified PTMG (polytetramethylene ether glycol) which is a copolymer of THF and 3-methyltetrahydrofuran (3-MeTHF), modified PTMG which is a copolymer of THF and 2,3-dimethyltetrahydrofuran, A polyether diol such as a copolymerized polyalkylene diol having a linear or random ether bond with 1 to 8 carbon atoms, a cyclic ether (polyethylene oxide, polypropylene oxide, trimethylene oxide, tetrahydro Polyether glycol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1 And polyether glycol obtained by polycondensation of glycol such as 1,5-pentanediol.
The hydrophilic polyol is a polyol having one or two or more groups selected from the group of repeating units of carboxyl group, sulfonic acid group, phosphoric acid group, amino group, and ethylene oxide. A hydrophilic polyol mainly composed of ethylene oxide is preferably used when imparting hydrophilicity. In order to control the hydrophilicity, it is also possible to copolymerize a polyol having no hydrophilic chain. Examples thereof include polyethylene glycol, polypropylene glycol, ethylene oxide / tetramethylene oxide copolymer polyol, ethylene oxide / propylene oxide copolymer, and the like.

  Examples of the polyester glycol include ethylene glycol, propylene glycol, hexamethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, At least one or more selected from glycols such as 1,3-dimethylolcyclohexane, 1,4-dimethylolcyclohexane, 3-methyl-1,5-pentanediol and succinic acid, malonic acid, glutaric acid, Polyester glycol obtained by polycondensation with at least one or two or more dibasic acids such as adipic acid, sebacic acid, maleic acid, itaconic acid, azelaic acid; lactones such as ε-caprolactone and valerolactone Ring opening Polyester glycol obtained by coupling are exemplified.

  Examples of the polycarbonate glycol include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; alkylene carbonates such as ethylene carbonate and propylene carbonate; at least one organic carbonate selected from diaryl carbonates such as diphenyl carbonate and dinaphthyl carbonate; and ethylene glycol. At least one aliphatic diol selected from propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and the like And carbonate glycol obtained by the transesterification reaction.

  The above exemplified polyether glycol, polyester glycol, or polycarbonate glycol can be used alone or in combination of two or more, but in the case of clothing use, the total amount used from the point of hydrolysis resistance It is desirable to use 30% by mass or more, preferably 60% by mass or more of the polyether diol component with respect to the polyol, and the polyether diol component may be 100% by mass. Of course, there is no problem even if the amount of the polyester glycol component is 100% by mass as long as the hydrolysis resistance is satisfied with a use that does not require hydrolysis resistance or a hydrolysis inhibitor such as a carbodiimide compound or a polycarbodiimide compound. As the polyether diol component, in particular, a copolymer containing polytetramethylene ether glycol and tetramethylene oxide can be preferably used. When imparting hydrophilicity, a hydrophilic polyol mainly composed of ethylene oxide, Polyethylene glycol, ethylene oxide / tetramethylene oxide copolymer polyol, and ethylene oxide / propylene oxide copolymer polyol are preferably used.

  As the diisocyanate constituting the prepolymers of the components (A) and (B), any diisocyanate usually used in the production of polyurethane such as aliphatic, alicyclic, aromatic and araliphatic is used. Can be used.

  Examples of such diisocyanates include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate. 1,6-hexamethylene diisocyanate, 1,4-phenylene diisocyanate, p-phenylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, meta-tetramethylxylene diisocyanate, para-tetramethylxylene diisocyanate These can be used, and one of these can be used alone or in combination of two or more. , Among others 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate are preferably used.

  The low molecular weight diol and the low molecular weight diamine which are chain extenders are preferably those having an appropriate reaction rate and suitable heat resistance, having two active hydrogen atoms capable of reacting with isocyanate, and generally having a molecular weight of 500. The following low molecular weight compounds are used:

  Examples of such low molecular weight diols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 3-methyl-1,5-pentane. Diol, cyclohexanediol, xylylene glycol, 1,4-bis (β-hydroxyethoxy) benzene, neopentyl glycol, 3,3-dichloro-4,4′-diaminodiphenylmethane, isophoronediamine, 4,4′-diaminodiphenylmethane Hydrazine, dihydrazide trimethylolpropane, glycerin, 2-methylpropanediol and the like can be used, and trifunctional glycols such as glycerin can be used as long as spinnability is not impaired. These can be used singly or in combination of two or more, but ethylene glycol and 1,4-butanediol are preferable from the viewpoint of giving workability and appropriate physical properties to the obtained fiber.

Examples of such low molecular weight diamines that can be used include ethylenediamine, butanediamine, propylenediamine, hexamethylenediamine, xylylenediamine, 4,4′-diaminodiphenylmethane, and hydrazine.
A low molecular weight diol and a low molecular weight diamine can be used in combination, but in the present invention, a low molecular weight diol can be more preferably used as a chain extender.
Moreover, monofunctional monools, such as butanol, and monofunctional monoamines, such as diethylamine and dibutylamine, can also be mixed and used as a reaction regulator or a polymerization degree regulator.

  As the inert solvent used in the polyurethane polymerization reaction or as the spinning solution, N, N-dimethylformamide, N, N-dimethylacetamide, N, N, N ′, N′-tetramethylurea, N— Examples include polar solvents such as methyl pyrrolidone and dimethyl sulfoxide.

  In order to improve weather resistance, heat oxidation resistance, and yellowing resistance, optional components such as ultraviolet absorbers, antioxidants, and light stabilizers may be added to the prepolymers of the above components (A) and (B). it can. For example, ultraviolet absorbers such as benzophenone compounds, triazine compounds, and benzotriazole compounds, antioxidants such as hindered phenol compounds, phosphite compounds, and thioether compounds, light stabilizers such as hindered amine compounds, and semicarbazides Stabilizers such as system compounds can be used, and specifically those similar to those exemplified above can be used. Furthermore, inorganic fine particles such as barium sulfate, magnesium oxide, magnesium silicate, calcium silicate, zinc oxide, hydrotalcite, titanium oxide, zirconium-containing compounds, adhesives such as magnesium stearate, calcium stearate, polytetrafluoroethylene, organosiloxane Inhibitors, antistatic agents such as fluorine or siloxane, inorganic colloidal sols such as colloidal silica or colloidal alumina, silane coupling agents, other colorants, pigments, brighteners, dyeing enhancers, gas discoloration inhibitors, fillers, Flame retardants, surface treatment agents, matting agents, antifungal agents, antiseptics, antifoaming agents, plasticizers, waxes, softeners, mold release agents, foaming agents, bulking agents, antibacterial agents such as silver and copper Antibacterial agent, deodorant, blocker with active metal supported on activated carbon, apatite, zeolite, etc. It can be added ring inhibitors like.

  Various inorganic pigments and organic pigments can be used as the pigment added in the production of the colored polyurethane fiber-containing nonwoven fabric, but it is necessary to have a heat resistance of 220 ° C. or higher. For example, blue, green, red, orange, yellow, brown, peach, purple pigment, MERKI JAPAN CO., Manufactured by Ciba Specialty Chemicals Co., Ltd. Examples thereof include gold and silver pigments manufactured by Tokai Carbon Co., Ltd. The pigment particle size is preferably 5 μm or less. Further, a desired hue can be easily obtained without performing a dyeing process.

Next, the method for obtaining the polyurethane fiber of the present invention is not particularly limited. For example, the following three methods are known as melt spinning methods.
(1) A method of melt spinning a polyurethane elastic chip (pellet).
(2) A method in which a polyurethane elastic chip (pellet) is melted and then a polyisocyanate compound is mixed and spun.
(3) A reactive spinning method in which a spinning polymer obtained by reacting a prepolymer obtained by reacting a polyol and diisocyanate with a low molecular weight diol is synthesized and then spun without solidification.

The method (1) is inferior in terms of heat resistance and physical properties, but small turning is effective, so if you want to change the basic physical properties greatly by changing the polymer composition, it is compatible with small lots such as a large number of colors but a small production amount. It is economical and particularly effective.
The method (2) is a method of spinning a polyurethane polymer chip (pellet) after mixing a polyurethane polymer chip (pellet) as a variation of the method (1). In particular, it is effective as a means for improving the heat resistance of the pellet spun product.

  The method (3) is simpler than the methods (1) and (2) because there is no process for handling the polyurethane elastic chip, and the injection rate of the prepolymer into the reactor is adjusted to perform spinning. This is a preferred method because the amount of residual NCO groups in the subsequent polyurethane fiber can be adjusted, and heat resistance can be improved by chain extension reaction with the residual NCO groups. Furthermore, in the method (3), as disclosed in Japanese Patent Publication No. 11-839030, a low molecular weight diol is reacted in advance with a part of the prepolymer, and the prepolymer having excess OH groups is added to the reactor. An injection method can also be performed.

When the method (1) is employed, ordinary thermoplastic polyurethane chips (pellets) can be used. There are generally two types of pellets that can be obtained by the one-shot method and the prepolymer method. The resin obtained by the one-shot method has strong crystallinity and poor melting characteristics during thermoforming. It is preferable to make with.

For example, two liquids (prepolymer method) of a prepolymer of a terminal isocyanate and a chain extender in which an excess of isocyanate is added to a polyol in advance at a temperature of 120 ° C. or less, preferably 100 ° C. or less, or a polymer polyol Two liquids (one-shot method) of polyol compound and isocyanate mixed with chain extender are weighed, mixed and stirred, and the above raw materials are weighed with a metering pump, stirred vigorously, and then poured onto a vat. Then, it is preferably produced by a method of reacting at a temperature of 80 to 200 ° C., more preferably 120 to 180 ° C., and then pulverizing.
The raw material is preferably supplied to an extruder set at 80 to 250 ° C., more preferably 120 to 250 ° C., and polymerization is performed while kneading and conveying the raw material in the extruder to extrude the thermoplastic polyurethane from the die. It can also be manufactured by a method. In general, a thermoplastic polyurethane resin having a good appearance can be obtained without requiring a high-precision raw material supply device for controlling a special reaction equivalent ratio.

  The reaction equivalent ratio of isocyanate and chain extender is not particularly limited, but is usually preferably 0.90 to 1.15, more preferably 0.95 to 1.10. The thermoplastic polyurethane usually has a production JISA hardness of 70 to 95, preferably 75 to 95. If the JISA hardness is less than 70, the releasability will be poor when molded, and the molded product will be deformed. Conversely, if the JISA hardness exceeds 95, molding will occur at the decomposition temperature of urethane, or melt viscosity. If the temperature is lowered a little, the melting will be poor, and if the temperature is raised a little, the viscosity will be drastically lowered or foaming will cause significant deterioration of the quality stability.

  The nitrogen atom content of the thermoplastic polyurethane is preferably in the range of 2.4 to 4.5 mass%. If the nitrogen content is less than 2.4% by mass, the releasability is poor when molded, and the molded product is deformed. Conversely, if the nitrogen content exceeds 4.5% by mass, the decomposition temperature of urethane The temperature dependence of the melt viscosity will be too high due to molding, and if the temperature falls a little, it will lead to poor melting, and if the temperature rises a little, the viscosity will drop drastically, or foaming will stabilize the quality. It will be seriously damaged.

  When the method (2) is employed, the polyisocyanate compound to be used is preferably a compound having a number average molecular weight of 400 or more and having at least two isocyanate groups. Usually, an excess isocyanate is reacted with a polyol. Polyisocyanate compounds can be used. As the polyol, a trifunctional compound or a small amount of an isocyanate compound having a trifunctional isocyanate group may be used in combination. 3-30 mass% is suitable for the addition amount of the polyisocyanate compound with respect to a polyurethane resin, and 5-20 mass% is especially preferable. When the addition amount is small, the modification effect of the polyurethane resin is poor, and when the addition amount is too large, the heat resistance becomes high, but the spinning stability becomes poor and the resulting nonwoven fabric becomes non-uniform.

  When the method (3) is adopted, the spinning polymer is synthesized by (I) synthesis of NCO group prepolymers at both ends, (II) synthesis of OH group prepolymers at both ends, and (III) these two prepolymers. It is composed of three reactions of synthesizing a spinning polymer that leads the polymer to the reactor and continuously reacts. The composition ratio of the raw materials is the sum of the above three reactions. And a molar ratio with respect to the total molar amount of all the low molecular weight diols is preferably 0.95 to 1.25, more preferably 1.03 to 1.15.

  Specifically, the NCO-based prepolymer at both ends (I) is prepared by, for example, charging a predetermined amount of diisocyanate into a tank equipped with a hot water jacket and a stirrer, and then injecting a predetermined amount of polyol while stirring. It can be obtained by stirring at -130 ° C for 30-100 minutes, preferably 60-120 ° C for 50-70 minutes under a nitrogen purge. Both terminal NCO group prepolymers obtained by this reaction are injected into a polyurethane fiber reactor using a jacketed gear pump (for example, KAP-1 manufactured by Kawasaki Heavy Industries, Ltd.).

The OH group prepolymer at both ends of (II) is charged with a predetermined amount of diisocyanate in a tank equipped with a warm water jacket and a stirrer, and then injected with a predetermined amount of polyol while stirring, and is 30-100 at 50-130 ° C. The precursor can be obtained by stirring under a nitrogen purge for 50 minutes to 70 minutes at 60 to 120 ° C., preferably by injecting a low molecular weight diol and stirring to react with the precursor. The obtained both terminal OH group prepolymers are injected into a polyurethane fiber reactor using a jacketed gear pump (for example, KAP-1 manufactured by Kawasaki Heavy Industries, Ltd.).
In addition, at the time of synthesis | combination of both these prepolymers, the said various chemicals for improving a weather resistance, heat oxidation resistance, yellowing resistance, etc. can be added.

  The synthesis of the spinning polymer (III) can be obtained by continuously reacting the prepolymers (A) and (B) fed at a constant ratio. In this case, the reactor may be one that is used in the usual melt spinning method of polyurethane fibers, and a reactor equipped with a mechanism that heats, stirs and reacts the spinning polymer in a molten state, and further transports it to the spinning head. preferable. The reaction conditions are 160 to 220 ° C. for 1 to 90 minutes, preferably 180 to 210 ° C. for 1 to 60 minutes.

The polyurethane fiber used in the present invention can be obtained by transferring the synthesized spinning polymer to the spinning head without solidifying, discharging from the nozzle, and spinning, but the average residence time of the spinning polymer in the reactor Depends on the type of reactor and is calculated by the following formula.
Average residence time in reactor = (reactor volume / spinning polymer discharge rate) x specific gravity of spinning polymer

  In general, about 1 hour is preferable when a cylindrical reactor is used, and 1 to 30 minutes is preferable when a twin screw extruder is used. (In the test with Mobilon K composition in the past, it was carried out in the range of 1.7 to 20 minutes. If it was shorter than this, the reaction did not proceed. On the other hand, if it was longer than this, deterioration, coloration and viscosity reduction occurred.) The (discharge) temperature is preferably equal to or higher than the above-mentioned reaction temperature, preferably 160 to 230 ° C., particularly preferably 180 to 220 ° C., continuously extruded from a nozzle, cooled, and attached with a spinning oil agent and wound. However, it is also possible to continuously perform a web forming process of the nonwoven fabric after being extruded from the nozzle.

  Here, the ratio of the NCO group prepolymer at both ends and the OH group prepolymer at both ends is 0.1 to 3.0% by mass, more preferably 0.3 to 1.2% by weight of NCO groups in the yarn immediately after spinning. It is preferable to adjust the rotation ratio of the injection gear pump as appropriate so that the mass% remains. If the NCO group is within the above range, physical properties such as high elongation and heat resistance can be improved by a chain extension reaction after spinning. If the NCO group is less than the above range, the productivity may decrease due to the increase in viscosity, and the heat resistance and elastic performance of the obtained polyurethane fiber-containing nonwoven fabric may be decreased. If the NCO group is too much, the viscosity of the spinning polymer is low. Spinnability such as broken yarn may be reduced.

The content of NCO groups in the spun yarn is measured as follows.
After the spun fiber (about 1 g) was dissolved in a dibutylamine / dimethylformamide / toluene solution, excess dibutylamine was reacted with NCO groups in the sample, and the remaining dibutylamine was titrated with hydrochloric acid to contain NCO groups. Calculate the amount.

  In addition to the polyurethane fibers obtained by the above reactive spinning method or melt spinning method, the fibers used in the present invention are parallel type (side-by-side type), split type (fiber cross section is divided into arcs) ), And sheath core type [sheath core type (concentric circular type and eccentric type)] and other composite fibers containing thermoplastic elastomer, particularly thermoplastic polyurethane may be used.

These composite fibers can be obtained by a known spinning method such as a melt spinning method or a reactive spinning method. In addition, when using a sheath-core type composite fiber, it is preferable to perform spinning so that the component having a lower melting point becomes a sheath.
The spinning temperature is a matter that can be appropriately determined depending on the melting point of the resin component to be used, but in general, it is preferable to perform composite melt spinning in the range of 180 to 280 ° C. If the temperature is lower than 180 ° C or higher than 280 ° C, stable spinning may be difficult.

  The composite fiber is preferably formed using a thermoplastic elastomer and a thermoplastic resin. However, the thermoplastic resin is not particularly limited, and for example, a thermoplastic material that takes a crystalline form with an amorphous thermoplastic elastomer. Examples thereof include a combination of resins or a combination of resins having a melting point difference of 10 ° C. or more from the melting point of the thermoplastic elastomer. Examples of such thermoplastic resins include polyolefin resins, polyamides, polyesters, polyester elastomers, low melting point copolymer polyesters, polyester / polyether copolymer elastomers, polyester / lactone copolymer elastomers, polystyrene, and the like. It is done. Examples of the polyolefin resin include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-α-olefin random copolymer, atactic polypropylene, polybutene and the like.

  When thermoplastic polyurethane is used as the thermoplastic elastomer, examples of the other resin used for forming the composite fiber include the thermoplastic resins described above. For example, when polypropylene is used, a non-woven fabric having different physical properties and texture from that of a single resin, such as being easy to finer and imparting a unique lightweight feeling and heat-retaining property, can be obtained. Also, it is the same thermoplastic polyurethane, using a resin having a different melting point or softening point, or when one type of thermoplastic polyurethane is spun at different molding temperatures, it is bulky and exhibits a crimping effect after stretching. Non-woven fabrics having different physical properties and textures can be suitably used as compared with the method in which composite spinning is not used.

  When thermoplastic polyurethane is used as the thermoplastic elastomer, the content thereof is preferably 10 to 90% by mass, more preferably 40 to 90% by mass, and particularly preferably 50 to 90% by mass. If the content of the thermoplastic polyurethane is 10% by mass or less, the stretchability is lowered, which may cause a decrease in the elongation recovery rate and the generation of pinholes during elongation, which is not preferable.

  Next, the product manufacturing method of the present invention assembles parts made of non-woven fabric or parts made of woven or knitted fabric according to the shape of the product into a product. Here, what was mentioned above is used as parts which consist of a nonwoven fabric, and parts which consist of a woven / knitted fabric.

  In this case, the above parts can be subjected to functional processing such as antibacterial processing, deodorization processing, flame retardant processing, pumping processing, rubbing processing, antifouling processing, moisture absorption processing, and antistatic processing. As a method, after impregnating a non-woven fabric into a processing liquid, it is uniformly squeezed with a Markle roll or the like, a method of undergoing a dry-curing process, or adjusting the processing liquid to an appropriate viscosity, a knife coater or a gravure roll coater, After applying by printing or the like, it can be carried out in accordance with a conventional method by a heat treatment method or the like. In addition, the nonwoven fabric part used by this invention can also bond or heat-seal | fuse a fabric and laminate sheets, such as another nonwoven fabric and a woven / knitted fabric.

  When assembling two or more fabric parts into a product, the parts to be joined to each other can be joined by any means, and in this case, the parts made of nonwoven fabric can be used in a cut-off state. In the case of joining, for example, they may be joined by heat fusion or stitched. In particular, when the parts to be joined are joined by thermal fusion, a product without stitching and without seams can be obtained, and manufacturing costs can be greatly reduced compared to products that require a conventional sewing process. preferable. In this case, the method of heat fusion is not particularly limited, and heat fusion using a heat press, heat fusion using ultrasonic waves or high frequency, and the like are possible. In any case, it is only necessary that the parts are bonded by fusion of the thermoplastic elastomer fiber-containing nonwoven fabric.

  Products of the present invention are mainly for briefs, panties, shorts, undershirts, camisole, girdle, bra, spats, body suits, underwear such as sanitary shorts, swimwear, leotards, resort wear, home wear, underwear, sports Tights, shirts, outerwear, gloves, socks, arm covers, medical clothing, surgical clothing, clothing for cleanroom work in semiconductor factories, clothing products such as dustproof clothing, supporters, eye masks, disposable diapers, incontinence pads, gauze High extensibility like industrial materials such as bandages, patch materials, packaging materials, sanitary products such as masks, sheets, towels, handkerchiefs, clothing interlining, filters for microfiltration, industrial wipers, protective covers, etc. Application to fields that require elongation recovery is preferred.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

In the following examples, the washing test of the product and various physical properties of the nonwoven fabric were measured according to the following methods.
Laundry test JIS L-1096 1.2 Tests were conducted in the following manner according to the test piece preparation of woven fabric and the home electric washing machine method of JIS L-1018.
1. Dimensional change rate (1) A 20 cm × 20 cm square was drawn on the sample as a measurement surface, and the length connecting the center points of both sides was measured.
(2) Using a fully automatic washing machine (102A, manufactured by NIPPRE), the water level was 30 L, the water temperature was 25 ° C., about 10 g of a sample was added, and 20 g of weak alkaline detergent (trade name: Attack, Kao Corporation) was added.
(3) After washing for 5 hours, rinsing for 10 minutes, dehydrating for 1 minute, taking out, and drying in an atmosphere of 25 ° C. and 65% RH for 2 hours.
(4) The dimensional change rate was determined by the following formula.
Dimensional change rate (%) = {[length after washing (mm) −length before washing (mm)] / length before washing (mm)} × 100
2. Fluffing, fraying, curling The nonwoven fabric surface after washing was visually observed.

The chargeability was measured according to the following procedure according to the method B of JIS L-1094.
(1) A sample was cut into 4 cm × 32 cm to obtain a test piece.
(2) The friction cloth was cut into 2.5 cm × 16.0 cm using a nylon No. 8 white cloth (attached white cloth for JIS L-0803 dyeing fastness test).
(3) Measurement was performed under constant temperature and humidity of 15 ° C. × 40% RH.
(4) A test piece is attached to a drum having an outer diameter of 31.4 cm, a friction cloth is placed at a position in contact with the lower side of the test piece, one side of the test piece is fixed, and a load of 500 g is applied to the other side to extend. I let you. At this time, the friction cloth was placed at a position in contact with the lower side of the test piece, one side of the test piece was fixed, and a load of 500 g was applied to the other side and extended.
(5) Next, the drum is rotated at 400 revolutions per minute, and using a digital electrostatic potential measuring device (trade name: KSD-0103S, manufactured by Kasuga Denki Co., Ltd.), static electricity is generated at a position 1 cm from the side of the drum. The amount was measured.

Quick-drying (1) A sample was cut into a 7.5 cm × 7.5 cm sample.
(2) The test piece was left in an atmosphere of 25 ° C. and 65% RH for 1 hour to measure the mass.
(3) According to the JIS L-1096 method, the sample piece was completely immersed in a 20 cm high water bath, left for 20 minutes, taken out, and dehydrated for 1 minute.
(4) Thereafter, the sample was left in an atmosphere of 25 ° C. and 65% RH, and the mass was measured over time.
(5) The time (minutes) when the water absorption rate became 1% or less was measured.

The moisture permeability was measured according to the water method of JIS L-1099.
(1) A sample was cut into a circle having a diameter of 8 cm to obtain a test piece.
(2) 40 ° C. distilled water was added to the position of 1 cm on the upper surface of a glass bottle having an inner diameter of 4.7 cm.
(3) A test piece was placed on the top of the cup, and the periphery of the opening (4.7 cm) of the glass bottle was sealed, and fixed so that moisture did not enter and exit from the periphery.
(4) It was put in a constant temperature and high humidity apparatus at 40 ° C. and 50% RH.
(5) The total mass after 1 hour was defined as A1 (g), and the total mass after 2 hours was defined as A2 (g). Note that S is a moisture permeable area.
Moisture permeability (g / m ² · 24h) = {(A1-A2) / S} × 24

The air permeability was measured by the following method according to the method B of JIS L-1096.
(1) The sample was cut into 5 cm x 5 cm, and it was set as the test piece.
(2) Two glass tubes having an inner diameter of 3.5 cm were joined so that air did not enter and exit from the outside, and an air permeation tester was obtained.
(3) Using an aspirator at the bottom of the glass tube, air was introduced from the top of the glass tube with an air volume of 300 mL per minute.
(4) This time, a test piece was sandwiched between two glass tubes, joined and fixed so as not to enter and exit from the outside, and the air volume passing through the test piece was measured.
(5) The air permeability was evaluated by calculating the time required for 300 mL of air to pass through the sample using the following formula.
Air permeability (seconds) = {300 mL / (air flow rate through the test piece, mL / min)} × 60

Heat retention was measured by the following method in accordance with the cooling method of JIS L-1096.
(1) A sample was cut into 6 cm × 11 cm to obtain a test piece.
(2) The periphery of a 50 ml screw bottle with an outer diameter of 3.4 cm was covered with a test piece and left in a room whose temperature was adjusted to 25 ° C. for 1 hour.
(3) 50 ml of distilled water heated to 50 ° C. was put into this screw bottle, and the water temperature after 1 hour was measured.
(4) The water temperature after 1 hour was measured in the same manner with a bare source body not covered with the test piece.
(5) The heat retention rate was calculated | required with the following formulas.
Thermal insulation rate (%) = {[1- (50-b)] / (50-a)} × 100
a: Temperature after cooling for 1 hour in a naked state (° C.)
b: Temperature after cooling for 1 hour when the specimen is attached (° C)

Snag evaluation Evaluation was performed as shown in Table 1 in accordance with JIS L 1058 A method.

Pilling Evaluation Evaluation was made as shown in Table 2 in accordance with JIS L 1076 A method.

Fraying evaluation A sample of 10 cm × 10 cm is collected, and after the washing test, after being left for 4 hours in a JIS standard condition (temperature 20 ± 2 ° C., humidity 65 ± 2% RH), the degree of fraying of the cut portion is measured with a microscope. It was doubled and compared before and after washing and evaluated as shown in Table 3.

A sample having a curl evaluation of 10 cm × 10 cm was taken, and after the washing test, the sample was allowed to stand for 4 hours in a JIS standard condition (temperature 20 ± 2 ° C., humidity 65 ± 2% RH), and the sample angle of the curled portion was measured. Evaluation was performed as follows.

_Yellowing resistance test and its evaluation [Related Standards] JIS Z 8701 _-1982
“Color Display Method Using XYZ Color System and X ₁₀ Y ₁₀ Z ₁₀ Color System”
The measured values in the L * a * b * color system are as follows.
L *: Lightness a *, b *: Indicates coordinates on the color chart.
a *: Red / green axis value (high value means strong red, low value means strong green)
b *: yellow / blue axis value (high value indicates yellow is strong, low value indicates blue is strong)

Measurement of yellowing change (Δb value):
The following NOx resistance test, chlorine resistance test, and light resistance test were carried out using a test piece (10 cm × 4 cm), and b values before and after the treatment were measured with a Minolta spectrocolorimeter (CM-3500d). The change (Δb value) was evaluated. A higher Δb value means that the sample has turned yellow.

NOx resistance test:
According to the JIS0855 strong test, the test piece was exposed three times under saturated steam with 650 ppm of nitric oxide gas until the discoloration of the standard dyed cloth reached a constant, and the yellowing index b value before and after treatment was measured, and the change The Δb value was determined.

Chlorine resistance test:
After the test piece was treated in an aqueous solution having a chlorine concentration (effective chlorine concentration) of 20 ppm for 3 hours based on the JISL0884B method, the yellowing index b value before and after the treatment was measured, and the change Δb value was obtained.

Light resistance test:
The test piece was irradiated for 32 hours with a UV fade meter U48S (temperature: 46 ° C., humidity: 50% RH) manufactured by Suga Test Instruments, the yellowing index b value before and after the treatment was measured, and the change Δb value was determined.

Measurement of average filament diameter The cross section of the filament was measured with a scanning electron microscope. The average filament diameter was determined with an average value of 5-10 pieces.

Skin irritation Evaluated by Kawai method of Japan Industrial Skin Hygiene Association.
(1) For 20 subjects, four test pieces cut in 1.5 cm square were pasted on the left and right upper arms.
(2) After 24 hours, the test piece was removed and a sump solution (manufactured by Sump Laboratories) was applied.
(3) After 1 minute, as a specimen peeled from the skin, the concave skin groove was observed using a stereomicroscope.
(4) Evaluation was made by the following method.
Standard: Negative Specimen stimulation index 0 or less
Semi-negative Specimen stimulation index 1-2
Quasi-positive specimen stimulation index 3
Positive Specimen stimulation index 4 or higher

[ Reference Example 1]
3,545 parts by weight of polyethylene adipate diol having a number average molecular weight of 2,000 as a polyol and 1,205 parts by weight of 4,4′-diphenylmethane diisocyanate as a diisocyanate component were stirred and reacted at 110 ° C. for 60 minutes in a nitrogen gas atmosphere. Both terminal NCO group prepolymers were synthesized. 250 parts by mass of 1,4-butanediol as a chain extender was added to the obtained NCO group prepolymer at both terminals and stirred for 15 minutes to obtain a polyurethane polymer. The NCO group content remaining in this polyurethane polymer was 0.4% by mass. This polyurethane polymer was heat-treated at 100 ° C. for 24 hours, ground into flakes, and then aged for 3 days in an atmosphere of 50 ° C. and 60% RH. Subsequently, the flaky polyurethane polymer was mixed with 25 parts by mass of an ultraviolet absorber (0.5% by mass) (2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole), an antioxidant (0 .5 mass%) (3,9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy) -1,1-dimethylethyl) -2,4, 8,10-tetraoxaspiro (5.5) undecane) 25 parts by mass, light stabilizer (0.5% by mass) dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6 succinate , 6-tetramethylpiperidine condensate 25 parts by mass, semicarbazide compound (0.1% by mass) 1,1,1 ′, 1′-tetramethyl-4,4 ′-(methylene-di-1,4-phenylene) 5 parts by weight of disemicarbazide And pressure, followed by uniformly mixing with heated extruder to 170 ° C., extruded in water in the discharge amount per minute 400 g, to obtain a polyurethane pellets by cutting diameter to 3mm cylindrical by using a pelletizer. The Shore A hardness of the polyurethane pellets was 75, and the melting start temperature was 165 ° C.

The polyurethane pellets were dehydrated and dried for 2 hours at a drying temperature of 80 ° C. using a hopper dryer, and the moisture content of the polyurethane pellets was adjusted to 50 ppm. This polyurethane pellet was fed to an extruder heated to 230 ° C. and melted, and then led to a melt blow spinning facility having 450 nozzles having a diameter of φ0.3 mm and a pitch of 1 mm in a row, and 0.12 g / nozzle per nozzle hole The polymer was extruded in minutes. The nozzle temperature at this time was 230 ° C. Next, air heated to 235 ° C. from the slit of the nozzle was sprayed at 1.9 m ³ per minute and laminated on a conveyor made of a 20-mesh wire net located 30 cm below the nozzle. The sheet was sucked from the lower part of the conveyor with a flow rate of 50 m ³ per minute to form a net, and the winding speed was set to 2.7 m / min to obtain a sheet-like nonwoven fabric wound on a paper tube. The obtained polyurethane fiber-containing nonwoven fabric had an average filament diameter of 10 μm, a basis weight of 50 g / m ² , and a thickness of 0.14 mm. The breaking elongation of this nonwoven fabric was 380% in warp and 430% in latitude, and the recovery rate after stretching 50% was 92% in both directions.

Here, the elongation at break and the recovery rate after 50% elongation were measured according to the following methods, respectively.
Elongation at break:
Measurement was carried out according to JIS L 1096 by the following method. A sample was cut into 25 mm × 130 mm. Next, using an autograph (AG-1) manufactured by Shimadzu Corporation, the test piece was stretched to break at a grasping length of 10 cm and an elongation rate of 20 cm / min, and the elongation of the test piece was measured. The elongation at break was determined by the following formula.
Elongation at break (%) = {(sample length at break (cm) −10) / 10} × 100
Elastic recovery after 50% elongation:
In accordance with the tensile modulus of elasticity of JIS L 1096 (general woven fabric test method), a tensile tester (Shimadzu Autograph (AG-1) was used to pull a test piece having a width of 2.5 cm from a point L ₀ with a grip interval of 10 cm from the point L _0. From the point L ₂ (5 cm) that was pulled at 10 cm / min and stretched to 50% of the gripping interval, when returning at the same speed, the length between the point L ₁ and the point L ₀ at which the stress became zero was set to A ₁ ( cm) and calculated by the following formula.
Elastic recovery rate after 50% elongation (%) = ((5-A ₁ ) / 5) × 100

  Using this non-woven fabric, shorts were prepared according to the L size for adult women described in JIS L-4006 1.2.2. First, the shorts were created by free-cutting two sheets on the front and back, and then overlaying the two sheets. Then, a mold heated to 130 ° C. was applied to a portion corresponding to 5 mm of overlap between the crotch portion and the left and right sides in total, and the product was heated and fused at 0.2 MPa for 5 seconds to obtain a product.

  When the obtained non-sewn shorts were subjected to a washing test, the dimensional change rate was 0% with no change. Further, the cut end had fraying resistance and curl resistance, and the nonwoven fabric had good pilling resistance and snag resistance, and was suitable as a garment.

Further, after dehydration, it was dried at 25 ° C. in an atmosphere of 65% RH, and it was dried in about 5 minutes and was excellent in quick drying property. On the other hand, the moisture permeability under an atmosphere of 50% RH at 40 ° C. was 4,400 g / m ² · 24 hours, which was a satisfactory result as a material for clothing. Furthermore, when the air permeability of the sample with an air passage area of 9.6 cm ² was measured, it was 62 seconds.
The heat retention was 6.3%, which was a superior result compared to other clothing materials made of yarn (Comparative Examples 1 and 2). In addition, the charging property was a good result at a low level of -0.2 kV.
As for yellowing resistance, good results were obtained as follows.
NOx yellowing: Δb value = 7.0
Chlorine water yellowing: Δb value = 18.4
UV fade meter yellowing: Δb value = 9.6

  As a result of a 16-hour wearing test on 10 monitors of the shorts of the present invention, it was judged that all members had good fit and 8 out of 10 people had good comfort. In addition, the feeling of stuffiness during wearing was not felt, and the point that it did not resonate with the outerwear because of no sewing was popular. Furthermore, the skin irritation by the Kawai method was semi-negative.

[ Reference Example 2]
When the polyurethane fiber-containing nonwoven fabric obtained in the same manner as in Reference Example 1 was held at 50% elongation for 24 hours, the breaking elongation was 350% in the warp direction, and the recovery rate after 50% elongation was 95% in both circumstances. Improved.

Using this nonwoven fabric, shorts were produced in the same manner as in Reference Example 1. As a result, the fit was further improved, and the comfort was judged to be good by 9 out of 10 monitors. Other characteristics were the same as the results of Reference Example 1 and were good, and the measured values of each physical property were as follows.
Results of washing test: 0% dimensional change rate, fray resistance at the cut edge, curl resistance, good pilling resistance and snag resistance of the nonwoven fabric. Chargeability: -0.2 kV Quick drying: 5 minutes Moisture permeability: 4,750 g / m ² · 24 hours Breathability: 62 seconds Thermal insulation: 5.8% Skin irritation: Semi-negative

[Example 1 ]
At the stage of synthesizing both terminal isocyanates using polyoxytetramethylene glycol having a number average molecular weight of 2,000 as a polyol, as a beige colorant, Irgalite Yellow WGP manufactured by Ciba Specialty Chemicals: 3 mass Parts, the same chromoftal yellow 3RLP: 53.4 parts by mass, the same irgarite blue WGP: 3 parts by mass, the same chromoftal bron 5R: 0.4 parts by mass, the same chromoftal red 2,030: 0.2 Part by mass, titanium oxide manufactured by Fuji Titanium Industry Co., Ltd. (TR-700): Polyurethane as in Reference Example 1 except that 4 parts by mass (0.2% by mass / polymer) of a mixture of 40 parts by mass was added. Pellets were obtained.

Then, the conveyor speed for nonwoven fabric formation 1.3 m / min, 1.0 m / min and, except for changing the reference example 1 and the same way a basis weight of 100 g / m ² and 150 g / m ² of the sheet-shaped polyurethane fiber-containing nonwoven fabric Got. In addition, a nonwoven fabric containing a three-dimensional urethane fiber of 100 g / m ^{2 in} the same manner as in Reference Example 1 except that the speed of the conveyor equipped with a silicone resin mold having a three-dimensional shape of the hip was changed to 1.2 m / min. Got. The thickness of the nonwoven fabric 100 g / m ² is 0.26 mm, 150 g / m ² is at 0.38 mm, KeiShindo of the nonwoven fabric 430% NukiShindo was 480%. The nonwoven fabric had an average filament diameter of 11 μm for a nonwoven fabric with a basis weight of 100 g / m ² and 13 μm for a nonwoven fabric with a basis weight of 150 g / m ^2. The nonwoven fabric had a warp elongation of 450% and a weft elongation of 500%. The 50% elongation recovery rate was 91%.

Subsequently, a 150 g / m ² non-woven fabric is used as the front center, waist, and thigh, and a three-dimensional non-woven fabric that is shaped at the hip is used at the rear, and 100 g / m ² is used for the other parts. Used to make a girdle by heat fusion. The use of non-woven fabrics with different thicknesses depending on the strength of body movement at the waist and thighs and the use of a three-dimensional non-woven fabric at the hips enhances the fit by following the curve of the human body. At the same time, we obtained a girdle with a body correction function in place and without excessive tightening. Furthermore, since an ether-based polyol is used as a polyurethane raw material, it has excellent hydrolysis resistance and is colored beige at the pellet stage, and can be used as a garment as it is without post-dyeing. The characteristics of the product were as good as in Reference Example 1, and the evaluation by the monitor judged that 9 out of 10 were good. In addition, the measured value of each physical property of a nonwoven fabric was as follows.
100 g / m ²
Results of washing test: 0% dimensional change rate, fraying resistance at the cut end, good curl resistance, good pilling resistance and snag resistance of the nonwoven fabric. Chargeability: -0.2 kV Quick drying: 10 minutes Moisture permeability: 3,050 g / m ² · 24 hours Breathability: 64 seconds Thermal insulation: 10.3% Skin irritation: Semi-negative
150 g / m ²
Results of washing test: 0% dimensional change rate, good fray resistance at cut edge, good curl resistance, good pilling resistance and snag resistance of the nonwoven fabric. Chargeability: -0.2 kV Quick drying: 15 minutes Moisture permeability: 2,900 g / m ² · 24 hours Breathability: 67 seconds Thermal insulation: 15.4% Skin irritation: Semi-negative

[ Reference Example 3 ]
Polyurethane pellets were synthesized in the same manner as in Reference Example 1 except that 10 parts by mass of a black colorant (trade name: Toka Black # 75550F, manufactured by Tokai Carbon Co., Ltd.) was added.
Next, in the same manner as in Reference Example 1 except that the filaments were directly blown onto a three-dimensional product made of polytetrafluoroethylene (PTFE) having the front and back surfaces of the spats, the average weight was 200 g / m ² by lamination. A nonwoven fabric with a filament diameter of 13 μm was obtained. The non-woven fabric consisting of two parts, the front and back, was superposed and the joint was heated and fused to complete the spats. As for comfort, 9 out of 10 monitors were judged good. This characteristic was as good as in Reference Example 1, and the measured values of each physical property were as follows. In addition, it was colored black at the pellet stage and could be used as clothing without any post-dyeing.
Results of washing test: 0% dimensional change rate, good fray resistance at cut edge, good curl resistance, good pilling resistance and snag resistance of the nonwoven fabric. Chargeability: -0.1 kV Quick drying: 20 minutes Moisture permeability: 2,600 g / m ² · 24 hours Breathability: 69 seconds Thermal insulation: 19.6% Skin irritation: Semi-negative

[Example 2 ]
The polyurethane pellets of Example 1 were formed by spraying filaments by the melt blow method. An average filament with a basis weight of 100 g / m ² by lamination in the same manner as in Example 1 except that the speed of the conveyor equipped with a polypropylene mold shaped strapless brassiere without shoulder straps was 1.2 m / min. A nonwoven fabric having a diameter of 8 μm was obtained. When a brassiere made by heating and fusing the back part was attached, 6 out of 10 monitors judged that the feeling of wearing was good. The measured values of each physical property were the same as in Example 1 .

[Example 3 ]
The following both-terminal NCO group prepolymer and both-terminal OH group prepolymers were synthesized as intermediate reactants for a polyurethane fiber-containing nonwoven fabric. Both terminal OH group prepolymers were charged with 28.34 parts by weight of 4,4′-diphenylmethane diisocyanate as a diisocyanate component in a 80 ° C. warm water jacketed reaction vessel sealed with nitrogen gas, and then absorbed with stirring. Agent (0.5% by mass) (2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole) 25 parts by mass, antioxidant (0.5% by mass) (3,9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5.5 ) Undecane) 25 parts by weight, light stabilizer (0.5% by weight) dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperi succinate 25 parts by mass of gin condensate, 5 parts by mass of semicarbazide compound (0.1% by mass) 1,1,1 ′, 1′-tetramethyl-4,4 ′-(methylene-di-1,4-phenylene) disemicarbazide And 78.12 parts by mass of polyoxytetramethylene glycol having a number average molecular weight of 2,000 was injected as a polyol component. After reacting for 1 hour, 40.94 parts by mass of 1,4-butanediol was injected as a low molecular weight diol.
On the other hand, the NCO group prepolymer at both ends was charged with 47.4 parts by mass of 4,4′-diphenylmethane diisocyanate as a diisocyanate component in a 80 ° C. warm water jacketed reactor sealed with nitrogen gas, and then a number average molecular weight of 2000 as a polyol. 100 parts by mass of polyoxytetramethylene glycol was injected and allowed to react for 1 hour.

The obtained both-end NCO group prepolymer and both-end OH group prepolymer were continuously fed at a mass ratio of 3: 1 to a total capacity 3,000 mL cylindrical reactor having a stirring blade. The feed rate was 40.5 g / min for the NCO group prepolymer at both ends and 13.5 g / min for the OH group prepolymer at both ends. The average residence time in the reactor was controlled to about 50 minutes, and the temperature in the reactor was controlled to about 190 ° C. Without solidifying the reaction mixture is introduced into a spinning head kept at a temperature of 220 ° C., and then introduced into a melt-blow spinning apparatus of Reference Example 1, in the same manner as in Reference Example 1, the nozzle hole per 0.12 g / The reaction mixture was discharged at a rate of min (total amount 54 g / min) to obtain a polyurethane fiber-containing nonwoven fabric having excellent heat resistance and an average filament diameter of 9 μm. The NCO group content of the polyurethane fiber immediately after discharge was 0.41% by mass.
Was evaluated to create the shorts in the same manner as in Reference Example 1, the same manner as in Example 1, comfort was judged to be good 10 people in nine monitor. The measured values of each physical property were also the same as in Reference Example 1. Since it does not contain an ester bond, it is excellent in hydrolysis resistance, and an excess NCO group is crosslinked in the nonwoven fabric, so that it is a shorts material excellent in heat resistance.
As for yellowing resistance, good results were obtained as follows.
NOx yellowing: Δb value = 7.8
Chlorine water yellowing: Δb value = 15.4
UV fade meter yellowing: Δb value = 6.4

[Example 4 ]
Polyurethane pellets were synthesized in the same manner as in Reference Example 1 except that dicyclohexylmethane-4,4′-diisocyanate was used as the isocyanate component. This was melted at 220 ° C., a hot hose and a pressure pump were attached to the end, and a hand gun equipped with 48 nozzles having a hole diameter of 0.5 mm was attached to the tip, and a discharge pressure of 18 kg / cm ² was attached. Then, it sprayed directly on the wire mesh-like three-dimensional object that shaped the waist for men.
After air-cooling for 10 minutes, the sprayed urethane nonwoven fabric was removed from the wire mesh-like three-dimensional object to obtain nonwoven fabric pants with a basis weight of 95 g / m ² and an average filament diameter of 12 μm. The elongation of the pants was 300% or more in all directions, the elongation in the warp direction was 430%, and the 50% elongation recovery was 94%. In the wearing test on the monitor, 7 out of 10 people judged good. Further, even when stored or used for a long period of time, it had excellent yellowing resistance. Other characteristics were as good as in Reference Example 1, and the measured values of each physical property were as follows.
Laundry test results: 0% dimensional change rate, fray resistance at cut edge, curl resistance, pilling resistance of the nonwoven fabric, snag resistance Chargeability: 0.1 kV Quick drying: 5 minutes Moisture permeability : 3,200 g / m ² · 24 hours Breathability: 62 seconds Thermal insulation: 5.9% Skin irritation: Semi-negative NOx yellowing: Δb value = 2.4
Chlorine water yellowing: Δb value = 0.5
UV fade meter yellowing: Δb value = 0.4

[ Reference Example 4 ]
In the same manner as in Reference Example 1, a fine filament was spun using a melt blow spinning equipment. At the position 30 cm below the nozzle, a conveyor in which a rotary roll having an outer diameter of 5 cm and a length of 40 cm is arranged in parallel with the nozzle is placed, and filaments are laminated on this roll to continuously form a tubular polyurethane fiber-containing nonwoven fabric Was molded.
After cooling, the nonwoven fabric was removed from the roll and cut into an arbitrary size to create a supporter. The weight of the supporter was 480 g / m ² , the average filament diameter was 15 μm, the longitudinal elongation was 530%, the 50% elongation recovery property was 97%, and the supporter was excellent in elongation property and elongation recovery property. Other characteristics were also good, and the measured values of each physical property were as follows.
Laundry test results: 0% dimensional change rate, good fray resistance at cut edge, good curl resistance, good pilling resistance and snag resistance of the nonwoven fabric Chargeability: -0.3 kV Quick drying: 20 minutes Moisture permeability: 1,800 g / m ² · 24 hours Breathability: 85 seconds Thermal insulation: 39% Skin irritation: Semi-negative

[ Reference Example 5 ]
Polyurethane pellets synthesized in the same manner as in Reference Example 1 were used as the first resin, and polypropylene pellets (Novatech SA06A, manufactured by Nippon Polypro Co., Ltd.) were used as the second resin. These are introduced separately into two series of melting equipment, and polyurethane is heated and melted at 235 ° C. and polypropylene is heated at 215 ° C. Then, the rotational speed of the metering gear pump is adjusted so that the mass ratio of polyurethane to polypropylene is 70:30. The composite filament was spun by adjusting and supplying it to the side-by-side nozzle pack.
Next, in the same manner as in Reference Example 3 , a spat made of nonwoven fabric composed of side-by-side structure composite filaments having a basis weight of 200 g / m ² , an average filament diameter of polyurethane equivalent to 7 μm and polypropylene equivalent to 5 μm was completed. The thickness of the spats is 1.6 mm, the elongation in the warp direction is 430%, the 50% elongation recovery property is 85%, and the bulk is about twice as high as that of the nonwoven fabric made only of polyurethane fibers, and the lightweight feeling It was excellent in heat retention, and also in tactile sensation, and 9 out of 10 monitors judged that the wearability was good. Other physical properties were also good as described below.
Washing test results: 0% dimensional change rate, fray resistance at the cut edge, curl resistance, pilling resistance and snag resistance of the nonwoven fabric. Chargeability: -0.5 kV Quick drying: 15 minutes Moisture permeability: 2,800 g / m ² · 24 hours Breathability: 69 seconds Thermal insulation: 41% Skin irritation: Semi-negative

[ Reference Example 6 ]
A 50 g / m ² sheet-like polyurethane fiber-containing non-woven fabric was formed in the same manner as in Reference Example 1 except that the temperature of the extruder and nozzle was 220 ° C, and the temperature of the heated air was 225 ° C. This nonwoven fabric has an average filament diameter of 25 μm, a breaking elongation of 410%, a 50% elongation recovery property of 90%, and a moisture permeability of 6,000 g / m ² · 24 hours. It was able to be used well.
However, since the filament diameter was large, the pore size was increased, and the water was able to slip through the nonwoven fabric freely, and the touch was firm, so it was not suitable as an inner material. For evaluation, shorts were produced in the same manner as in Reference Example 1 and a wearing test using a monitor was performed. As a result, no one out of 10 people judged that the comfort was good. The heat retention was as low as 3.5%, and the physical properties were as follows.
Washing test results: 0% dimensional change rate, fray resistance at the cut end, curl resistance, pilling resistance of the nonwoven fabric, and snag resistance Charging: -0.2kV Quick drying: 5 minutes Ventilation Sex: 60 seconds

[Comparative Example 1]
Shorts were prepared in the same manner as in Reference Example 1 using a melt blown nonwoven fabric having an average filament diameter of polypropylene of 7 μm and a basis weight of 50 g / m ² . Since the non-woven fabric has low heat-fusibility and is easily charged with static electricity, it has been necessary to repeatedly press it in the heat-sealing process.
The shorts had a breaking elongation of 30%, and the fusion between the filaments peeled off at the fitting stage and could not be worn. Furthermore, when the sheet-like non-woven fabric was washed, it was not a material that can be used in the present invention because of its strong standing. In addition, the measured values of each physical property were as follows.
Laundry test results: Dimensional change rate is not measurable, frayed at the free cut end, curling resistance, pilling and snag generation of the nonwoven fabric Chargeability: -4.5 kV Quick drying: 5 minutes Moisture permeability: 3,900 g / M ² · 24 hours Breathability: 63 seconds Thermal insulation: 17.8%

[Comparative Example 2]
Shorts were made by ordinary sewing from a Russell fabric having a basis weight of 130 g / m ^{2 made} of 311 decitex polyurethane elastic fibers and 33 decitex 10 filaments. Although the elongation at break was 370% and the recovery rate of elongation was 93%, the wearing feeling of the sewn part was evaluated by monitoring, and 8 out of 10 responded that the sewn part felt uncomfortable. Next, improved shorts were created by free-cutting avoiding sewing around the waist and hem, but fraying and curling were severe due to washing and were not suitable for use as general clothing. Furthermore, in terms of functions such as moisture permeability, breathability, and heat retention, the results were all inferior to the shorts made of the urethane fiber-containing nonwoven fabric of the present invention. The physical properties of the improved shorts were as follows.
Washing test result: dimensional change rate 0%, frayed cut edge, curled, knitted fabric with pilling resistance and snag resistance Chargeability: 1.3 kV Quick drying: 10 minutes Moisture permeability: 1,700 g / M ² · 24 hours Breathability: 88 seconds Thermal insulation: 1.8% Skin irritation: Semi-negative

Claims (14)

Highly stretchable, comprising a plurality of fabric parts shaped according to the shape of the product, joined together at the joint, and at least a part of the parts contains polyurethane fibers with an average filament diameter of 0.5-60 μm A clothing product composed of highly stretchable nonwoven parts,
The polyurethane fiber is obtained by melt spinning a polymer obtained by reacting polyol, diisocyanate and low molecular weight diol, and contains 30% by mass or more of polyether diol with respect to the total amount of polyol.
The nonwoven fabric part has a three-dimensional shape obtained by spraying the polymer on a three-dimensional object from a position 10 to 50 cm away, or has a sheet shape obtained by spraying on a net, and has a basis weight of 20 to 500 g. / M ² , a clothing product having a thickness of 0.05 to 3 mm.   The polyurethane fiber is obtained by melt spinning a polymer obtained by reacting a both-end isocyanate group prepolymer obtained from a polyol and a diisocyanate with a both-end hydroxyl group prepolymer obtained from a polyol, a diisocyanate and a low molecular weight diol. 1. The product according to 1.   The product according to claim 1 or 2, wherein the joining portion is joined by heat fusion.   The product according to any one of claims 1 to 3, wherein the content of the isocyanate group contained in the yarn immediately after spinning of the polyurethane fiber is 0.1 to 3.0 mass%.   The product according to any one of claims 1 to 4, wherein the polyurethane fiber is a side-by-side type composite fiber.   The product according to any one of claims 1 to 5, wherein the nonwoven fabric has a 50% elongation recovery rate of 60% or more.   7. Briefs, panties, shorts, undershirts, camisole, girdle, bra, spats, body suits, sanitary shorts, underwear, swimwear, sports tights, supporters or leotards. Product. A clothing product comprising a single high-stretchability / high-stretch recovery nonwoven fabric containing polyurethane fibers having an average filament diameter of 0.5-60 μm,
The polyurethane fiber is obtained by melt spinning a polymer obtained by reacting polyol, diisocyanate and low molecular weight diol,
The nonwoven fabric has a three-dimensional shape obtained by spraying the polymer on a three-dimensional object from a position 10 to 50 cm away, and has a basis weight of 20 to 500 g / m ² and a thickness of 0.05 to 3 mm. And clothing products.   The product according to claim 8, wherein the content of the isocyanate group contained in the yarn immediately after spinning of the polyurethane fiber is 0.1 to 3.0% by mass.   The product according to claim 8 or 9, wherein the polyurethane fiber is a side-by-side type composite fiber.   The product according to any one of claims 8 to 10, wherein the nonwoven fabric has a 50% elongation recovery rate of 60% or more.   The brief according to any one of claims 8 to 11, which is a brief, panty, shorts, undershirt, camisole, girdle, bra, spats, body suit, sanitary shorts, underwear, swimsuit, sports tights, supporter or leotard. Product. After obtaining a plurality of fabric parts shaped according to the shape of the product, it is a method for manufacturing a clothing product in which the parts are assembled and joined at a joint, and at least a part of the parts has an average filament diameter of 0.5 Including a polyurethane fiber containing 30% by mass or more of a polyether diol based on the total amount of the polyol in a polymer obtained by melt spinning a polymer obtained by reacting a polyol, diisocyanate and a low molecular weight diol. It has a three-dimensional shape obtained by spraying the polymer on a three-dimensional object from a position 10 to 50 cm away or a sheet shape obtained by spraying on a net, and has a basis weight of 20 to 500 g / m ² and a thickness of 0.05. characterized in that it consists of high extensibility and high elongation recovery nonwoven parts are ~3mm claims 1 to 7 or 1 Kouki of Method of manufacturing the clothing products. A method for producing a clothing product comprising a single nonwoven fabric shaped according to the shape of the product, the nonwoven fabric having an average filament diameter of 0.5-60 μm, obtained by reacting polyol, diisocyanate and low molecular weight diol Including a polyurethane fiber obtained by melt spinning the obtained polymer, and having a three-dimensional shape obtained by spraying the polymer on a three-dimensional object from a position 10 to 50 cm away, having a basis weight of 20 to 500 g / m ² and a thickness of 0.05 to The method for producing a garment product according to any one of claims 8 to 12, wherein a non-woven fabric having high extensibility and high extensibility which is 3 mm is used.