WO2012090533A1 - Hydrophobized hygroscopic heat-releasing fiber and fibrous structure using same - Google Patents
Hydrophobized hygroscopic heat-releasing fiber and fibrous structure using same Download PDFInfo
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- WO2012090533A1 WO2012090533A1 PCT/JP2011/064652 JP2011064652W WO2012090533A1 WO 2012090533 A1 WO2012090533 A1 WO 2012090533A1 JP 2011064652 W JP2011064652 W JP 2011064652W WO 2012090533 A1 WO2012090533 A1 WO 2012090533A1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
- D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/65—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing epoxy groups
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/657—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing fluorine
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
Definitions
- the present invention relates to a hydrophobized moisture-absorbing exothermic fiber that repels water even when subjected to a large amount of sweat or rain, and a fiber structure using the same.
- Exothermic fiber using heat generated when adsorbing moisture has higher heat retention than conventional fibers and is often used mainly for sports clothing such as winter clothing and mountaineering.
- a typical fiber that generates heat by this heat of adsorption is a highly crosslinked polyacrylate fiber proposed by some of the present inventors (Patent Document 1).
- This fiber is a fiber obtained by modifying acrylic fiber as a raw material, hydrophilizing the molecule, and at the same time highly cross-linking, and forms a fiber form with high hygroscopicity and suppressed swelling.
- the exothermic fiber was first used in the skiing batting of the Japanese team at the Winter Olympics held in 1994 in Lillehammer, Norway. Opened (Non-Patent Documents 1 and 2).
- a general highly crosslinked polyacrylate fiber can be obtained by crosslinking acrylic fiber with hydrazine or the like to suppress swelling when wet and introduce a hydrophilic group.
- the hydrophilic group can be introduced by hydrolyzing a part of the functional group of the fiber to form a carboxyl group (—COOH) and / or an alkali metal salt type carboxyl group (for example, —COONa).
- Patent Document 2 proposals of exothermic fibers using heat of moisture adsorption continued, and applied to underwear (Patent Document 2), application to other fibers as well as acrylic fibers (Patent Document 3), and wool to acid
- Patent Document 4 proposals for treating and hollowing out heat (Patent Document 4), proposals for blending acrylic fibers and viscose rayon fibers (Patent Document 5), and the like.
- the properties of the exothermic fiber by moisture adsorption of the prior art are inevitably due to the introduction of a large amount of hydrophilic groups and the heat of adsorption generated from the original moisture adsorption properties of cellulosic fibers. Affinity with water increases. Therefore, the fibers are easy to get wet with sweat in the liquid phase (liquid) at the time of sweating, and once they get wet with rain, they do not generate heat, and on the contrary, the hydrophilic group has the property of not releasing the water in the liquid phase, so it dries out. On the other hand, there was a problem that the feeling of cooling increased and the comfort was poor.
- the present invention improves the highly crosslinked polyacrylate fiber that generates heat by moisture adsorption, repels water even when it comes into contact with liquid phase moisture, and adsorbs moisture in the gas phase (vapor).
- a hydrophobized highly cross-linked polyacrylate fiber and a fiber structure using the same are provided.
- the hydrophobized highly cross-linked polyacrylate fiber of the present invention has a liquid phase by binding, adsorbing or adhering a hydrophobizing agent to the highly cross-linked polyacrylate fiber that generates heat by adsorbing moisture by containing a hydrophilic group. It is characterized by repelling water with respect to moisture and generating moisture by absorbing moisture in the gas phase (steam).
- the fiber structure of the present invention is characterized in that the hydrophobized highly crosslinked polyacrylate fiber is contained in an amount of 5% by weight to less than 100% by weight, and other fibers are contained in an amount of more than 0% by weight and 95% by weight or less.
- the hydrophobized highly cross-linked polyacrylate fiber of the present invention is a liquid such as a large amount of sweat or rain due to binding, adsorbing or adhering a hydrophobizing agent to the highly cross-linked polyacrylate fiber that generates heat by adsorbing moisture. Even when it comes into contact with the water of the phase (liquid), it repels water and continues to absorb moisture. That is, the hydrophobized highly cross-linked polyacrylate fiber of the present invention is hydrophobic with respect to water in the liquid phase. Adsorption and heat generation continues.
- FIG. 1 is a partial cross-sectional explanatory view for measuring heat generation due to moisture adsorption by bringing a spun yarn into contact with liquid water in one embodiment of the present invention.
- the inventors of the present invention performed sports involving mountain climbing and sweating under various conditions while wearing conventional clothing using fibers that generate heat by adsorbing moisture. Mountain climbing often sweats a lot and sometimes gets wet in the rain. When wet with a large amount of sweat or rain, conventional heat-generating fibers that adsorb moisture have a problem of cooling. The reason for this is that conventional exothermic fibers that adsorb moisture use the heat of adsorption resulting from the addition of hydrophilic groups and the original properties of cellulosic fibers, so they also have a high affinity for liquid phase moisture.
- the hydrophilic group has the property of not releasing water in the liquid phase. Occurred. Particularly in high mountains, winter mountains, and cold seasons, it was necessary to develop clothing that is less susceptible to cooling due to water absorption and that maintains moisture absorption and heat generation.
- the highly cross-linked polyacrylate fiber used in the present invention is a fiber in which the fiber is superhydrophilic and highly cross-linked by modification of acrylic fiber, and is a fiber having a carboxyl group and / or a salt-type carboxyl group as a hydrophilic group.
- a hydrophilic group a sulfonic acid group and / or a sulfonic acid group may be used.
- Examples of such highly crosslinked polyacrylate fibers include Toyobo's trade name “N-38, Ex” and Toho Textile's trade name “Sunburner”.
- the fibers of the present invention preferably do not sink in water for more than 10 minutes when the opened fibers are dropped into still water. That is, by its own weight, it does not sink in water for 10 minutes or more, preferably 20 minutes or more, more preferably 30 minutes or more, particularly preferably 60 minutes or more.
- the fiber of the present invention continues to absorb moisture and generate heat even when subjected to a large amount of sweat or rain, and is warm, has high heat retention, and is comfortable to wear.
- the fiber of the present invention repels water with respect to liquid phase moisture, and moisture in the gas phase (vapor) absorbs heat to generate heat, in an atmosphere of temperature 20 ° C. and humidity 45% RH (RH is relative humidity).
- RH is relative humidity
- the duration of heat generation to a temperature of 21 ° C. or higher is preferably 10 minutes or longer. More preferably, the duration of heat generation at a temperature of 21 ° C. or more is 20 minutes or more, more preferably 30 minutes or more, and particularly preferably 60 minutes or more.
- a hydrophobic substance is bound, adsorbed or adhered to the highly crosslinked polyacrylate fiber.
- fluorine is bonded by bringing fluorine gas into contact with the surface of the highly crosslinked polyacrylate fiber.
- it is expressed by binding, adsorbing or adhering a hydrophobizing agent containing a fluorine-containing compound, a silicone compound, a fluorine-containing silicone compound or a hydrocarbon compound.
- the hydrophobizing agent is a compound that hydrophobizes the partner substance, for example, a water repellent.
- the term “bond” includes a chemical bond
- the term “adsorption” includes physical adsorption
- the term “adhesion” refers to a state in which the degree of adhesion between substances is lower than that of the bond or adsorption but is not released.
- the fiber of the present invention has hydrophilic functional groups in the side chains, and the hydrophobizing agent is preferably bonded to these functional groups. This is because even if washing is repeated, the hydrophobicity is not lowered.
- the fluorinated hydrophobizing agent that can be used in the present invention include commercially available products “Asahi Guard AG7000” (trade name), “Asahi Guard AG 970” (trade name), “Asahi Guard AG-E082” (trade name), and the like.
- Modified silicone “X-22-163A” (trade name, both-end type epoxy-modified silicone) “KF-8012” (trade name, both-terminal amino-modified silicone), both manufactured by Shin-Etsu Silicone Co., Ltd.
- fluorine-containing silicone compounds commercially available products are “NK Guard S-07” and “NK Guard S-09” manufactured by Nikka Chemical Co., Ltd.
- the hydrocarbon compound there is a high melting point wax emulsion, manufactured by Nikka Chemical Co., Ltd., and trade name “TH-44”. These hydrophobizing agents are preferably attached to the fiber in a state dispersed in water.
- the fiber can be contacted by a method of immersing the fiber in a treatment liquid, spraying the fiber, or padding, and then fixing by heat treatment with a cure set.
- the adhesion amount of the hydrophobizing agent is preferably 0.01 to 2.00 owf% (owf is an abbreviation for on the weight of fiber), more preferably 0.1 to 1.0 owf%.
- the treatment with the hydrophobizing agent of the present invention may be performed in a fiber state, but may be performed in a yarn state, or may be performed in a fabric state (woven fabric, knitted fabric, non-woven fabric).
- a commonly used treatment method such as dipping, padding, printing or the like can be adopted.
- the hydrophobized moisture-absorbing exothermic fiber of the present invention preferably has a moisture adhesion amount of 400% or less of its own weight when the opened fiber is dropped into still water.
- Conventional highly cross-linked polyacrylate fibers have a high affinity for moisture, and some of them have a water absorption rate exceeding 400% of their own weight.
- the water absorption rate can be lowered by the hydrophobization treatment of the present invention. Lowering the water absorption rate has the advantage of making it easier to dry.
- the texture of the fiber may become coarse and hard, and in such cases, it may be used in combination with a softener.
- Any known softening agent can be used.
- the adhesion amount of the softening agent is preferably 0.01 to 2.00 owf%, more preferably 0.1 to 1.0 owf%.
- the hydrophobized highly crosslinked polyacrylate fiber of the present invention has hygroscopicity. That is, it exhibits hygroscopicity as in the case where it is not hydrophobically processed.
- the moisture absorption rate in an atmosphere at a temperature of 20 ° C. and a relative humidity of 95% is preferably 40% or more of its own weight. When the moisture absorption rate is high, it is easy to absorb vapor in the vapor phase during sweating, and comfort is good.
- the hydrophobized highly crosslinked polyacrylate fiber of the present invention may be 5 to 100% by weight, and the other fibers may be 0 to 95% by weight.
- Other fibers include polyester, polyolefin, nylon, polypropylene, rayon (manufactured by Lenzing, including "Tencel"), cupra, acetate, ethylene vinyl alcohol (example: Kuraray, "Sofista”), It may be any fiber such as cotton (cotton), hemp, silk, animal fiber represented by wool (wool), general acrylic fiber, and highly crosslinked polyacrylate fiber. Includes stuffing like feathers.
- Blending is a blending of two or more fibers at the cotton stage. For example, blending with mixed cotton, card, strips, sliver and the like. Used mainly for uniform mixing of spun yarn, non-woven fabric, and stuffed cotton.
- Combined yarn Combined yarn is a mixture of two or more yarns twisted together. For example, in the case of twin yarn, it is a mixture in which the fiber yarn of the present invention and other fiber yarns are twisted together. Used for twisting spun yarns, spun yarns and filament yarns, and filament yarns.
- Mixed fiber Mixed fiber is used when mixing single fibers of filament yarns.
- Interwoven is a mixture when a plurality of types of yarns constituting a woven fabric are used to form a woven fabric.
- the warp and the weft may be different types, or a plurality of warps and wefts may be used.
- Knit Knit is a mixture when multiple types of yarn are used when manufacturing a knitted fabric.
- a plurality of laminated fiber layers are mixed by needle punching and hydroentanglement in the production of a nonwoven fabric.
- the fiber structure of the present invention preferably contains 5% by weight or more of the fiber of the present invention. More preferably, it is mixed with other fibers.
- the other fibers are as described above. The reason why it is preferable to mix with other fibers is to maintain the liquid phase moisture in the other fibers when wetted with a large amount of sweat or rain, and to keep the moisture absorption heat generation of the fibers of the present invention. If it does in this way, although it will be in the wet state as a whole fiber, since the hygroscopic heat_generation
- the moisture absorption heat generation effect of the fiber of the present invention can be obtained because the polyester fiber absorbs and dries liquid water quickly against a large amount of sweat or rain. As a result, evaporative cooling is less likely to occur and the temperature becomes warmer. Furthermore, as a synergistic effect, the heat generation persistence of the fiber of the present invention also promotes the (water absorption) drying property of the polyester fiber itself, resulting in faster drying and better comfort.
- yarn, woven fabric, knitted fabric, non-woven fabric or stuffing is preferable. In the case of stuffing, it may be used by mixing with feathers.
- one end of the structure is immersed in still water at a temperature of 20 ° C. for 2 minutes and 30 seconds, and evaporative cooling is not observed or is lower than that of a hydrophobized untreated product by subsequent thermography measurement. preferable. This indicates that it is difficult to get wet, and it is related to the fact that when worn, there is less feeling of cooling and comfort can be obtained.
- ⁇ Measurement method> Measuring method of moisture absorption exothermic test of raw cotton (1) The opened raw cotton and water were left in an indoor environment at a temperature of 20 ° C. and 45% RH for 2 hours or more. Thereby, the moisture absorption of the raw cotton was terminated in the measurement environment. The water was kept at room temperature so that the temperature did not fluctuate during the test. (2) 16 g of water was placed in a petri dish having a diameter of 75 mm. (3) 1 g of raw cotton was taken out. (4) Grasping raw cotton with tweezers and placing it on petri dish water.
- thermography for example, product name “H2630” manufactured by NEC Avio Infrared Technology Co., Ltd.
- Observation was made until the end of heat generation at intervals of 5 seconds, the heat generation was photographed with a camera, and the data was stored in a personal computer. At the end of heat generation, the maximum temperature of the sample was less than 21 ° C.
- the duration of heat generation was measured.
- the weight increase rate (water absorption rate) of a sample with a constant contact time with water and weight was measured.
- the measurement method is as follows. (1) 1 g of the opened raw cotton was weighed (A). (2) In an indoor environment at a temperature of 20 ° C. and a humidity of 45% RH, 200 g of water was put into a 300 cc beaker, and the raw cotton was floated on the water surface. The judgment was as follows. Float: The one that floated during the fever duration. Semi-sink: The fiber partly sinks in the water during the fever duration, but floats as a whole. Sink: The entire fiber sinks within the duration of the fever. The time to sink was measured.
- Weight increase rate (water absorption) (BA) ⁇ 100 / A
- Measuring method of average temperature The average temperature of the entire sample surface from the water surface at the time of 2 minutes 30 seconds to the upper clip 2 was measured by thermography.
- Example 1 Highly cross-linked polyacrylate fiber
- hydrophilic groups such as carboxyl groups and / or carboxyl salts are introduced
- Toyobo Co., Ltd. trade name “N-38, Ex” single fiber fineness: 2.4 dtex, fiber Length: 35 mm
- Hydrophobic processing The following hydrophobizing agents were used. The hydrophobic processing is also described. In the following, processed products using a hydrophobizing agent are indicated as “modified”.
- Experiment number 1 As a side-chain both-end type epoxy-modified silicone that is a hydrophobizing agent, the adhesion rate of the 0.1% aqueous solution is obtained after the fibers are immersed in a 0.1% aqueous solution of the trade name “X-22-9002” manufactured by Shin-Etsu Silicone Co., Ltd. After dehydrating with a dehydrator to 100 owf% (pure content adhesion rate 0.1 owf%), drying was performed at 105 ° C. for 30 minutes, and then cured at 170 ° C. for 30 minutes.
- Experiment number 2 In Experiment No.
- Remark 1 * is a comparative example (the same applies to the following table).
- the fibers of Experiment Nos. 1-1 to 1-5 repel water even when they come into contact with liquid phase moisture, and the hygroscopic heat generation continues. Even when they come into contact with liquid phase moisture, the rate of water increase is low. It was also confirmed that the moisture absorption rate in an atmosphere at a temperature of 20 ° C. and a humidity of 45% RH was 20% or more of its own weight. Moreover, the fiber during the exothermic duration on water floated and did not sink. Experiment number 1-2 was “half-sinking” but did not sink.
- Example 2 30% by weight of the fibers of Experiment Nos. 1-1 to 1-6 in Example 1 and 70% by weight of polyethylene terephthalate fiber (single fiber fineness: 1.1 dtex, fiber length: 35 mm) were blended with a card device, A 40-meter spun yarn was produced by applying Z twist (890 times / m) with a ring spinning device.
- experiment numbers 2-1 to 2-6 Experiments corresponding to the fibers of experiment numbers 1-1 to 1-6 are designated as experiment numbers 2-1 to 2-6.
- Various measurement results of the spun yarn obtained as described above are summarized in Table 3 below.
- the fibers of Experiment Nos. 2-1 to 2-5 repel water even when they come into contact with water in the liquid phase, the heat of moisture absorption continues, and there is no evaporative cooling or it is lower than the comparative product. I was able to confirm. It was also confirmed that the moisture increase rate was low even when it was in contact with liquid phase moisture.
Abstract
These hydrophobized hypercrosslinked polyacrylate fibers undergo hygroscopic heat release with respect to vapor phase water and repel liquid phase water by means of further causing a hydrophobizing agent to be bonded, adsorbed, or attached to hypercrosslinked polyacrylate fibers that release heat by adsorbing water by means of containing a hydrophilic group. Preferably, the fibers have the property of not sinking in water for at least 10 minutes when the hydrophobized hypercrosslinked polyacrylate fibers are opened and dropped onto still water. The fibrous structure of the present invention contains at least 5 wt% and less than 100 wt% of the hydrophobized hypercrosslinked polyacrylate fiber and over 0 wt% and no greater than 95 wt% of another fiber. As a result, provided are: the hydrophobized hypercrosslinked polyacrylate fibers, which have sustained hygroscopic heat release, repel water even if contacting liquid phase water, and improve on hypercrosslinked polyacrylate fibers that generate heat by adsorbing water; and a fibrous structure using the hydrophobized hypercrosslinked polyacrylate fibers.
Description
本発明は、多量発汗や雨がかかっても水をはじき、吸湿発熱が持続する疎水化吸湿発熱繊維及びこれを用いた繊維構造物に関するものである。
The present invention relates to a hydrophobized moisture-absorbing exothermic fiber that repels water even when subjected to a large amount of sweat or rain, and a fiber structure using the same.
水分を吸着する時に発生する熱（吸着熱）を利用した発熱性繊維は、従来繊維に比べより高い保温性を有し、主に冬物衣料や登山などのスポーツ衣料に使用される場合が多い。この吸着熱によって発熱する代表的繊維は、本発明者らの一部が提案した高架橋ポリアクリレート系繊維である（特許文献１）。この繊維は、アクリル系繊維を原料にして改質し、分子を親水化し同時に高架橋化した繊維であり、吸湿性が高く、かつ膨潤性が抑制された繊維形態をなす。発熱性繊維は、１９９４年ノルウェーのリレハンメルで開催された冬季オリンピックで日本チームのスキーウエアの中綿に採用されたのが最初であり、それまでの衣料分野にはなかった「発熱保温」という概念を切り開いた（非特許文献１、２）。本出願人らは商品名“ブレスサーモ”（登録商標）という繊維製品を開発し、現在においても好評を博している。一般的な高架橋ポリアクリレート系繊維は、アクリル系繊維をヒドラジン等で架橋して湿潤時の膨潤を抑制し、かつ親水性基を導入することによって得られる。親水性基は繊維が有する官能基の一部を加水分解してカルボキシル基（－ＣＯＯＨ）及び／又はアルカリ金属塩型カルボキシル基（例えば－ＣＯＯＮａ）にすることで導入できる。
Exothermic fiber using heat generated when adsorbing moisture (adsorption heat) has higher heat retention than conventional fibers and is often used mainly for sports clothing such as winter clothing and mountaineering. A typical fiber that generates heat by this heat of adsorption is a highly crosslinked polyacrylate fiber proposed by some of the present inventors (Patent Document 1). This fiber is a fiber obtained by modifying acrylic fiber as a raw material, hydrophilizing the molecule, and at the same time highly cross-linking, and forms a fiber form with high hygroscopicity and suppressed swelling. The exothermic fiber was first used in the skiing batting of the Japanese team at the Winter Olympics held in 1994 in Lillehammer, Norway. Opened (Non-Patent Documents 1 and 2). The present applicants have developed a textile product named “Breath Thermo” (registered trademark), which has been well received today. A general highly crosslinked polyacrylate fiber can be obtained by crosslinking acrylic fiber with hydrazine or the like to suppress swelling when wet and introduce a hydrophilic group. The hydrophilic group can be introduced by hydrolyzing a part of the functional group of the fiber to form a carboxyl group (—COOH) and / or an alkali metal salt type carboxyl group (for example, —COONa).
その後も水分の吸着熱を利用した発熱性繊維の提案は続いており、肌着への適用（特許文献２）、アクリル系繊維のみならず他の繊維への応用（特許文献３）、ウールを酸処理して中空にして発熱させる提案（特許文献４）、アクリル系繊維とビスコースレーヨン繊維を混紡する提案（特許文献５）等がある。
After that, proposals of exothermic fibers using heat of moisture adsorption continued, and applied to underwear (Patent Document 2), application to other fibers as well as acrylic fibers (Patent Document 3), and wool to acid There are proposals (Patent Document 4) for treating and hollowing out heat (Patent Document 4), proposals for blending acrylic fibers and viscose rayon fibers (Patent Document 5), and the like.
しかし、従来技術の水分吸着による発熱性繊維の特性は、大量の親水性基を導入することやセルロース系繊維の元来の水分吸着特性から生じる吸着熱を利用することから、必然的に繊維は水との親和性が高くなる。したがって、繊維は発汗時の液相（液体）の汗で濡れ易くなったり、また、いったん雨で濡れると発熱は起こらず、逆に親水性基が液相の水を離さない性質を有するので乾きにくく、却って冷感が増加し、着心地が悪いという問題があった。
However, the properties of the exothermic fiber by moisture adsorption of the prior art are inevitably due to the introduction of a large amount of hydrophilic groups and the heat of adsorption generated from the original moisture adsorption properties of cellulosic fibers. Affinity with water increases. Therefore, the fibers are easy to get wet with sweat in the liquid phase (liquid) at the time of sweating, and once they get wet with rain, they do not generate heat, and on the contrary, the hydrophilic group has the property of not releasing the water in the liquid phase, so it dries out. On the other hand, there was a problem that the feeling of cooling increased and the comfort was poor.
本発明は、前記従来の問題を解決するため、水分吸着によって発熱する高架橋ポリアクリレート系繊維を改良し、液相の水分と接触しても水をはじき、気相（蒸気）の水分を吸着して発熱が持続する疎水化高架橋ポリアクリレート系繊維及びこれを用いた繊維構造物を提供する。
In order to solve the above-mentioned conventional problems, the present invention improves the highly crosslinked polyacrylate fiber that generates heat by moisture adsorption, repels water even when it comes into contact with liquid phase moisture, and adsorbs moisture in the gas phase (vapor). A hydrophobized highly cross-linked polyacrylate fiber and a fiber structure using the same are provided.
本発明の疎水化高架橋ポリアクリレート系繊維は、親水性基を含むことにより水分を吸着して発熱する高架橋ポリアクリレート系繊維に、さらに疎水化剤を結合、吸着又は付着させることにより、液相の水分に対しては水をはじき、気相（蒸気）の水分に対しては吸湿発熱することを特徴とする。
The hydrophobized highly cross-linked polyacrylate fiber of the present invention has a liquid phase by binding, adsorbing or adhering a hydrophobizing agent to the highly cross-linked polyacrylate fiber that generates heat by adsorbing moisture by containing a hydrophilic group. It is characterized by repelling water with respect to moisture and generating moisture by absorbing moisture in the gas phase (steam).
本発明の繊維構造体は、前記の疎水化高架橋ポリアクリレート系繊維が５重量％以上１００重量％未満、その他の繊維が０重量％を超え９５重量％以下含むことを特徴とする。
The fiber structure of the present invention is characterized in that the hydrophobized highly crosslinked polyacrylate fiber is contained in an amount of 5% by weight to less than 100% by weight, and other fibers are contained in an amount of more than 0% by weight and 95% by weight or less.
本発明の疎水化高架橋ポリアクリレート系繊維は、水分を吸着して発熱する高架橋ポリアクリレート系繊維に対して疎水化剤を結合、吸着又は付着させたことにより、多量発汗や雨がかかる等、液相（液体）の水分と接触しても水をはじき、吸湿発熱が持続する。すなわち、本発明の疎水化高架橋ポリアクリレート系繊維は液相の水分に対しては疎水性であり、液相の水分と接触しても濡れないか又は濡れにくく、気相（蒸気）の水分を吸着して発熱が持続する。この結果、多量発汗や雨がかかっても冷えにくく、蒸発した水分（気相）を吸着し吸着熱に位相転換し発熱することによって、繊維は温かくなり且つ温かさをより長く持続することによって、快適な着心地となる。
The hydrophobized highly cross-linked polyacrylate fiber of the present invention is a liquid such as a large amount of sweat or rain due to binding, adsorbing or adhering a hydrophobizing agent to the highly cross-linked polyacrylate fiber that generates heat by adsorbing moisture. Even when it comes into contact with the water of the phase (liquid), it repels water and continues to absorb moisture. That is, the hydrophobized highly cross-linked polyacrylate fiber of the present invention is hydrophobic with respect to water in the liquid phase. Adsorption and heat generation continues. As a result, it is difficult to cool even when a large amount of sweat or rain is applied, and it absorbs evaporated water (gas phase), changes phase to adsorption heat and generates heat, so that the fiber becomes warm and the warmth lasts longer, so it is comfortable It will be comfortable to wear.
本発明者らは、従来の水分を吸着して発熱する繊維を用いた衣類を着用して様々な条件の登山や発汗を伴うスポーツをした。登山においては多量の発汗をすることが多く、また雨に濡れる場合もある。多量の発汗や雨で濡れてしまうと、従来の水分を吸着する発熱繊維は冷たくなる問題があった。その理由は、従来の水分を吸着する発熱繊維は親水性基の付与やセルロース系繊維の元来の特性から生じる吸着熱を利用するため、液相の水分とも親和性が高く、液相の水分と接触すると吸水して濡れてしまい、発熱も止まってしまうばかりでなく、逆に親水性基が液相の水を離さない性質を有するので、却って冷感が増加し、着心地を害するという現象が生じた。特に高山や冬山や寒い時期には、吸水による冷感が生じにくく且つ吸湿発熱性が持続する衣類の開発が必要であった。
The inventors of the present invention performed sports involving mountain climbing and sweating under various conditions while wearing conventional clothing using fibers that generate heat by adsorbing moisture. Mountain climbing often sweats a lot and sometimes gets wet in the rain. When wet with a large amount of sweat or rain, conventional heat-generating fibers that adsorb moisture have a problem of cooling. The reason for this is that conventional exothermic fibers that adsorb moisture use the heat of adsorption resulting from the addition of hydrophilic groups and the original properties of cellulosic fibers, so they also have a high affinity for liquid phase moisture. When it comes into contact with water, it absorbs water and gets wet, the heat generation stops, and conversely, the hydrophilic group has the property of not releasing water in the liquid phase. Occurred. Particularly in high mountains, winter mountains, and cold seasons, it was necessary to develop clothing that is less susceptible to cooling due to water absorption and that maintains moisture absorption and heat generation.
そこで、気相の水分（蒸気）は吸着するが、液相（液体）の水分は吸着しない繊維材料の着想に至った。具体的には、（１）高架橋ポリアクリレート系繊維の水分を吸着して発熱する性質に加えて、（２）疎水化剤を結合、吸着又は付着させて液相の水分に対しては疎水性を付与することにより、液相の水分と接触しても濡れないか又は濡れにくく、蒸気や人体からの不感蒸泄などの気相の水分から吸湿して発熱が持続する繊維である。
Therefore, the idea of a fiber material that adsorbs gas phase moisture (vapor) but does not adsorb liquid phase (liquid) moisture has been reached. Specifically, (1) In addition to the property of generating heat by adsorbing moisture from the highly crosslinked polyacrylate fiber, (2) Hydrophobic agent is bonded, adsorbed or adhered to make it hydrophobic to liquid phase moisture It is a fiber that does not get wet even when it comes into contact with water in the liquid phase, or that does not easily get wet, absorbs moisture from the gas phase such as vapor or insensitive excretion from the human body, and continues to generate heat.
１．高架橋ポリアクリレート系繊維について
本発明において高架橋ポリアクリレート系繊維を選択したのは、表１（前記非特許文献１から転載）に示すとおり、他の繊維に比べて吸着熱が高いからである。 1. About the highly cross-linked polyacrylate-based fiber The reason why the highly cross-linked polyacrylate-based fiber is selected in the present invention is that the heat of adsorption is higher than other fibers as shown in Table 1 (reprinted from Non-Patent Document 1).
本発明において高架橋ポリアクリレート系繊維を選択したのは、表１（前記非特許文献１から転載）に示すとおり、他の繊維に比べて吸着熱が高いからである。 1. About the highly cross-linked polyacrylate-based fiber The reason why the highly cross-linked polyacrylate-based fiber is selected in the present invention is that the heat of adsorption is higher than other fibers as shown in Table 1 (reprinted from Non-Patent Document 1).
（備考）Ｃ８０熱量計を用いて、試料を絶乾から２５℃、８０．５％ＲＨの条件下で測定した値（前記非特許文献１の４６５頁表３・１４，但しコットンについては熱量単位がｃａｌで示されており、Ｊ／ｇに換算して修正した）。
(Remarks) Values measured using a C80 calorimeter under conditions of absolutely dry to 25 ° C. and 80.5% RH (Table 3 and 14 on page 465 of
本発明に使用する高架橋ポリアクリレート系繊維は、アクリル繊維の改質により繊維を超親水化、高架橋化した繊維であり、親水性基としてカルボキシル基及び／又は塩型カルボキシル基を有する繊維である。親水性基の別の例としては、スルホン酸基及び／又はスルホン酸塩基であっても良い。
The highly cross-linked polyacrylate fiber used in the present invention is a fiber in which the fiber is superhydrophilic and highly cross-linked by modification of acrylic fiber, and is a fiber having a carboxyl group and / or a salt-type carboxyl group as a hydrophilic group. As another example of the hydrophilic group, a sulfonic acid group and / or a sulfonic acid group may be used.
かかる高架橋ポリアクリレート系繊維としては、例えば東洋紡社製商品名“Ｎ－３８、エクス”、東邦テキスタイル社製商品名“サンバーナー”などがある。
Examples of such highly crosslinked polyacrylate fibers include Toyobo's trade name “N-38, Ex” and Toho Textile's trade name “Sunburner”.
２．疎水性について
本発明の繊維は、開繊した繊維を静水に落下させたとき、１０分以上水に沈まないことが好ましい。すなわち、自重では１０分以上、好ましくは２０分以上、さらに好ましくは３０分以上、とくに好ましくは６０分以上水に沈まない。この疎水性の付与により、本発明の繊維は多量発汗や雨がかかっても繊維の吸湿発熱は持続し、温かく、保温性も高く、着心地は良いものとなる。 2. Hydrophobicity The fibers of the present invention preferably do not sink in water for more than 10 minutes when the opened fibers are dropped into still water. That is, by its own weight, it does not sink in water for 10 minutes or more, preferably 20 minutes or more, more preferably 30 minutes or more, particularly preferably 60 minutes or more. By imparting this hydrophobicity, the fiber of the present invention continues to absorb moisture and generate heat even when subjected to a large amount of sweat or rain, and is warm, has high heat retention, and is comfortable to wear.
本発明の繊維は、開繊した繊維を静水に落下させたとき、１０分以上水に沈まないことが好ましい。すなわち、自重では１０分以上、好ましくは２０分以上、さらに好ましくは３０分以上、とくに好ましくは６０分以上水に沈まない。この疎水性の付与により、本発明の繊維は多量発汗や雨がかかっても繊維の吸湿発熱は持続し、温かく、保温性も高く、着心地は良いものとなる。 2. Hydrophobicity The fibers of the present invention preferably do not sink in water for more than 10 minutes when the opened fibers are dropped into still water. That is, by its own weight, it does not sink in water for 10 minutes or more, preferably 20 minutes or more, more preferably 30 minutes or more, particularly preferably 60 minutes or more. By imparting this hydrophobicity, the fiber of the present invention continues to absorb moisture and generate heat even when subjected to a large amount of sweat or rain, and is warm, has high heat retention, and is comfortable to wear.
本発明の繊維は、液相の水分に対しては水をはじき、かつ気相の水分（蒸気）は吸湿して発熱し、温度２０℃、湿度４５％ＲＨ（ＲＨは相対湿度）の雰囲気で液相の水分と接触させたとき、２１℃以上の温度に発熱している持続時間が１０分以上であることが好ましい。さらに好ましくは、２１℃以上の温度に発熱している持続時間が２０分以上、さらに好ましくは、３０分以上、とくに好ましくは、６０分以上である。
The fiber of the present invention repels water with respect to liquid phase moisture, and moisture in the gas phase (vapor) absorbs heat to generate heat, in an atmosphere of temperature 20 ° C. and humidity 45% RH (RH is relative humidity). When contacted with liquid phase moisture, the duration of heat generation to a temperature of 21 ° C. or higher is preferably 10 minutes or longer. More preferably, the duration of heat generation at a temperature of 21 ° C. or more is 20 minutes or more, more preferably 30 minutes or more, and particularly preferably 60 minutes or more.
前記高架橋ポリアクリレート系繊維を疎水化する方法について説明する。前記高架橋ポリアクリレート系繊維を疎水化するには、前記高架橋ポリアクリレート系繊維に対して疎水性物質を結合、吸着又は付着させる。例えば、前記高架橋ポリアクリレート系繊維の表面にフッ素ガスを接触させてフッ素を結合させる。あるいは、フッ素含有化合物、シリコーン化合物、フッ素含有シリコーン化合物又は炭化水素系化合物を含む疎水化剤を結合、吸着又は付着させることにより発現される。
The method for hydrophobizing the highly crosslinked polyacrylate fiber will be described. In order to hydrophobize the highly crosslinked polyacrylate fiber, a hydrophobic substance is bound, adsorbed or adhered to the highly crosslinked polyacrylate fiber. For example, fluorine is bonded by bringing fluorine gas into contact with the surface of the highly crosslinked polyacrylate fiber. Alternatively, it is expressed by binding, adsorbing or adhering a hydrophobizing agent containing a fluorine-containing compound, a silicone compound, a fluorine-containing silicone compound or a hydrocarbon compound.
疎水化剤とは、相手物質を疎水化する化合物であり、例えば撥水剤のことをいう。
The hydrophobizing agent is a compound that hydrophobizes the partner substance, for example, a water repellent.
本発明において結合とは化学結合を含み、吸着とは物理吸着を含み、付着とは結合や吸着よりは物質間の密着の程度は低いが遊離していない状態を言う。
In the present invention, the term “bond” includes a chemical bond, the term “adsorption” includes physical adsorption, and the term “adhesion” refers to a state in which the degree of adhesion between substances is lower than that of the bond or adsorption but is not released.
本発明の繊維は、側鎖に親水性の官能基を有しており、疎水化剤はこれらの官能基と結合させるのが好ましい。洗濯を繰り返しても疎水性を低下させないためである。本発明で使用できるフッ素系疎水化剤としては、例えば市販品の“アサヒガードＡＧ７０００”（商品名）、“アサヒガードＡＧ９７０”（商品名）、“アサヒガードＡＧ－Ｅ０８２”（商品名）等のＡＧシリーズ、“アサヒガードＧＳ１０”（商品名）（いずれも旭硝子社製、フッ素系疎水剤エマルジョン）、“ＮＫガードＦＧＮ７００Ｔ”（商品名）、“ＮＫガードＮＤＮ７０００”（商品名）（いずれも日華化学社製、フッ素系疎水剤エマルジョン）等がある。変性シリコーン系疎水化剤としては、エポキシ変性シリコーン系疎水化剤、アミノ変性シリコーン系疎水化剤等があり、市販品としては、“Ｘ－２２－９００２”（商品名、側鎖両末端型エポキシ変性シリコーン）、“Ｘ－２２－１６３Ａ”（商品名、両末端型エポキシ変性シリコーン）“ＫＦ－８０１２”（商品名、両末端アミノ変性シリコーン）、いずれも信越シリコーン社製などがある。フッ素含有シリコーン化合物としては、市販品として日華化学社製、商品名“ＮＫガードＳ－０７”、“ＮＫガードＳ－０９”がある。炭化水素系化合物としては、高融点ワックスエマルジョン：日華化学社製、商品名“ＴＨ－４４”がある。これら疎水化剤は水に分散させた状態で繊維に付着させるのが好ましい。繊維を処理液に浸漬する、繊維に噴霧する、あるいはパッドする方法などにより接触させ、その後キュアセットによる熱処理により固定できる。疎水化剤の付着量は、０．０１～２．００owf%(owfはon the weight of fiberの略)が好ましく、さらに好ましくは０．１～１．０owf%である。
The fiber of the present invention has hydrophilic functional groups in the side chains, and the hydrophobizing agent is preferably bonded to these functional groups. This is because even if washing is repeated, the hydrophobicity is not lowered. Examples of the fluorinated hydrophobizing agent that can be used in the present invention include commercially available products “Asahi Guard AG7000” (trade name), “Asahi Guard AG 970” (trade name), “Asahi Guard AG-E082” (trade name), and the like. AG series, “Asahi Guard GS10” (trade name) (all manufactured by Asahi Glass, fluorine-based hydrophobic emulsion), “NK Guard FGN700T” (product name), “NK Guard NDN7000” (trade name) (all Nikka) Chemical-made, fluorine-based hydrophobic agent emulsion). Examples of modified silicone hydrophobizing agents include epoxy-modified silicone hydrophobizing agents and amino-modified silicone hydrophobizing agents. Commercially available products include “X-22-9002” (trade name, both side chain type epoxy resins). Modified silicone), “X-22-163A” (trade name, both-end type epoxy-modified silicone) “KF-8012” (trade name, both-terminal amino-modified silicone), both manufactured by Shin-Etsu Silicone Co., Ltd. As fluorine-containing silicone compounds, commercially available products are “NK Guard S-07” and “NK Guard S-09” manufactured by Nikka Chemical Co., Ltd. As the hydrocarbon compound, there is a high melting point wax emulsion, manufactured by Nikka Chemical Co., Ltd., and trade name “TH-44”. These hydrophobizing agents are preferably attached to the fiber in a state dispersed in water. The fiber can be contacted by a method of immersing the fiber in a treatment liquid, spraying the fiber, or padding, and then fixing by heat treatment with a cure set. The adhesion amount of the hydrophobizing agent is preferably 0.01 to 2.00 owf% (owf is an abbreviation for on the weight of fiber), more preferably 0.1 to 1.0 owf%.
本発明の疎水化剤による処理は、繊維状態で行っても良いが、糸の状態で行っても良いし、布帛（織物、編物、不織布）の状態で行っても良い。疎水化処理方法は、浸漬、パッド、プリント等の一般的に行われている処理方法を採用できる。
The treatment with the hydrophobizing agent of the present invention may be performed in a fiber state, but may be performed in a yarn state, or may be performed in a fabric state (woven fabric, knitted fabric, non-woven fabric). As the hydrophobizing treatment method, a commonly used treatment method such as dipping, padding, printing or the like can be adopted.
３．重量増加率（吸水率）
本発明の疎水化吸湿発熱繊維は、開繊した前記繊維を静水に落下させたときの水分付着量が自重の４００％以下であることが好ましい。従来の高架橋ポリアクリレート系繊維は水分との親和性が高いため、自重の４００％を越える吸水率となるものもあるが、本発明の疎水化処理により吸水率を低くすることができる。吸水率を低くすると乾き易くなる利点がある。 3. Weight increase rate (water absorption rate)
The hydrophobized moisture-absorbing exothermic fiber of the present invention preferably has a moisture adhesion amount of 400% or less of its own weight when the opened fiber is dropped into still water. Conventional highly cross-linked polyacrylate fibers have a high affinity for moisture, and some of them have a water absorption rate exceeding 400% of their own weight. However, the water absorption rate can be lowered by the hydrophobization treatment of the present invention. Lowering the water absorption rate has the advantage of making it easier to dry.
本発明の疎水化吸湿発熱繊維は、開繊した前記繊維を静水に落下させたときの水分付着量が自重の４００％以下であることが好ましい。従来の高架橋ポリアクリレート系繊維は水分との親和性が高いため、自重の４００％を越える吸水率となるものもあるが、本発明の疎水化処理により吸水率を低くすることができる。吸水率を低くすると乾き易くなる利点がある。 3. Weight increase rate (water absorption rate)
The hydrophobized moisture-absorbing exothermic fiber of the present invention preferably has a moisture adhesion amount of 400% or less of its own weight when the opened fiber is dropped into still water. Conventional highly cross-linked polyacrylate fibers have a high affinity for moisture, and some of them have a water absorption rate exceeding 400% of their own weight. However, the water absorption rate can be lowered by the hydrophobization treatment of the present invention. Lowering the water absorption rate has the advantage of making it easier to dry.
４．柔軟剤との併用
疎水剤の種類や加工条件によっては、繊維の風合いが粗硬になる場合もあるので、このような場合には柔軟剤と併用しても良い。柔軟剤は公知のいかなるものも使用できる。例えば市販品として明成化学社製、商品名“メイシリコーンＳＦ”（アミノ変性シリコーン）がある。柔軟剤の付着量は、０．０１～２．００owf%が好ましく、さらに好ましくは０．１～１．０owf%である。 4). Combined use with softeners Depending on the type and processing conditions of the hydrophobic agent, the texture of the fiber may become coarse and hard, and in such cases, it may be used in combination with a softener. Any known softening agent can be used. For example, as a commercial product, there is a product name “May Silicone SF” (amino-modified silicone) manufactured by Meisei Chemical Co., Ltd. The adhesion amount of the softening agent is preferably 0.01 to 2.00 owf%, more preferably 0.1 to 1.0 owf%.
疎水剤の種類や加工条件によっては、繊維の風合いが粗硬になる場合もあるので、このような場合には柔軟剤と併用しても良い。柔軟剤は公知のいかなるものも使用できる。例えば市販品として明成化学社製、商品名“メイシリコーンＳＦ”（アミノ変性シリコーン）がある。柔軟剤の付着量は、０．０１～２．００owf%が好ましく、さらに好ましくは０．１～１．０owf%である。 4). Combined use with softeners Depending on the type and processing conditions of the hydrophobic agent, the texture of the fiber may become coarse and hard, and in such cases, it may be used in combination with a softener. Any known softening agent can be used. For example, as a commercial product, there is a product name “May Silicone SF” (amino-modified silicone) manufactured by Meisei Chemical Co., Ltd. The adhesion amount of the softening agent is preferably 0.01 to 2.00 owf%, more preferably 0.1 to 1.0 owf%.
５．吸湿性
本発明の疎水化高架橋ポリアクリレート系繊維は吸湿性を有する。すなわち、疎水加工しないものと同様に吸湿性を発揮する。一例として、温度２０℃、相対湿度９５％の雰囲気での吸湿率が自重の４０％以上であるのが好ましい。吸湿率が高いと、発汗時の気相の汗を吸収しやすく、着心地は良好となる。 5. Hygroscopicity The hydrophobized highly crosslinked polyacrylate fiber of the present invention has hygroscopicity. That is, it exhibits hygroscopicity as in the case where it is not hydrophobically processed. As an example, the moisture absorption rate in an atmosphere at a temperature of 20 ° C. and a relative humidity of 95% is preferably 40% or more of its own weight. When the moisture absorption rate is high, it is easy to absorb vapor in the vapor phase during sweating, and comfort is good.
本発明の疎水化高架橋ポリアクリレート系繊維は吸湿性を有する。すなわち、疎水加工しないものと同様に吸湿性を発揮する。一例として、温度２０℃、相対湿度９５％の雰囲気での吸湿率が自重の４０％以上であるのが好ましい。吸湿率が高いと、発汗時の気相の汗を吸収しやすく、着心地は良好となる。 5. Hygroscopicity The hydrophobized highly crosslinked polyacrylate fiber of the present invention has hygroscopicity. That is, it exhibits hygroscopicity as in the case where it is not hydrophobically processed. As an example, the moisture absorption rate in an atmosphere at a temperature of 20 ° C. and a relative humidity of 95% is preferably 40% or more of its own weight. When the moisture absorption rate is high, it is easy to absorb vapor in the vapor phase during sweating, and comfort is good.
６．他の繊維との混合
本発明の疎水化高架橋ポリアクリレート系繊維が５～１００重量％、その他の繊維が０～９５重量％であってもよい。その他の繊維としては、ポリエステル、ポリオレフィン、ナイロン、ポリプロピレン、レーヨン（レンチング社製、商品名“テンセル”を含む）、キュプラ、アセテート、エチレンビニルアルコール（一例としてクラレ社製、商品名“ソフィスタ”）、コットン（木綿）、麻、絹、ウール（羊毛）に代表される獣毛繊維、及び一般アクリル繊維、高架橋ポリアクリレート系繊維などいかなる繊維であっても良い。羽毛のような詰め物も含む。 6). Mixing with other fibers The hydrophobized highly crosslinked polyacrylate fiber of the present invention may be 5 to 100% by weight, and the other fibers may be 0 to 95% by weight. Other fibers include polyester, polyolefin, nylon, polypropylene, rayon (manufactured by Lenzing, including "Tencel"), cupra, acetate, ethylene vinyl alcohol (example: Kuraray, "Sofista"), It may be any fiber such as cotton (cotton), hemp, silk, animal fiber represented by wool (wool), general acrylic fiber, and highly crosslinked polyacrylate fiber. Includes stuffing like feathers.
本発明の疎水化高架橋ポリアクリレート系繊維が５～１００重量％、その他の繊維が０～９５重量％であってもよい。その他の繊維としては、ポリエステル、ポリオレフィン、ナイロン、ポリプロピレン、レーヨン（レンチング社製、商品名“テンセル”を含む）、キュプラ、アセテート、エチレンビニルアルコール（一例としてクラレ社製、商品名“ソフィスタ”）、コットン（木綿）、麻、絹、ウール（羊毛）に代表される獣毛繊維、及び一般アクリル繊維、高架橋ポリアクリレート系繊維などいかなる繊維であっても良い。羽毛のような詰め物も含む。 6). Mixing with other fibers The hydrophobized highly crosslinked polyacrylate fiber of the present invention may be 5 to 100% by weight, and the other fibers may be 0 to 95% by weight. Other fibers include polyester, polyolefin, nylon, polypropylene, rayon (manufactured by Lenzing, including "Tencel"), cupra, acetate, ethylene vinyl alcohol (example: Kuraray, "Sofista"), It may be any fiber such as cotton (cotton), hemp, silk, animal fiber represented by wool (wool), general acrylic fiber, and highly crosslinked polyacrylate fiber. Includes stuffing like feathers.
他の繊維との混合は、例えば下記の方法を採用できる。
（１）混紡：混紡は綿段階において２種以上の繊維の混合である。例えば混打綿、カード、練条、スライバーなどでの混合である。紡績糸、不織布、詰め綿の主に均一混合の場合に使用される。
（２）合糸：合糸は２種以上の糸を撚り合わせる混合である。例えば双糸の場合、本発明の繊維糸と他の繊維糸とを撚り合せる混合である。紡績糸同士、紡績糸とフィラメント糸、フィラメント糸同士の撚り合わせに使用される。
（３）混繊：混繊は、フィラメント糸同士の単繊維を混合するときに使用される。
（４）交織：交織は、織物を構成する糸を複数種類使用して織物にする場合の混合である。例えば、経糸と緯糸を別な種類の糸にするとか、経糸、緯糸をそれぞれ複数種使用することもできる。
（５）交編：交編は編物を製造する際に複数種類の糸を使用する場合の混合である。
（６）不織布製造におけるニードルパンチ、水流交絡によって、積層した複数種類の繊維層を混合する。 For example, the following method can be used for mixing with other fibers.
(1) Blending: Blending is a blending of two or more fibers at the cotton stage. For example, blending with mixed cotton, card, strips, sliver and the like. Used mainly for uniform mixing of spun yarn, non-woven fabric, and stuffed cotton.
(2) Combined yarn: Combined yarn is a mixture of two or more yarns twisted together. For example, in the case of twin yarn, it is a mixture in which the fiber yarn of the present invention and other fiber yarns are twisted together. Used for twisting spun yarns, spun yarns and filament yarns, and filament yarns.
(3) Mixed fiber: Mixed fiber is used when mixing single fibers of filament yarns.
(4) Interweaving: Interwoven is a mixture when a plurality of types of yarns constituting a woven fabric are used to form a woven fabric. For example, the warp and the weft may be different types, or a plurality of warps and wefts may be used.
(5) Knit: Knit is a mixture when multiple types of yarn are used when manufacturing a knitted fabric.
(6) A plurality of laminated fiber layers are mixed by needle punching and hydroentanglement in the production of a nonwoven fabric.
（１）混紡：混紡は綿段階において２種以上の繊維の混合である。例えば混打綿、カード、練条、スライバーなどでの混合である。紡績糸、不織布、詰め綿の主に均一混合の場合に使用される。
（２）合糸：合糸は２種以上の糸を撚り合わせる混合である。例えば双糸の場合、本発明の繊維糸と他の繊維糸とを撚り合せる混合である。紡績糸同士、紡績糸とフィラメント糸、フィラメント糸同士の撚り合わせに使用される。
（３）混繊：混繊は、フィラメント糸同士の単繊維を混合するときに使用される。
（４）交織：交織は、織物を構成する糸を複数種類使用して織物にする場合の混合である。例えば、経糸と緯糸を別な種類の糸にするとか、経糸、緯糸をそれぞれ複数種使用することもできる。
（５）交編：交編は編物を製造する際に複数種類の糸を使用する場合の混合である。
（６）不織布製造におけるニードルパンチ、水流交絡によって、積層した複数種類の繊維層を混合する。 For example, the following method can be used for mixing with other fibers.
(1) Blending: Blending is a blending of two or more fibers at the cotton stage. For example, blending with mixed cotton, card, strips, sliver and the like. Used mainly for uniform mixing of spun yarn, non-woven fabric, and stuffed cotton.
(2) Combined yarn: Combined yarn is a mixture of two or more yarns twisted together. For example, in the case of twin yarn, it is a mixture in which the fiber yarn of the present invention and other fiber yarns are twisted together. Used for twisting spun yarns, spun yarns and filament yarns, and filament yarns.
(3) Mixed fiber: Mixed fiber is used when mixing single fibers of filament yarns.
(4) Interweaving: Interwoven is a mixture when a plurality of types of yarns constituting a woven fabric are used to form a woven fabric. For example, the warp and the weft may be different types, or a plurality of warps and wefts may be used.
(5) Knit: Knit is a mixture when multiple types of yarn are used when manufacturing a knitted fabric.
(6) A plurality of laminated fiber layers are mixed by needle punching and hydroentanglement in the production of a nonwoven fabric.
７．繊維構造物
本発明の疎水化高架橋ポリアクリレート系繊維を含む繊維構造物について説明する。本発明の繊維構造物は、本発明の繊維を５重量％以上含むことが好ましい。他の繊維と混合するのはさらに好ましい。他の繊維は前記したとおりである。他の繊維と混合するのが好ましい理由は、多量の発汗や雨で濡れたときには他の繊維に液相の水分を保持させ、本発明の繊維の吸湿発熱を持続させるためである。このようにすると、繊維全体としては濡れた状態になるが、本発明の繊維の吸湿発熱は持続するため、繊維は温かく、保温性は高く、着心地は良好となる。 7. Fiber Structure A fiber structure containing the hydrophobized highly crosslinked polyacrylate fiber of the present invention will be described. The fiber structure of the present invention preferably contains 5% by weight or more of the fiber of the present invention. More preferably, it is mixed with other fibers. The other fibers are as described above. The reason why it is preferable to mix with other fibers is to maintain the liquid phase moisture in the other fibers when wetted with a large amount of sweat or rain, and to keep the moisture absorption heat generation of the fibers of the present invention. If it does in this way, although it will be in the wet state as a whole fiber, since the hygroscopic heat_generation | fever of the fiber of this invention continues, a fiber is warm, heat retention is high, and comfort becomes favorable.
本発明の疎水化高架橋ポリアクリレート系繊維を含む繊維構造物について説明する。本発明の繊維構造物は、本発明の繊維を５重量％以上含むことが好ましい。他の繊維と混合するのはさらに好ましい。他の繊維は前記したとおりである。他の繊維と混合するのが好ましい理由は、多量の発汗や雨で濡れたときには他の繊維に液相の水分を保持させ、本発明の繊維の吸湿発熱を持続させるためである。このようにすると、繊維全体としては濡れた状態になるが、本発明の繊維の吸湿発熱は持続するため、繊維は温かく、保温性は高く、着心地は良好となる。 7. Fiber Structure A fiber structure containing the hydrophobized highly crosslinked polyacrylate fiber of the present invention will be described. The fiber structure of the present invention preferably contains 5% by weight or more of the fiber of the present invention. More preferably, it is mixed with other fibers. The other fibers are as described above. The reason why it is preferable to mix with other fibers is to maintain the liquid phase moisture in the other fibers when wetted with a large amount of sweat or rain, and to keep the moisture absorption heat generation of the fibers of the present invention. If it does in this way, although it will be in the wet state as a whole fiber, since the hygroscopic heat_generation | fever of the fiber of this invention continues, a fiber is warm, heat retention is high, and comfort becomes favorable.
他の繊維として例えばポリエステル繊維に吸水速乾加工したものを用いると、多量の発汗や雨による濡れに対して、ポリエステル繊維が液相の水分を吸水速乾する為、本発明繊維の吸湿発熱効果が持続しやすくなり、その結果、気化冷却も生じにくく、より温かくなる。更に相乗効果として、本発明繊維の発熱持続性により、ポリエステル繊維自体の（吸水）乾燥性も助長され、乾きが早くなり、より優れた着心地となる。
For example, when using a polyester fiber that has been water-absorbing and quick-drying as other fibers, the moisture absorption heat generation effect of the fiber of the present invention can be obtained because the polyester fiber absorbs and dries liquid water quickly against a large amount of sweat or rain. As a result, evaporative cooling is less likely to occur and the temperature becomes warmer. Furthermore, as a synergistic effect, the heat generation persistence of the fiber of the present invention also promotes the (water absorption) drying property of the polyester fiber itself, resulting in faster drying and better comfort.
本発明の繊維構造物としては、糸、織物、編物、不織布又は詰め物などが好ましい。詰め物の場合は羽毛と混合して使用しても良い。さらに前記繊維構造物としては、衣類、帽子、耳掛け、マフラー、手袋、靴下、寝袋、布団、枕、クッション、毛布、ひざ掛け又はカーペットや資材関連として、住宅関連のフロアー材、壁材、畳なども挙げられる。とくに寒い時期の衣類や登山、スキーなどのスポーツウエアに好適である。衣類としては、肌着、下着、シャツ、ジャンパー、セーター、パンツ、ヤッケ、ウインドブレーカー、トレーニングウエア、雨着、タイツ、腹巻、マフラー、帽子、手袋、靴下、耳あてなどがある。
As the fiber structure of the present invention, yarn, woven fabric, knitted fabric, non-woven fabric or stuffing is preferable. In the case of stuffing, it may be used by mixing with feathers. Furthermore, as the fiber structure, clothes, hats, ear hooks, mufflers, gloves, socks, sleeping bags, futons, pillows, cushions, blankets, rugs, carpets, and materials related to housing-related floor materials, wall materials, tatami mats, etc. Also mentioned. It is especially suitable for sportswear such as clothing, mountain climbing and skiing in cold weather. Clothing includes underwear, underwear, shirts, jumpers, sweaters, pants, jackets, windbreakers, training wear, rainwear, tights, stomachbands, mufflers, hats, gloves, socks and ear pads.
本発明の繊維構造物は、温度２０℃の静水に構造物の一端を２分３０秒間浸漬し、その後のサーモグラフィ測定により、気化冷却が観察されないか又は疎水化未処理品に比べて低いことが好ましい。このことは、濡れにくいことを示しており、着用時には冷感が少なく、快適性が得られることに関連する。
In the fiber structure of the present invention, one end of the structure is immersed in still water at a temperature of 20 ° C. for 2 minutes and 30 seconds, and evaporative cooling is not observed or is lower than that of a hydrophobized untreated product by subsequent thermography measurement. preferable. This indicates that it is difficult to get wet, and it is related to the fact that when worn, there is less feeling of cooling and comfort can be obtained.
以下実施例により本発明を具体的に説明する。なお本発明は下記の実施例に限定されるものではない。
Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to the following examples.
＜測定方法＞
１．原綿の吸湿発熱テストの測定方法
（１）開繊した原綿、及び水を温度２０℃、４５％ＲＨの室内環境に２時間以上放置した。これにより、測定環境下で原綿の吸湿を終了させた。水は試験中に温度が変動しないように室温に合わせておいた。
（２）直径７５ｍｍのシャーレに水１６ｇを入れた。
（３）原綿を１ｇ取り出した。
（４）ピンセットで原綿をつかみ、シャーレの水に載せた。
（５）サーモグラフィ（例えばＮＥＣ Ａｖｉｏ赤外線テクノロジー社製、商品名“Ｈ２６３０”）で熱履歴を計測した。
（６）５秒間隔で発熱終了まで観察し、発熱をカメラで撮影しデータをパソコンに記憶させた。発熱終了はサンプルの最高温度が２１℃未満とした。
（７）以上の条件下（サーモグラフィ測定結果を解析）し、発熱持続時間を計測した。 <Measurement method>
1. Measuring method of moisture absorption exothermic test of raw cotton (1) The opened raw cotton and water were left in an indoor environment at a temperature of 20 ° C. and 45% RH for 2 hours or more. Thereby, the moisture absorption of the raw cotton was terminated in the measurement environment. The water was kept at room temperature so that the temperature did not fluctuate during the test.
(2) 16 g of water was placed in a petri dish having a diameter of 75 mm.
(3) 1 g of raw cotton was taken out.
(4) Grasping raw cotton with tweezers and placing it on petri dish water.
(5) Thermal history was measured with a thermography (for example, product name “H2630” manufactured by NEC Avio Infrared Technology Co., Ltd.).
(6) Observation was made until the end of heat generation at intervals of 5 seconds, the heat generation was photographed with a camera, and the data was stored in a personal computer. At the end of heat generation, the maximum temperature of the sample was less than 21 ° C.
(7) Under the above conditions (analyzing the thermographic measurement results), the duration of heat generation was measured.
１．原綿の吸湿発熱テストの測定方法
（１）開繊した原綿、及び水を温度２０℃、４５％ＲＨの室内環境に２時間以上放置した。これにより、測定環境下で原綿の吸湿を終了させた。水は試験中に温度が変動しないように室温に合わせておいた。
（２）直径７５ｍｍのシャーレに水１６ｇを入れた。
（３）原綿を１ｇ取り出した。
（４）ピンセットで原綿をつかみ、シャーレの水に載せた。
（５）サーモグラフィ（例えばＮＥＣ Ａｖｉｏ赤外線テクノロジー社製、商品名“Ｈ２６３０”）で熱履歴を計測した。
（６）５秒間隔で発熱終了まで観察し、発熱をカメラで撮影しデータをパソコンに記憶させた。発熱終了はサンプルの最高温度が２１℃未満とした。
（７）以上の条件下（サーモグラフィ測定結果を解析）し、発熱持続時間を計測した。 <Measurement method>
1. Measuring method of moisture absorption exothermic test of raw cotton (1) The opened raw cotton and water were left in an indoor environment at a temperature of 20 ° C. and 45% RH for 2 hours or more. Thereby, the moisture absorption of the raw cotton was terminated in the measurement environment. The water was kept at room temperature so that the temperature did not fluctuate during the test.
(2) 16 g of water was placed in a petri dish having a diameter of 75 mm.
(3) 1 g of raw cotton was taken out.
(4) Grasping raw cotton with tweezers and placing it on petri dish water.
(5) Thermal history was measured with a thermography (for example, product name “H2630” manufactured by NEC Avio Infrared Technology Co., Ltd.).
(6) Observation was made until the end of heat generation at intervals of 5 seconds, the heat generation was photographed with a camera, and the data was stored in a personal computer. At the end of heat generation, the maximum temperature of the sample was less than 21 ° C.
(7) Under the above conditions (analyzing the thermographic measurement results), the duration of heat generation was measured.
２．重量増加率（吸水率）の測定方法
水との接触時間及び重量を一定にした試料の重量増加率（吸水率）を測定した。測定方法は次のとおりである。
（１）開繊した原綿を１ｇ秤った（Ａ）。
（２）温度２０℃、湿度４５%ＲＨの室内環境下で、３００ｃｃビーカーに水２００ｇを入れ、原綿を水面に浮かべた。判定は次のとおりとした。
浮き：発熱持続時間中、浮いていたもの。
半沈み：発熱持続時間中、繊維が部分的に水中に沈むが、全体としては浮いていたもの。
沈み：発熱持続時間内に繊維全体が沈んだもの。沈むまでの時間を測定した。
（３）１分経過後、ネットに全量移し替え余剰水を除去した。
（４）１分経過後、重量測定し（Ｂ）、下記式より重量増加率（吸水率）を算出した。
重量増加率（吸水率）＝（Ｂ－Ａ）×１００/Ａ 2. Method for Measuring Weight Increase Rate (Water Absorption Rate) The weight increase rate (water absorption rate) of a sample with a constant contact time with water and weight was measured. The measurement method is as follows.
(1) 1 g of the opened raw cotton was weighed (A).
(2) In an indoor environment at a temperature of 20 ° C. and a humidity of 45% RH, 200 g of water was put into a 300 cc beaker, and the raw cotton was floated on the water surface. The judgment was as follows.
Float: The one that floated during the fever duration.
Semi-sink: The fiber partly sinks in the water during the fever duration, but floats as a whole.
Sink: The entire fiber sinks within the duration of the fever. The time to sink was measured.
(3) After 1 minute, the entire amount was transferred to a net to remove excess water.
(4) After 1 minute, the weight was measured (B), and the weight increase rate (water absorption rate) was calculated from the following formula.
Weight increase rate (water absorption) = (BA) × 100 / A
水との接触時間及び重量を一定にした試料の重量増加率（吸水率）を測定した。測定方法は次のとおりである。
（１）開繊した原綿を１ｇ秤った（Ａ）。
（２）温度２０℃、湿度４５%ＲＨの室内環境下で、３００ｃｃビーカーに水２００ｇを入れ、原綿を水面に浮かべた。判定は次のとおりとした。
浮き：発熱持続時間中、浮いていたもの。
半沈み：発熱持続時間中、繊維が部分的に水中に沈むが、全体としては浮いていたもの。
沈み：発熱持続時間内に繊維全体が沈んだもの。沈むまでの時間を測定した。
（３）１分経過後、ネットに全量移し替え余剰水を除去した。
（４）１分経過後、重量測定し（Ｂ）、下記式より重量増加率（吸水率）を算出した。
重量増加率（吸水率）＝（Ｂ－Ａ）×１００/Ａ 2. Method for Measuring Weight Increase Rate (Water Absorption Rate) The weight increase rate (water absorption rate) of a sample with a constant contact time with water and weight was measured. The measurement method is as follows.
(1) 1 g of the opened raw cotton was weighed (A).
(2) In an indoor environment at a temperature of 20 ° C. and a humidity of 45% RH, 200 g of water was put into a 300 cc beaker, and the raw cotton was floated on the water surface. The judgment was as follows.
Float: The one that floated during the fever duration.
Semi-sink: The fiber partly sinks in the water during the fever duration, but floats as a whole.
Sink: The entire fiber sinks within the duration of the fever. The time to sink was measured.
(3) After 1 minute, the entire amount was transferred to a net to remove excess water.
(4) After 1 minute, the weight was measured (B), and the weight increase rate (water absorption rate) was calculated from the following formula.
Weight increase rate (water absorption) = (BA) × 100 / A
３．繊維の浮沈測定
前記の発熱測定（サーモグラフィ測定結果を解析）した後、サンプルの浮沈状況を観察した。 3. Measurement of the rise and fall of the fiber After the exothermic measurement (analysis of the thermographic measurement result), the state of the rise and fall of the sample was observed.
前記の発熱測定（サーモグラフィ測定結果を解析）した後、サンプルの浮沈状況を観察した。 3. Measurement of the rise and fall of the fiber After the exothermic measurement (analysis of the thermographic measurement result), the state of the rise and fall of the sample was observed.
４．紡績糸の吸湿発熱テストの測定方法
（１）図１に示す方法で測定した。紡績糸１を１６０本束ねて幅約１００ｍｍとし、重量を測定した（Ａ）。両端をクリップ２，３で挟み、一方の端は棒４とともに挟み、他方の端はクリップ３を錘にして下に吊り下げた。下には水６を入れたビーカー５を置き、水６の中に紡績糸１のクリップ３側の端が１ｃｍ漬かるまで下ろした。
（２）環境条件、サーモグラフィ測定条件は、前記原綿の場合と同様である。試験終了後の試験体重量（Ｂ）を測定した。下記式より重量増加率（吸水率）を算出した。
重量増加率（吸水率）＝（Ｂ－Ａ）×１００/Ａ
更に紡績糸の場合は、気化冷却時の温度を表３に示した。この気化冷却温度は、環境温度２０℃を基準にした温度である。 4). Measuring method of moisture absorption exothermic test of spun yarn (1) Measurement was performed by the method shown in FIG. 160 spunyarns 1 were bundled to a width of about 100 mm, and the weight was measured (A). Both ends were sandwiched between clips 2 and 3, one end was sandwiched with a rod 4, and the other end was suspended downward using clip 3 as a weight. A beaker 5 containing water 6 was placed underneath, and the beaker 5 was lowered in the water 6 until the end of the spun yarn 1 on the clip 3 side was immersed 1 cm.
(2) Environmental conditions and thermographic measurement conditions are the same as in the case of the raw cotton. The specimen weight (B) after completion of the test was measured. The weight increase rate (water absorption rate) was calculated from the following formula.
Weight increase rate (water absorption) = (BA) × 100 / A
Further, in the case of spun yarn, the temperature during vaporization cooling is shown in Table 3. This evaporative cooling temperature is a temperature based on an environmental temperature of 20 ° C.
（１）図１に示す方法で測定した。紡績糸１を１６０本束ねて幅約１００ｍｍとし、重量を測定した（Ａ）。両端をクリップ２，３で挟み、一方の端は棒４とともに挟み、他方の端はクリップ３を錘にして下に吊り下げた。下には水６を入れたビーカー５を置き、水６の中に紡績糸１のクリップ３側の端が１ｃｍ漬かるまで下ろした。
（２）環境条件、サーモグラフィ測定条件は、前記原綿の場合と同様である。試験終了後の試験体重量（Ｂ）を測定した。下記式より重量増加率（吸水率）を算出した。
重量増加率（吸水率）＝（Ｂ－Ａ）×１００/Ａ
更に紡績糸の場合は、気化冷却時の温度を表３に示した。この気化冷却温度は、環境温度２０℃を基準にした温度である。 4). Measuring method of moisture absorption exothermic test of spun yarn (1) Measurement was performed by the method shown in FIG. 160 spun
(2) Environmental conditions and thermographic measurement conditions are the same as in the case of the raw cotton. The specimen weight (B) after completion of the test was measured. The weight increase rate (water absorption rate) was calculated from the following formula.
Weight increase rate (water absorption) = (BA) × 100 / A
Further, in the case of spun yarn, the temperature during vaporization cooling is shown in Table 3. This evaporative cooling temperature is a temperature based on an environmental temperature of 20 ° C.
５．吸湿率の測定方法
試料約５．０ｇを熱風乾燥器で１０５℃、１６時間乾燥して重量を測定した（Ａ）。次に該試料を温度２０℃、４５％ＲＨあるいは９５％ＲＨに調節した恒温恒湿器に２４時間入れた。このようにして吸湿した試料の重量を測定した（Ｂ）。以上の測定結果から、次式によって算出した。
吸湿率［％］＝｛（Ｂ－Ａ）／Ａ｝×１００ 5. Method of measuring moisture absorption About 5.0 g of a sample was dried with a hot air drier at 105 ° C. for 16 hours, and the weight was measured (A). Next, the sample was placed in a thermo-hygrostat controlled at a temperature of 20 ° C. and 45% RH or 95% RH for 24 hours. The weight of the sample thus absorbed was measured (B). From the above measurement results, calculation was performed according to the following equation.
Moisture absorption [%] = {(BA) / A} × 100
試料約５．０ｇを熱風乾燥器で１０５℃、１６時間乾燥して重量を測定した（Ａ）。次に該試料を温度２０℃、４５％ＲＨあるいは９５％ＲＨに調節した恒温恒湿器に２４時間入れた。このようにして吸湿した試料の重量を測定した（Ｂ）。以上の測定結果から、次式によって算出した。
吸湿率［％］＝｛（Ｂ－Ａ）／Ａ｝×１００ 5. Method of measuring moisture absorption About 5.0 g of a sample was dried with a hot air drier at 105 ° C. for 16 hours, and the weight was measured (A). Next, the sample was placed in a thermo-hygrostat controlled at a temperature of 20 ° C. and 45% RH or 95% RH for 24 hours. The weight of the sample thus absorbed was measured (B). From the above measurement results, calculation was performed according to the following equation.
Moisture absorption [%] = {(BA) / A} × 100
６．平均温度の測定方法
２分３０秒経過時の水面から、上部クリップ２までの試料全面の平均温度をサーモグラフィで計測した。 6). Measuring method of average temperature The average temperature of the entire sample surface from the water surface at the time of 2 minutes 30 seconds to the upper clip 2 was measured by thermography.
２分３０秒経過時の水面から、上部クリップ２までの試料全面の平均温度をサーモグラフィで計測した。 6). Measuring method of average temperature The average temperature of the entire sample surface from the water surface at the time of 2 minutes 30 seconds to the upper clip 2 was measured by thermography.
（実施例１）
１．高架橋ポリアクリレート系繊維
カルボキシル基及び／又はカルボキシル塩等の親水性基を導入した高架橋ポリアクリレート系繊維として、東洋紡績社製商品名“Ｎ－３８、エクス”（単繊維繊度：２．４dtex、繊維長：３５ｍｍ）を使用した。
２．疎水加工
疎水化剤としては下記に示すものを使用した。疎水加工も併せて記載した。以下において、疎水化剤を使用した加工品を「改質」と表示した。
（１）実験番号１
疎水化剤である側鎖両末端型エポキシ変性シリコーンとして、信越シリコーン社製、商品名“Ｘ－２２－９００２”の０．１％水溶液に繊維を浸漬後、０．１％水溶液の付着率が１００ｏｗｆ％（純分付着率0.1owf%）になるよう脱水機で脱水後、１０５℃、３０分間乾燥後、１７０℃で３０分間キュアセットした。
（２）実験番号２
実験番号１において、側鎖両末端型エポキシ変性シリコーンに替えて両末端型アミノ変性シリコーンとして、信越シリコーン社製、製品名“ＫＦ－８０１２”を濃度０．０４重量%水溶液とした以外は実験番号１と同様に処理した。
（３）実験番号３
実験番号２において、“ＫＦ－８０１２”を濃度０．４重量％水溶液とした以外は実験番号２と同様に処理した。
（４）実験番号４
実験番号１において、側鎖両末端型エポキシ変性シリコーンに替えて、旭硝子社製、フッ素系疎水剤エマルジョン“アサヒガードＡＧ－Ｅ０８２”（商品名）を０．８重量％水溶液にして使用した以外は実験番号１と同様に処理した。
（５）実験番号５
実験番号１において、側鎖両末端型エポキシ変性シリコーンに替えて、日華化学社製、商品名“Ｓ－０９”（フッ素シリコーン疎水剤）を０．８重量％水溶液にして使用した以外は実験番号１と同様に処理した。
（６）実験番号６
疎水化処理をしない繊維（未処理品）を使用した。 Example 1
1. Highly cross-linked polyacrylate fiber As a highly cross-linked polyacrylate fiber into which hydrophilic groups such as carboxyl groups and / or carboxyl salts are introduced, Toyobo Co., Ltd. trade name “N-38, Ex” (single fiber fineness: 2.4 dtex, fiber Length: 35 mm) was used.
2. Hydrophobic processing The following hydrophobizing agents were used. The hydrophobic processing is also described. In the following, processed products using a hydrophobizing agent are indicated as “modified”.
(1)Experiment number 1
As a side-chain both-end type epoxy-modified silicone that is a hydrophobizing agent, the adhesion rate of the 0.1% aqueous solution is obtained after the fibers are immersed in a 0.1% aqueous solution of the trade name “X-22-9002” manufactured by Shin-Etsu Silicone Co., Ltd. After dehydrating with a dehydrator to 100 owf% (pure content adhesion rate 0.1 owf%), drying was performed at 105 ° C. for 30 minutes, and then cured at 170 ° C. for 30 minutes.
(2) Experiment number 2
In Experiment No. 1 except that the side-chain both-end type epoxy-modified silicone was replaced with a double-end-type amino-modified silicone manufactured by Shin-Etsu Silicone Co., Ltd., and the product name “KF-8012” was a 0.04 wt% aqueous solution. 1 was processed.
(3)Experiment number 3
In Experiment No. 2, the same treatment as in Experiment No. 2 was conducted except that “KF-8012” was changed to a 0.4 wt% aqueous solution.
(4)Experiment number 4
In Experiment No. 1, except that the side chain double-ended epoxy-modified silicone was used, a fluorine-based hydrophobic agent emulsion “Asahi Guard AG-E082” (trade name) manufactured by Asahi Glass Co., Ltd. was used as a 0.8 wt% aqueous solution. The same treatment as in Experiment No. 1 was performed.
(5)Experiment number 5
Experiment No. 1 except that instead of the side chain double-ended epoxy-modified silicone, a product name “S-09” (fluorine silicone hydrophobic agent) manufactured by Nikka Chemical Co., Ltd. was used as a 0.8 wt% aqueous solution. Treated as innumber 1.
(6)Experiment number 6
Fibers that were not hydrophobized (untreated) were used.
１．高架橋ポリアクリレート系繊維
カルボキシル基及び／又はカルボキシル塩等の親水性基を導入した高架橋ポリアクリレート系繊維として、東洋紡績社製商品名“Ｎ－３８、エクス”（単繊維繊度：２．４dtex、繊維長：３５ｍｍ）を使用した。
２．疎水加工
疎水化剤としては下記に示すものを使用した。疎水加工も併せて記載した。以下において、疎水化剤を使用した加工品を「改質」と表示した。
（１）実験番号１
疎水化剤である側鎖両末端型エポキシ変性シリコーンとして、信越シリコーン社製、商品名“Ｘ－２２－９００２”の０．１％水溶液に繊維を浸漬後、０．１％水溶液の付着率が１００ｏｗｆ％（純分付着率0.1owf%）になるよう脱水機で脱水後、１０５℃、３０分間乾燥後、１７０℃で３０分間キュアセットした。
（２）実験番号２
実験番号１において、側鎖両末端型エポキシ変性シリコーンに替えて両末端型アミノ変性シリコーンとして、信越シリコーン社製、製品名“ＫＦ－８０１２”を濃度０．０４重量%水溶液とした以外は実験番号１と同様に処理した。
（３）実験番号３
実験番号２において、“ＫＦ－８０１２”を濃度０．４重量％水溶液とした以外は実験番号２と同様に処理した。
（４）実験番号４
実験番号１において、側鎖両末端型エポキシ変性シリコーンに替えて、旭硝子社製、フッ素系疎水剤エマルジョン“アサヒガードＡＧ－Ｅ０８２”（商品名）を０．８重量％水溶液にして使用した以外は実験番号１と同様に処理した。
（５）実験番号５
実験番号１において、側鎖両末端型エポキシ変性シリコーンに替えて、日華化学社製、商品名“Ｓ－０９”（フッ素シリコーン疎水剤）を０．８重量％水溶液にして使用した以外は実験番号１と同様に処理した。
（６）実験番号６
疎水化処理をしない繊維（未処理品）を使用した。 Example 1
1. Highly cross-linked polyacrylate fiber As a highly cross-linked polyacrylate fiber into which hydrophilic groups such as carboxyl groups and / or carboxyl salts are introduced, Toyobo Co., Ltd. trade name “N-38, Ex” (single fiber fineness: 2.4 dtex, fiber Length: 35 mm) was used.
2. Hydrophobic processing The following hydrophobizing agents were used. The hydrophobic processing is also described. In the following, processed products using a hydrophobizing agent are indicated as “modified”.
(1)
As a side-chain both-end type epoxy-modified silicone that is a hydrophobizing agent, the adhesion rate of the 0.1% aqueous solution is obtained after the fibers are immersed in a 0.1% aqueous solution of the trade name “X-22-9002” manufactured by Shin-Etsu Silicone Co., Ltd. After dehydrating with a dehydrator to 100 owf% (pure content adhesion rate 0.1 owf%), drying was performed at 105 ° C. for 30 minutes, and then cured at 170 ° C. for 30 minutes.
(2) Experiment number 2
In Experiment No. 1 except that the side-chain both-end type epoxy-modified silicone was replaced with a double-end-type amino-modified silicone manufactured by Shin-Etsu Silicone Co., Ltd., and the product name “KF-8012” was a 0.04 wt% aqueous solution. 1 was processed.
(3)
In Experiment No. 2, the same treatment as in Experiment No. 2 was conducted except that “KF-8012” was changed to a 0.4 wt% aqueous solution.
(4)
In Experiment No. 1, except that the side chain double-ended epoxy-modified silicone was used, a fluorine-based hydrophobic agent emulsion “Asahi Guard AG-E082” (trade name) manufactured by Asahi Glass Co., Ltd. was used as a 0.8 wt% aqueous solution. The same treatment as in Experiment No. 1 was performed.
(5)
Experiment No. 1 except that instead of the side chain double-ended epoxy-modified silicone, a product name “S-09” (fluorine silicone hydrophobic agent) manufactured by Nikka Chemical Co., Ltd. was used as a 0.8 wt% aqueous solution. Treated as in
(6)
Fibers that were not hydrophobized (untreated) were used.
以上のようにして得られた繊維を各種測定した。測定結果を下記の表２にまとめて示す。
Various measurements were performed on the fibers obtained as described above. The measurement results are summarized in Table 2 below.
備考１：＊は比較例（以下の表においても同じ）。
Remark 1: * is a comparative example (the same applies to the following table).
表２から、実験番号1-1～1-5の繊維は、液相の水分と接触しても水をはじき、吸湿発熱が持続する、液相の水分と接触しても水分増加率は低いこと、温度２０℃、湿度４５％ＲＨの雰囲気での吸湿率が自重の２０％以上であることも確認できた。また、水上における発熱持続時間中の繊維は浮いており、沈まなかった。実験番号1-2は「半沈み」であるが、沈まなかった。
From Table 2, the fibers of Experiment Nos. 1-1 to 1-5 repel water even when they come into contact with liquid phase moisture, and the hygroscopic heat generation continues. Even when they come into contact with liquid phase moisture, the rate of water increase is low. It was also confirmed that the moisture absorption rate in an atmosphere at a temperature of 20 ° C. and a humidity of 45% RH was 20% or more of its own weight. Moreover, the fiber during the exothermic duration on water floated and did not sink. Experiment number 1-2 was “half-sinking” but did not sink.
（実施例２）
実施例１の実験番号1-1～1-6の繊維を３０重量％と、ポリエチレンテレフタレート繊維（単繊維繊度：１．１dtex、繊維長：３５ｍｍ）７０重量％をカード装置で混紡し、通常のリング紡績装置でＺ撚り（８９０回／ｍ）をかけてメートル番手４０番の紡績糸を製造した。実験番号1-1～1-6の繊維に対応する実験を実験番号2-1～2-6とする。以上のようにして得られた紡績糸の各種測定結果を下記の表３にまとめた。 (Example 2)
30% by weight of the fibers of Experiment Nos. 1-1 to 1-6 in Example 1 and 70% by weight of polyethylene terephthalate fiber (single fiber fineness: 1.1 dtex, fiber length: 35 mm) were blended with a card device, A 40-meter spun yarn was produced by applying Z twist (890 times / m) with a ring spinning device. Experiments corresponding to the fibers of experiment numbers 1-1 to 1-6 are designated as experiment numbers 2-1 to 2-6. Various measurement results of the spun yarn obtained as described above are summarized in Table 3 below.
実施例１の実験番号1-1～1-6の繊維を３０重量％と、ポリエチレンテレフタレート繊維（単繊維繊度：１．１dtex、繊維長：３５ｍｍ）７０重量％をカード装置で混紡し、通常のリング紡績装置でＺ撚り（８９０回／ｍ）をかけてメートル番手４０番の紡績糸を製造した。実験番号1-1～1-6の繊維に対応する実験を実験番号2-1～2-6とする。以上のようにして得られた紡績糸の各種測定結果を下記の表３にまとめた。 (Example 2)
30% by weight of the fibers of Experiment Nos. 1-1 to 1-6 in Example 1 and 70% by weight of polyethylene terephthalate fiber (single fiber fineness: 1.1 dtex, fiber length: 35 mm) were blended with a card device, A 40-meter spun yarn was produced by applying Z twist (890 times / m) with a ring spinning device. Experiments corresponding to the fibers of experiment numbers 1-1 to 1-6 are designated as experiment numbers 2-1 to 2-6. Various measurement results of the spun yarn obtained as described above are summarized in Table 3 below.
表３から、実験番号2-1～2-5の繊維は、液相の水分と接触しても水をはじき、吸湿発熱が持続し、かつ気化冷却がないか又は比較例品に比べて低いことが確認できた。また液相の水分と接触しても水分増加率は低いことも確認できた。
From Table 3, the fibers of Experiment Nos. 2-1 to 2-5 repel water even when they come into contact with water in the liquid phase, the heat of moisture absorption continues, and there is no evaporative cooling or it is lower than the comparative product. I was able to confirm. It was also confirmed that the moisture increase rate was low even when it was in contact with liquid phase moisture.
１ 紡績糸
２，３ クリップ
４ 棒
５ ビーカー
６ 水 1 Spinningyarn 2, 3 Clip 4 Stick 5 Beaker 6 Water
２，３ クリップ
４ 棒
５ ビーカー
６ 水 1 Spinning
Claims (9)
- 親水性基を含むことにより水分を吸着して発熱する高架橋ポリアクリレート系繊維に、さらに疎水化剤を結合、吸着又は付着させることにより、液相の水分に対しては水をはじき、気相の水分に対しては吸湿発熱する疎水化高架橋ポリアクリレート系繊維。 By binding, adsorbing or adhering a hydrophobizing agent to the highly crosslinked polyacrylate fiber that generates heat by adsorbing moisture due to the inclusion of a hydrophilic group, it repels water against moisture in the liquid phase. Hydrophobized highly cross-linked polyacrylate fiber that absorbs moisture and generates heat.
- 前記疎水化高架橋ポリアクリレート系繊維を開繊し、静水に落下させたとき、１０分以上水に沈まない請求項１に記載の疎水化高架橋ポリアクリレート系繊維。 The hydrophobized highly cross-linked polyacrylate fiber according to claim 1, which does not sink in water for 10 minutes or more when the hydrophobized highly cross-linked polyacrylate fiber is opened and dropped in still water.
- 前記疎水化高架橋ポリアクリレート系繊維は、温度２０℃、湿度４５％ＲＨの雰囲気下で液相水分と接触させたとき、２１℃以上の温度に発熱している持続時間が１０分以上である請求項１又は２に記載の疎水化高架橋ポリアクリレート系繊維。 When the hydrophobized highly crosslinked polyacrylate fiber is brought into contact with liquid phase moisture in an atmosphere of a temperature of 20 ° C. and a humidity of 45% RH, the duration of heating to a temperature of 21 ° C. or higher is 10 minutes or longer. Item 3. The hydrophobized highly crosslinked polyacrylate fiber according to Item 1 or 2.
- 前記疎水化高架橋ポリアクリレート系繊維は、開繊した前記繊維を静水に落下させたときの水分付着量が自重の４００％以下である請求項１～３のいずれか１項に記載の疎水化高架橋ポリアクリレート系繊維。 The hydrophobized highly crosslinked polyacrylate fiber according to any one of claims 1 to 3, wherein the amount of moisture adhering to the hydrophobized highly crosslinked polyacrylate fiber when the opened fiber is dropped into still water is 400% or less of its own weight. Polyacrylate fiber.
- 前記疎水化高架橋ポリアクリレート系繊維は、温度２０℃、湿度９５％ＲＨの雰囲気下での吸湿率が自重の４０％以上である請求項１～４のいずれか１項に記載の疎水化高架橋ポリアクリレート系繊維。 5. The hydrophobized highly crosslinked polyacrylate fiber according to claim 1, wherein the hydrophobized highly crosslinked polyacrylate fiber has a moisture absorption rate of 40% or more of its own weight in an atmosphere at a temperature of 20 ° C. and a humidity of 95% RH. Acrylate fiber.
- 前記疎水化は、高架橋ポリアクリレート系繊維の表面にフッ素、フッ素含有化合物、シリコーン化合物、フッ素含有シリコーン化合物又は炭化水素系化合物を含む疎水化剤が結合、吸着又は付着して発現している請求項１～５のいずれか１項に記載の疎水化高架橋ポリアクリレート系繊維。 The hydrophobization is expressed by bonding, adsorbing or adhering a hydrophobizing agent containing fluorine, a fluorine-containing compound, a silicone compound, a fluorine-containing silicone compound or a hydrocarbon compound to the surface of a highly crosslinked polyacrylate fiber. 6. The hydrophobized highly crosslinked polyacrylate fiber according to any one of 1 to 5.
- 請求項１～６のいずれか１項に記載の疎水化高架橋ポリアクリレート系繊維が５重量％以上１００重量％未満、その他の繊維が０重量％を超え９５重量％以下含む繊維構造物。 A fiber structure comprising the hydrophobized highly crosslinked polyacrylate fiber according to any one of claims 1 to 6 in an amount of 5% by weight to less than 100% by weight, and other fibers in excess of 0% by weight to 95% by weight.
- 前記繊維構造物が、糸、織物、編物、不織布又は詰め物である請求項７に記載の繊維構造物。 The fiber structure according to claim 7, wherein the fiber structure is a yarn, a woven fabric, a knitted fabric, a nonwoven fabric or a stuffing.
- 前記繊維構造物を温度２０℃の静水に２分３０秒間浸漬後のサーモグラフィ測定により、気化冷却が観察されないか、又は疎水化未処理品に比べて気化冷却が生じにくい請求項７又は８に記載の繊維構造物。 9. The evaporative cooling is not observed by thermography measurement after the fiber structure is immersed in still water at a temperature of 20 ° C. for 2 minutes and 30 seconds, or evaporative cooling is less likely to occur compared to a hydrophobized untreated product. Fiber structure.
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| Application Number | Priority Date | Filing Date | Title |
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| PCT/JP2011/080091 WO2012090942A1 (en) | 2010-12-28 | 2011-12-26 | Hydrophobized hygroscopic heat-releasing fiber and fibrous structure using same |
| JP2012550939A JP5721746B2 (en) | 2010-12-28 | 2011-12-26 | Hydrophobic hygroscopic exothermic fiber and fiber structure using the same |
| CN201180063332.9A CN103282576B (en) | 2010-12-28 | 2011-12-26 | Hydrophobized hygroscopic heat-eleasing fiber and fibrous structure using same |
| KR1020137013483A KR101876818B1 (en) | 2010-12-28 | 2011-12-26 | Hydrophobized hygroscopic heat-releasing fiber and fibrous structure using same |
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| PCT/JP2011/080091 WO2012090942A1 (en) | 2010-12-28 | 2011-12-26 | Hydrophobized hygroscopic heat-releasing fiber and fibrous structure using same |
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| CN106248713A (en) * | 2016-07-13 | 2016-12-21 | 天纺标检测科技有限公司 | A kind of method of testing of weaving face fabric moisture absorption heating |
| CN106820297A (en) * | 2016-12-30 | 2017-06-13 | 浙江吡嘟服饰有限公司 | Sweat-absorbing breathable gym suit |
| TR201812422A2 (en) * | 2018-08-31 | 2018-09-21 | Bursa Teknik Ueniversitesi | A QUANTITATIVE ANALYSIS METHOD FOR FIBER MIXTURES |
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| JP2003003374A (en) * | 2001-06-25 | 2003-01-08 | Unitika Textiles Ltd | Method for producing low wetting heat-generating animal hair protein-based fiber |
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| JP3196855B2 (en) * | 1991-11-11 | 2001-08-06 | 東洋紡績株式会社 | High moisture absorption and release fiber |
| US6695889B2 (en) * | 2000-09-18 | 2004-02-24 | Sakaren Co., Ltd. | Pre-dyeing treatment process and dyeing process for textile products containing highly crosslinked polyacrylic fibers, pretreated and undyed textile product, and dyed textile product |
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| JPH0931796A (en) * | 1995-07-18 | 1997-02-04 | Toyobo Co Ltd | Knitted woven fabric |
| JP2003003374A (en) * | 2001-06-25 | 2003-01-08 | Unitika Textiles Ltd | Method for producing low wetting heat-generating animal hair protein-based fiber |
| JP2003183978A (en) * | 2001-09-26 | 2003-07-03 | Mizuno Corp | Moisture absorbing and releasing fiber, method for producing the same and fiber product using the same |
| JP2003129312A (en) * | 2001-10-19 | 2003-05-08 | Toyobo Co Ltd | Ski suit |
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| JP2022125927A (en) * | 2021-02-17 | 2022-08-29 | 毅 荻野 | Spun yarn, fabric using the spun yarn, processed fabric, and method of producing processed fabric |
| JP7184265B2 (en) | 2021-02-17 | 2022-12-06 | 毅 荻野 | Spun yarn, fabric using this spun yarn, processed fabric, and method for producing processed fabric |
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| CN103282576B (en) | 2015-04-29 |
| JP5721746B2 (en) | 2015-05-20 |
| WO2012090942A1 (en) | 2012-07-05 |
| KR101876818B1 (en) | 2018-07-10 |
| JPWO2012090942A1 (en) | 2014-06-05 |
| KR20130141553A (en) | 2013-12-26 |
| CN103282576A (en) | 2013-09-04 |
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