KR101876818B1 - Hydrophobized hygroscopic heat-releasing fiber and fibrous structure using same - Google Patents

Abstract

The hydrophobic high-purity polyacrylate-based fiber of the present invention is a high-purity polyacrylate-based fiber which absorbs moisture in the vapor phase to generate heat and has a hydrophobizing agent in a range of 0.2 omf% to 2.5 omf% And is hydrophobic with regard to the water in the liquid phase and repels moisture even when coming into contact with the water in the liquid phase to adsorb the moisture in the vapor phase to absorb moisture and generate heat and to obtain a liquid water content in an atmosphere at a temperature of 20 DEG C and a humidity of 45% (Water), the duration of heat generation at a temperature of 21 ° C or higher is 10 minutes or more. The fibrous structure of the present invention contains 5% by mass or more and less than 100% by mass of the hydrophobic high-crosslinking polyacrylate-based fibers, and 0% by mass or more and 95% by mass or less of other fibers. As a result, even when brought into contact with the liquid water, it is not wetted or wetted with water, adsorbs moisture of the vapor (steam), and the heat generation is continued, and the feeling is good and the spinning process passability is good.

Description

HYDROPHOBIZED HYGROSCOPIC HEAT-RELEASING FIBER AND FIBROUS STRUCTURE USING SAME [0002]

The present invention relates to a hydrophobic moisture-absorbing heat-generating fiber in which water is repelled by a large amount of perspiration or rain to continue moisture absorption and heat generation, and a fiber structure using the same.

BACKGROUND ART Heat-generating fibers using heat (adsorption heat) generated when moisture is adsorbed have a higher thermal insulation than conventional fibers and are often used in sports clothing such as winter clothes and mountain climbing. Representative fibers that generate heat by the adsorption heat include high-ply polyacrylate fibers proposed by some of the present inventors (Patent Document 1). The fiber is a fiber obtained by modifying an acrylic fiber as a raw material, hydrophilizing a molecule and high-temperature-curing the same, and forming a fiber having high hygroscopicity and suppressing swelling. The pyrogenic fiber was the first to be employed in the skiing wear of the Japanese team at the Winter Olympics held in Lillehammer in Norway in 1994 and pioneered the concept of "thermal insulation" which has not existed in the medical field until now (see Non-Patent Document 1 , 2). The present applicants have developed a textile product such as the trade name " Breath Thermo " (registered trademark) and have received favorable hitherto. Common high-bridged polyacrylate fibers are obtained by crosslinking acrylic fibers with hydrazine or the like to suppress swelling during wetting, and further introducing a hydrophilic group. The hydrophilic group can be introduced by hydrolyzing a part of functional groups of the fiber to form a carboxyl group (-COOH) and / or an alkali metal salt type carboxyl group (for example, -COONa).

(Patent Document 2), application to other fibers as well as acrylic fibers (Patent Document 3), treatment of wool with an acid treatment to form a hollow fiber, (Japanese Patent Application Laid-Open No. 2002-241259), a proposal to blend acrylic fiber and viscose rayon fiber (patent document 5), a polyfunctional amine as a crosslinking agent in an acrylate fiber and hydrolysis to produce a carboxyl group And a proposal to perform a reduction treatment after staining so as to leave a carboxyl group (Patent Document 6). Patent Document 7 discloses that hydrophilic fibers such as aminoacrylic copolymer resin and acrylic ester resin are added by oxidizing the hair-like protein fiber to make the surface of the fiber anionized.

However, the characteristics of the heat-generating fiber by moisture adsorption of the prior art involve the necessity of introducing a large amount of hydrophilic groups or adsorption heat resulting from the original moisture adsorption characteristics of the cellulose-based fibers, so that the affinity of the fibers with water necessarily becomes high . Therefore, the fibers tend to be wet by sweating of the liquid phase (liquid) at the time of sweating, or heat does not occur once they are wetted by the rain. On the contrary, since the hydrophilic group has a property of not releasing liquid water, The feeling of coldness was rather increased, and there was a problem that the feeling of fit was poor. In Patent Document 7, the amount of the hydrophobic resin to be applied is 10% based on the mass of the fiber, which has been actually confirmed by experiments. When such a large amount of the hydrophobic resin is applied, the texture of the fiber becomes rough and hard, There is a problem that the hydrophobic resin falls off and the process passability is deteriorated.

Japanese Patent Application Publication No. 7-59762 Japanese Patent Application Laid-Open No. 2004-52187 Japanese Patent Application Laid-Open No. 2004-218111 Japanese Patent Application Laid-Open No. 2010-13791 Japanese Patent Application Laid-Open No. 2010-216053 Japanese Patent Application Laid-Open No. 2003-183978 Japanese Patent Application Laid-Open No. 2003-3374

Textile Society "Textile Handbook" 3rd edition, pp. 464-465, Maruzen, December 15, 2004 Textile Society Magazine (Vol.57), pages 320-323, December 2001

In order to solve the above-mentioned conventional problems, the present invention has been made to solve the above-mentioned conventional problems by improving the high-bridging polyacrylate fibers that generate heat by moisture adsorption, and to repel water even in contact with the water in the liquid phase to remove moisture of the vapor phase A hydrophobic high-purity polyacrylate-based fiber which adsorbs and keeps generating heat, is good in touch, and is good in permeability to the spinning process, and a fiber structure using the same.

The hydrophobic high-purity polyacrylate-based fiber of the present invention binds to a high-crosslinked polyacrylate-based fiber that absorbs gaseous moisture and generates heat, and the hydrophobic agent binds in a range of 0.2 omf% to 2.5 omf% (Water) of 20 ° C and a humidity of 45% RH, the water-repellency of the water-absorbing material is not lower than 21 ° C Is 10 minutes or more.

The fibrous structure of the present invention is characterized by containing 5% by mass or more and less than 100% by mass of the hydrophobic high-crosslinked polyacrylate-based fibers, and 0% by mass or more and 95% by mass or less of other fibers.

The hydrophobic high-purity polyacrylate-based fiber of the present invention is a high-purity polyacrylate-based fiber which adsorbs gaseous moisture to generate heat, and binds a specific amount of hydrophobic agent to a liquid phase (liquid) Even when coming into contact with the water of the water, the moisture absorption heat generation continues. That is, the hydrophobic high-purity polyacrylate fiber of the present invention is hydrophobic with regard to the liquid water, and is not wet or wetted even when it comes into contact with the water in the liquid phase, and absorbs moisture of the vapor (steam) As a result, even if a large amount of perspiration or rain is encountered, it is hard to get cold, the evaporated water (vapor phase) is adsorbed and the phase is converted into the adsorption heat to generate heat, and the fiber is warmed and the warmth is maintained for a longer time. In addition, by bonding the hydrophobicizing agent to the fibers within the range of 0.2 omf% to 2.5 omf%, the feeling can be maintained favorably, and also the spinning process passability is good.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a partial cross-sectional explanatory view of a method for measuring the heat generation by adsorption of water by bringing a yarn yarn into contact with liquid water according to an embodiment of the present invention. Fig.
Fig. 2 is a cross-sectional photograph (magnification 8000 times) of a scanning electron microscope (SEM) of a hydrophobic high-purity polyacrylate fiber according to an embodiment of the present invention and a distribution of a hydrophobic agent from the surface to the inside at the same time, Fig.

The inventors of the present invention performed sports involving climbing or sweating under various conditions by wearing clothes using fibers that absorb heat and absorb heat. In mountain climbing, a lot of sweating often occurs, and there is also a case where the rain is wet. If the fibers are soaked with a large amount of perspiration or rain, there has been a problem that the heat-generating fibers absorbing moisture in the past are liable to become cold. The reason is that the exothermic fiber which absorbs moisture conventionally has a high affinity with the water in the liquid phase and absorbs and gets wet when it comes into contact with the water in the liquid phase since it utilizes the adsorption heat generated from the original property of the cellulose- Not only the heat is stopped but also the hydrophilic group has a property of not releasing the water in the liquid phase, so that the feeling of coldness increases and the feeling of fit is deteriorated. In particular, it was necessary to develop clothing that does not readily feel cold due to absorption in a high mountain, winter mountain, or cold season, and that continues to exhibit hygroscopic exothermicity.

Thus, a fiber material that adsorbs moisture (vapor) in the vapor phase but does not adsorb the liquid (liquid) water has been implanted. Specifically, in addition to (1) a property of adsorbing moisture by adsorbing moisture of a high-ply polyacrylate fiber, (2) a hydrophobic agent is adsorbed by ion adsorption to impart hydrophobicity to the liquid water, It is a fiber which is not wetted or hard to be wetted, and which absorbs moisture from moisture such as vapor or insensitivity from the human body, and keeps generating heat.

It is generally difficult to uniformly coat the hydrophobic agent on the surface of the fiber when imparting hydrophobicity to the surface of the hydrophilic fiber at a level that floats on the surface when floated on the water surface. Therefore, in the conventional technology (for example, Patent Document 7), the problem has been solved by making the amount of the hydrophobic agent to be 10 mass%. However, if the applied amount is made too large, the fibers adhere to each other or the hydrophobic agent having a film forming agent causes adhesion between the fibers, resulting in not only a poor feeling, but also a high permeability in a subsequent step, (E. G., Flammability).

Even when the surface of the high-ply polyacrylate fiber is hydrophobized, the surface of the fiber surface does not reach the level at which the surface is floated if the hydrophilic surface of the fiber is highly hydrophilic and the hydrophobic agent is not adhered thereto. Therefore, an excess of the hydrophobic agent is required, which causes sticking or adhesion problems.

As a preferred example, the present inventors have found that when a cationic hydrophobic agent that ionically adsorbs to a salt type carboxyl group (hydrophilic group) present on the surface of a high-purity polyacrylate-based fiber is selected, Adsorbing and bonding, and can uniformly hydrophobicize in a small amount. Further, since the hydrophobic agent molecules are fixed by ion adsorption bonding, they have also been found to have high durability.

In addition, the inventors of the present invention found that when the hydrophobic agent is bound in a limited range of 0.2 omf% or more and 2.5 omf% or less to the high-crosslinked polyacrylate-based fiber, the feeling can be maintained satisfactorily, Respectively.

1. On high-ply polyacrylate fibers

The reason why the high-crosslinked polyacrylate fibers are selected in the present invention is that as shown in Table 1 (from Non-Patent Document 1 to Transcription), the heat of adsorption is higher than that of other fibers.

[Table 1]

(Remark) A value measured under the conditions of 25 ° C and 80.5% RH after the sample is completely dried (using a C 80 calorimeter (see Table 3 · 14 on page 465 of the above non-patent document 1, cotton ), Calorimetric units are indicated by cal, and are converted into J / g.

The high-purity polyacrylate-based fiber used in the present invention is a fiber obtained by modifying an acrylic fiber by hydration and high-temperature treatment of the fiber, and having a carboxyl group and / or a salt-type carboxyl group as a hydrophilic group. Other examples of the hydrophilic group may be a sulfonic acid group and / or a sulfonic acid group.

Examples of such high-ply polyacrylate-based fibers include trade names "Moiseker" manufactured by Toyo Bosa Company, "Sanbana" manufactured by Toho Textile Co., Ltd., and the like.

2. About hydrophobicity

The fiber of the present invention does not sink into water for 10 minutes or more when the open fiber is dropped in still water. That is, it does not submerge in water for 10 minutes or more, preferably 20 minutes or more, more preferably 30 minutes or more, particularly preferably 60 minutes or more depending on its own weight. By the impartation of the hydrophobicity, the fibers of the present invention continue to absorb and generate heat even when subjected to a large amount of perspiration or rain, so that they are warm, high in warmth, and comfortable to wear.

In the fiber of the present invention, water is repelled with respect to the liquid water, and the moisture (vapor) of the vapor phase is absorbed by the moisture absorption and is heated to a temperature of 20 ° C and a humidity of 45% RH (RH is relative humidity) Water), it is preferable that the duration of heat generation at a temperature of 21 占 폚 or more is 10 minutes or more. More preferably, the duration of heat generation at a temperature of 21 占 폚 or higher is 20 minutes or more, more preferably 30 minutes or more, particularly preferably 60 minutes or more.

A method of hydrophobing the high-ply polyacrylate-based fibers will be described. In order to hydrophobize the high-purity polyacrylate-based fiber, a hydrophobic substance is adsorbed and bonded to the highly-crosslinked polyacrylate-based fiber. For example, fluorine gas is brought into contact with the surface of the above-mentioned highly-crosslinked polyacrylate-based fibers to bind fluorine. Or by binding a hydrophobic agent comprising a fluorine-containing compound, a silicone compound, a fluorine-containing silicone compound or a hydrocarbon-based compound. The hydrophobing agent is a compound for hydrophobizing a counterpart material, and for example, there is a water repellent agent.

It is preferable that the fiber of the present invention has a hydrophilic functional group in the side chain and that the hydrophobic agent binds to these functional groups. This is because the hydrophobicity does not decrease even if washing is repeated. Examples of the fluorine-based hydrophobing agent usable in the present invention include commercially available products such as "Asahi Guard GS10" (trade name) (fluorine-based hydrophobic emulsion made by Asahi Glass Co., Ltd.), "NK Guard FGN700T" (Trade name) (all of which are fluorine-based hydrophobic emulsions manufactured by Nikka Chemical Co., Ltd.). Examples of commercially available products include "X-22-9002" (trade name, side chain double-ended epoxy-modified silicone) and "X-22-9002" 163A " (trade name, both end type epoxy modified silicone) and " KF-8012 " (trade name, cationic amino modified silicone at both ends) manufactured by Shinsei Silicone Co., As the cationic fluorine-containing silicone compound, there are commercial products "NK Guard S-07" and "NK Guard S-09" manufactured by Nikka Chemical Company. As the cationic fluorine compound, "AG-E061" (trade name), "AG-E081" (trade name), "AG-E082" (trade name), "AG- Trade name " TH-44 ", trade name, all manufactured by Asahi Glass Co., Ltd., cationic fluorine-based hydrophobic emulsion) and cationic hydrocarbon compound: high melting point wax emulsion: Nikka Chemical Co.,

Of these, at least one hydrophobic agent selected from a cationic fluorine-containing silicone compound, a cationic fluorine-containing compound, a cationic amino-modified silicone compound and a cationic hydrocarbon compound is preferable. The reason for this is that the high-purity polyacrylate fiber used in the present invention is a fiber having a salt-type carboxyl group as a hydrophilic group, for example, a -COONa group as described above, and if it is a cationic hydrophobic agent, It is easy to do. Particularly, a cationic fluorine-containing silicone compound is preferable. Examples of the cationic fluorine-containing silicone compound include a compound containing a fluoroalkyl group, a silicon group (organic silicon group), and a cation group such as a quaternary ammonium salt. As another example, a cationic surfactant is mixed with a compound containing a fluoroalkyl group and a silicon group (organosilicon group) to prepare an aqueous emulsion.

These hydrophobic agents are preferably adhered to the fibers while being dispersed in water. The fibers may be immersed in the treatment liquid, sprayed onto the fibers, or brought into contact by padding or the like, and then bonded and fixed by heat treatment by a curing set.

The binding amount of the hydrophobizing agent is 0.2 to 2.5 mass% (omf is abbreviated as on the mass of fiber), and preferably 0.22 to 2.0 omf%, based on the fiber. In the above-mentioned range, even if the fibers come into contact with the liquid water, the fibers repel water, adsorb moisture in the vapor phase (steam), and the heat generation continues, and the feeling is good and the spinning process passability is good. When the binding amount of the hydrophobizing agent is less than 0.2 mass%, the desired hydrophobicity is difficult to obtain. When the amount of the hydrophobizing agent is more than 2.5 mass%, the permeability to the touching spinning process also deteriorates.

The treatment with the hydrophobic agent of the present invention may be performed in a fiber surface state, but may be performed in a yarn state or in a state of a fabric (fabric, knitted fabric, nonwoven fabric). As a hydrophobic treatment method, a generally used treatment method such as immersion, overlay, or printing can be employed.

3. Mass increase rate due to absorption (absorption rate)

In the hydrophobic hygroscopic heat-generating fiber of the present invention, it is preferable that the water adhesion amount when dropping the open fiber into purified water is 400% or less of its own weight. Although the conventional high-purity polyacrylate fibers have a high affinity for moisture, they may exhibit an absorption rate exceeding 400% of their own weight, but the water absorption rate can be lowered by the hydrophobic treatment of the present invention. When the water absorption rate is lowered, there is an advantage that it becomes easy to dry.

4. Combined with softener

Depending on the kind of the hydrophobic agent and the processing conditions, the feel of the fiber may become rough and hard, and in such a case, it may be used in combination with a softening agent. The softening agent may be any known one. For example, as a commercial product, there is a trade name " Meisilicon SF " (amino-modified silicone) manufactured by Meisei Chemical Industries, Ltd. The adhesion amount of the softening agent is preferably 0.01 to 2.00 omf%, more preferably 0.1 to 1.0 omf%.

5. Hygroscopicity

The hydrophobic high-purity polyacrylate-based fiber of the present invention has a high property of absorbing moisture of a gas. In other words, it exhibits substantially the same hygroscopicity as that of a small number of not processed. As an example, it is preferable that the moisture absorption rate in an atmosphere at a temperature of 20 ° C and a relative humidity of 65% is not less than 21.6% and not more than 61.8% of the self weight. When the moisture absorption rate is high, sweat in the vapor phase at the time of sweating is easily absorbed, and the feeling of wearing is good.

6. Mixing with other fibers

The hydrophobic high-crosslinked polyacrylate-based fibers of the present invention may be contained in an amount of 5 to 100 mass%, and the other fibers may be 0 to 95 mass%. Examples of the other fibers include polyester, polyolefin, nylon, polypropylene, rayon (including tencel), cupra, acetate, ethylene vinyl alcohol (manufactured by Kureza Co., Quot;), cotton (cotton), hemp, silk, wool (wool), and ordinary fibers such as acrylic fiber and high-ply polyacrylate fiber. Also, a filler such as a feather may be included.

When mixing with other fibers, for example, the following method can be employed.

(1) Blending: Blending is a mixture of two or more kinds of fibers at the cotton level. For example, they are mixed with cotton, cardboard, drawing, and sliver. It is mainly used for uniformly mixing yarns, nonwoven fabrics, and filling surfaces.

(2) Ties: Ties are two or more threads twisted together. For example, in the case of twin yarns, the fiber yarn of the present invention is twisted with another fiber yarn. It is used when yarn yarns, twine yarns, filament yarns and filament yarns are twisted and mixed.

(3) Fusing: Fusing is used when mixing short fibers between filament yarns.

(4) Teaching (teaching): Teaching is a mixture of making a fabric using a plurality of kinds of yarns constituting the fabric. For example, the warp yarns and the weft yarns may be used in different kinds of yarns, or a plurality of warp yarns and weft yarns may be respectively used.

(5) Texture: Texture is a mixture when a plurality of kinds of yarns are used to produce a knitted fabric.

(6) A plurality of kinds of laminated fiber layers are mixed by a needle punch and a water flow interlace in the production of nonwoven fabric.

7. Fiber structure

The fiber structure including the hydrophobic high-purity polyacrylate-based fiber of the present invention will be described. The fibrous structure of the present invention preferably contains 5% by mass or more of the fibers of the present invention. Mixing with other fibers is more preferred. Other fibers are as described above. The reason why it is preferable to mix with other fibers is that, when wetted with a large amount of perspiration or rain, liquid moisture is retained in other fibers to continue the moisture absorption and heat generation of the fibers of the present invention. In this case, although the fiber as a whole becomes wet, the fiber of the present invention continues to absorb and generate heat, so that the fibers are warm, high in thermal insulation, and comfortable to wear.

As the other fibers, for example, those obtained by quick-drying the absorbent polyester fibers are used to quickly absorb moisture in the liquid phase, while the polyester fibers tend to sweat a large amount of sweat or rain, So that the vaporization cooling does not easily occur and the temperature becomes warmer. Further, as a synergistic effect, due to the persistence of heat generation of the fibers of the present invention, the (absorbent) drying property of the polyester fiber itself is promoted, and it dries quickly, and the feeling of wearing becomes better.

As the fibrous structure of the present invention, yarns, fabrics, knitted fabrics, nonwoven fabrics or fillers are preferable. In case of filling, it may be mixed with feather. Examples of the fiber structure include a flooring material, a wall material, and a tatami mat of a house, such as clothes, hats, earrings, mufflers, gloves, socks, sleeping bags, quilts, pillows, cushions, blankets, . Especially, it is very suitable for clothing in cold weather, sporting goods such as climbing and skiing. Examples of clothing include undergarments, underwear, shirts, jumpers, sweaters, pants, jackets, windbreakers (trademark), training wear, raincoats, tights, bags, mufflers, hats, gloves, socks and earplugs.

The fibrous structure of the present invention is obtained by immersing one end of a structure at a temperature of 20 캜 for 2 minutes and 30 seconds, and thereafter, by thermography measurement, there is no vaporization cooling, Lt; 0 > C or more. This means that it is difficult to wet, and when it is worn, the feeling of coldness is small, and comfort is obtained.

Example

Hereinafter, the present invention will be described in detail with reference to Examples. The present invention is not limited to the following examples.

<Measurement method>

1. Measurement method of hygroscopic heat generation test of raw cotton

(1) The open face and the water were allowed to stand in an indoor environment at 20 캜 and 45% RH for 2 hours or more. Thus, the moisture absorption of the raw cotton was terminated under 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 put into a chalet having a diameter of 75 mm.

(3) 1 g of the raw cotton was withdrawn.

(4) Using tweezers, pick up the wafer and place it in the chalet water.

(5) Thermal history was measured by thermography (for example, trade name "H2630", manufactured by NEC Avio Infrared Technologies, Inc.).

(6) Observations were made at 5-second intervals until the end of fever, and the fever was photographed with a camera and the data were stored in a PC. When the maximum temperature of the sample was less than 21 캜, the heat generation was terminated.

(7) Under the above conditions (the result of thermography measurement was analyzed), the duration of heat generation was measured in an indoor environment at a temperature of 20 ° C and a humidity of 45% RH.

2. Measurement method of mass increase rate (absorption rate)

The mass increase rate (absorption rate) of the sample with constant contact time and mass with water was measured. The measurement method is as follows.

(1) 1 g of the opened cotton was weighed (A).

(2) Under an indoor environment of a temperature of 20 DEG C and a humidity of 45% RH, 200 g of water was put into a 300 cc beaker, and the wafer was floated on the surface of the water. The judgment was made as follows.

Floating: Floating during the fever duration.

Half of the sinking: During the duration of fever, the fibers partially float in the water, but float as a whole.

Sinking: The entire fiber sinks within the duration of the fever. The time until sinking was measured.

(3) After 1 minute, the whole amount was transferred to the net and the remaining water was removed.

(4) After one minute, the mass was measured (B), and the mass increase rate (absorptance) was calculated from the following equation.

Mass increase rate (absorption rate) = (BA) x 100 / A

3. Measurement of fiber floatation

After the above-described exothermic measurement (analysis of thermogravimetric measurement results), the state of inflow of the sample was observed.

4. Measurement method of hygroscopic heating test of yarn yarn

(1) was measured by the method shown in Fig. 160 spun yarns (1) were bundled to have a width of about 100 mm and the mass was measured (A). The both ends are fitted with the clips (2, 3), one end is put together with the rod (4), and the other end is hanged downward with the clip (3). The beaker 5 containing the water 6 was placed underneath and the end of the sponge 1 on the side of the clip 3 in the water 6 was lowered by 1 cm.

(2) The environmental conditions and the thermography measurement conditions are the same as those in the case of the above-mentioned raw cotton. The mass (B) of the test piece after the completion of the test was measured. The mass increase rate (absorption rate) was calculated from the following formula.

Mass increase rate (absorption rate) = (BA) x 100 / A

In the case of yarn spun yarn, the temperature at the time of vaporization cooling is shown in Table 3. The vaporization cooling temperature is a temperature based on an environmental temperature of 20 占 폚.

5. Measurement method of moisture absorption rate

Approximately 5.0 g of the sample was dried in a hot-air drier at 105 ° C for 16 hours and the mass was measured (a). Next, the sample was adjusted to a temperature of 20 ° C, 45% RH, 65% RH or 95% RH and placed in a thermostatic chamber for 24 hours. The mass of the sample thus absorbed was measured (b). From the above measurement results, it was calculated by the following formula.

Moisture absorption rate [%] = {(b-a) / a} x 100

6. Measuring Average Temperature

The average temperature of the entire surface of the sample from the water surface at the elapsed time of 2 minutes and 30 seconds to the upper clip (2) was thermographed.

7. Quantitative test of bonding amount of hydrophobizing agent to fiber

The cationic hydrophobic agent (for example, a cationic fluorine-containing silicon compound) used in this embodiment selectively adsorbs ions to a salt-type carboxyl group on the surface of a high-purity polyacrylate-based fiber to calculate the difference in abundance To obtain a binding amount.

(Amount of the hydrophobic agent present in the emulsion liquid before the fiber immersion) - (amount present in the emulsion liquid after the fiber immersion) = (amount of adsorbed fiber)

(Remark: The abundance of the hydrophobic agent is calculated by the concentration (% by mass) × liquid amount.

8. Texture

Sensory evaluation was carried out by touching by touching with hand, and examined whether flexible or hard and hard.

9. Spinning processability

The fabric was opened by a card to make a web, and it was judged whether or not each process smoothly passed when a spinning yarn was manufactured by a soft yarn, a crude yarn, and a ring spinning process. If the processability is not good, it is difficult to make practical ones. Evaluation was made as follows.

A: No problems in spinning process passability

B: There is a problem in passing through the spinning process, so it can not be actually produced

(Example 1)

1. Highly crosslinked polyacrylate fiber

Crosslinked polyacrylate-based fibers having a carboxyl group content of 3.1 mmol / g, 4.8 mmol / g and 7.7 mmol / g were prepared according to a known method described in Japanese Patent Application Laid-Open No. 5-132858.

2. Small number processing

As the hydrophobizing agent, those shown below were used. Minority processing is also described in parallel.

(1) Experimental Nos. 1-1 to 1-4, 1-8 to 1-9

S-09 &quot; manufactured by Nikka Chemical Company as a cationic fluorine silicone hydrophobic agent was used as an emulsion aqueous solution. After immersing in the aqueous solution emulsion, it was dehydrated by a dehydrator, dried at 105 ° C for 30 minutes, and cured at 170 ° C for 30 minutes.

(2) Experiment No. 1-5

As the cationic amino-modified silicone, trade name "KF-8012" manufactured by Shin-Etsu Silicone Co., Ltd. was used as an emulsion aqueous solution. The fibers were dipped, dehydrated with a dehydrator, dried at 105 ° C for 30 minutes, and cured at 170 ° C for 30 minutes.

(3) Experiment No. 1-6

&Quot; TH-44 &quot;, a cationic high melting point wax manufactured by Nikkuka Chemical Co., Ltd., was used as an aqueous emulsion solution. The fibers were dipped, dehydrated with a dehydrator, dried at 105 ° C for 30 minutes, and cured at 170 ° C for 30 minutes.

(4) Experiment No. 1-7

(Untreated product) which had not been subjected to hydrophobic treatment.

Various measurements were made on the fibers thus obtained. The measurement results are shown in Table 2 below.

[Table 2]

Remark 1: * indicates a comparative example (same in the following table)

It can be seen from Table 2 that the fibers of Experimental Nos. 1-1 to 1-6 repelled water even when brought into contact with the water in the liquid phase, It was confirmed that the moisture absorption rate in the atmosphere of% RH was not less than 26.1% and not more than 61.8% of the self weight. Further, during the heating period of the water phase, the fibers were floating and did not sink. Experiment Nos. 1-6 were "halfway down," but did not sink. In Experiment Nos. 1-1, 1-2 and 1-5-1-7, the concentration of the salt type carboxyl group was the same, and the type and binding amount of the cationic hydrophobic agent were different. The moisture absorption rate was untreated fiber (Experiment No. 1-7 ). Next, the heat generation amount of moisture absorption was measured. The measurement conditions were as follows: the sample was vacuum-dried at 80 DEG C for 6 hours, and then the amount of heat of absorption and desorption measured when the sample was left at 25 DEG C and 95% RH was measured. The heat absorption amount of the fiber of Experiment No. 1-2 was 2037 J / g, and that of Experiment No. 1-7 (untreated fiber) was 2168 J / g. The properties described above did not change even after repeated washing at home.

Fig. 2 is a cross-sectional photograph (magnification 8000 times) of a hydrophobic high-crosslinked polyacrylate fiber of Experiment No. 1-1 through a scanning electron microscope (SEM), and a multi-point elemental analysis was performed to measure the distribution of the hydrophobizing agent from the surface to the inside And Fig. The elemental analysis method is based on the energy dispersive X-ray spectroscopy (EDX) attached to the SEM. After repeated washing at home, the cross-sectional directions of the hydrophobic fibers were divided into 10 equal parts, and the elemental analysis of each zone was performed. The element F was 11.89 mass% in No.1 zone, 2.84 mass% in No.10 zone, (0) mass%, and the Si element was 1.02 mass% in the No.1 zone, 0.34 mass% in the No.10 zone, and zero mass% in the other zones. From these facts, it was confirmed that the cationic fluorine-containing silicone compound was fixed on the fiber surface.

(Example 2)

30% by mass of the fibers of all the experimental numbers of Example 1 and 70% by mass of polyethylene terephthalate fibers (PET surface, 1.1 dtex of single fiber and fiber length of 35 mm) were blended in a card device, (890 times / m) was carried out to fabricate 40 yarn counting metric counts. Experiments Nos. 2-1 to 2-9 correspond to the fibers of Experiments Nos. 1-1 to 1-9. The results of various measurements of the spinning yarn thus obtained are shown in Table 3 below.

[Table 3]

It can be seen from Table 3 that the yarns of Experiments Nos. 2-1 to 2-6 repel water even when brought into contact with the water in the liquid phase, and the moisture absorption and heat generation is continued and there is no vaporization cooling or -1.2 deg. I could confirm. It was also confirmed that the water increase rate was low even in contact with the liquid water. These properties did not change even after repeated home washing. In Test Nos. 2-8 and 2-9, dropouts occurred in the spinning process, and yarns were not obtained.

(Example 3)

1. Highly crosslinked polyacrylate fiber

Crosslinked polyacrylate fibers having an amount of a salt type carboxyl group of 4.8 mmol / g were produced according to a known method described in Japanese Patent Application Laid-Open No. 5-132858.

2. Small number processing

As the hydrophobizing agent, those shown below were used. Minority processing is also described.

(1) Experiment No. 3-1

X-22-9002 &quot; manufactured by Shin-Etsu Silicone Co., Ltd. was used as an emulsion aqueous solution as a side-chain double-ended epoxy-modified silicone which is a hydrophobicizing agent. The fibers were dipped, dehydrated with a dehydrator, dried at 105 ° C for 30 minutes, and cured at 170 ° C for 30 minutes.

(2) Experiment No. 3-2-3-3

The same procedure as in Experiment No. 3-1 was carried out except that the cationic aminomodified silicone as the hydrophobicizing agent was the product name "KF-8012" manufactured by Shin-Etsu Silicone Co., Ltd.

(3) Experiment No. 3-4

Except that emulsion &quot; Asahi Guard AG-E082 &quot; (trade name) of cationic fluorine-based hydrophobic agent manufactured by Asahi Glass Co., Ltd. was used as a hydrophobicizing agent.

(4) Experiment No. 3-5

S-09 &quot; (a cationic fluorine silicon hydrophobic agent) manufactured by Nikka Chemical Company was used as a hydrophobicizing agent in the same manner as in Experiment No. 3-1.

(5) Experiment No. 3-6

The fibers (untreated products) without hydrophobic treatment were used.

Various measurements were made on the fibers thus obtained. The measurement results are summarized in Table 4 below.

[Table 4]

It can be seen from Table 4 that the fibers of Experiments Nos. 3-1 to 3-5 repel water even when brought into contact with the water in the liquid phase, It was also confirmed that the moisture absorption rate in an atmosphere of 45% RH was 20% or more of its own weight. In addition, the fibers did not sink during the heating period of the water phase. Experiment No. 3-2 was "halfway down," but did not sink. These properties did not change even after repeated home washing.

(Example 4)

30% by mass of the fibers of Experimental Nos. 3-1 to 3-6 of Example 3 and 70% by mass of polyethylene terephthalate fibers (single fiber fineness: 1.1 dtex, fiber length: 35 mm) were blended in a card device, Z twist (890 turns / m) was performed on the ring spinning apparatus to produce yarns of 40 metric counts. Tests corresponding to the fibers of Experiments Nos. 3-1 to 3-6 are referred to as Experiments Nos. 4-1 to 4-6. The results of various measurements of the spinning yarn thus obtained are shown in Table 5 below.

[Table 5]

It can be seen from Table 5 that the yarns of Experiments Nos. 4-1 to 4-5 repel water even when brought into contact with water in the liquid phase, I could confirm. In addition, it was confirmed that the water increase rate was low even in contact with the liquid water. These properties did not change even after repeated home washing.

1: Cotton yarn
2, 3: Clip
4: Rod
5: Beaker
6: Water

Claims (9)

Crosslinked polyacrylate fiber having a carboxyl group and / or a salt type carboxyl group as a hydrophilic group and absorbing moisture of a gas phase to generate heat and a hydrophobic agent in a range of 0.2 omf% to 2.5 omf% And is hydrophobic with respect to the liquid in the liquid phase. Even if it comes into contact with the liquid water, it repulsives moisture, adsorbs moisture in the gas phase, absorbs heat,
Is a hydrophobic high-crosslinking polyacrylate-based fiber having a duration of heat generation of not less than 10 占 폚 at a temperature of 21 占 폚 or more when it is floated on liquid water (water) under an atmosphere of a temperature of 20 占 폚 and a humidity of 45%
Wherein the hydrophobic high-purity polyacrylate-based fiber has a moisture absorption rate of not less than 21.6% and not more than 61.8% of its own weight in an atmosphere at a temperature of 20 ° C and a humidity of 65% RH. The method according to claim 1,
The hydrophobic property is that at least one hydrophobic agent selected from a cationic fluorine-containing silicone compound, a cationic fluorine-containing compound, a cationic amino-modified silicone compound, and a cationic hydrocarbon compound on the surface of the high- Hydrophobic high-molecular-weight polyacrylate-based fibers. The method according to claim 1,
The hydrophobic property is the hydrophobic high-purity polyacrylate-based fiber wherein at least one hydrophobic agent selected from fluorine and an epoxy-modified silicone compound is bonded to and expressed on the surface of the high-purity polyacrylate-based fiber. The method according to claim 1,
Wherein the hydrophobic high-purity polyacrylate-based fiber is opened and does not sink into water for 10 minutes or more when dropped into a still water. The method according to claim 1,
Wherein the hydrophobic high-purity polyacrylate-based fiber has a water adhesion amount of not more than 400% of its own weight when the opened fiber is dropped into purified water. 5 to less than 100% by mass of the hydrophobic high-purity polyacrylate-based fibers according to any one of claims 1 to 5; And
0% by mass to 95% by mass or less of fibers other than the high-
&Lt; / RTI &gt; The method according to claim 6,
Wherein the fibrous structure is a yarn, a fabric, a knitted fabric, a nonwoven fabric or a filling material. The method according to claim 6,
Wherein the fiber structure is free of vaporization cooling or has a vaporization cooling temperature of less than 0 占 폚 -1.2 占 폚 or more by thermography measurement after immersing the fiber structure at a constant temperature of 20 占 폚 for 2 minutes and 30 seconds. delete

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