JP2003119671A - Vapor/liquid water-absorbing heat-generating structure for padding cloth - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vapor/liquid water-absorbing heat-generating structure capable of giving an excellent rate of heat generation which is brought about by absorption of vapor or liquid water, temperature effected by the heat generation, and retention of the heat generation, and therefore capable of being suitably used as a padding cloth. SOLUTION: This vapor/liquid water-absorbing heat-generating structure for the padding cloth is given by applying highly vapor water-absorbing fine particles to the structure, wherein the structure has a maximum temperature rise of >=3 deg.C, when the vapor and/or liquid water are absorbed. The structure preferably retains the heat generation brought about by the absorption of the vapor water for a period of >=30 min, and/or the heat generation brought about by the absorption of the liquid water for a period of >=1 min. Thus, such a fiber structure is simply and stably obtained that absorbs the vapor water or the liquid water from the external environment, the human body or artificial sources, generates the heat rapidly and stably, and is suitable for the padding cloth.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a moisture-absorbing / water-absorbing exothermic structure suitable for interlining that absorbs sweat and moisture in clothes and enhances heat storage and heat retention to make clothes comfortable.

[0002]

2. Description of the Related Art General clothing, cold clothing,
Various sports clothing and uniforms for low temperature warehouses have been put to practical use. Conventional methods for improving heat retention include the use of hollow cross-section fibers and ultrafine fibers to increase the air layer with low thermal conductivity, aluminum vapor deposition that reflects body heat, the use of coating or metal sputtering, and metal oxidation. A method of expecting a far-infrared effect by kneading materials and ceramics (JP-A-63-105107, JP-A-7-
No. 331584), and a method of mixing a hygroscopic heat-generating fiber with a fabric or batting by spinning, mixing, or the like (JP-A-6-2940).
No. 06, JP-A-8-197661, etc.) or a vinyl monomer such as acrylic acid or methacrylic acid is introduced into the surface or inside of the fiber by a graft polymerization method to introduce a carboxylic acid terminal into the fiber or metal chloride such as sodium chloride. There have been various proposals for a method of imparting. However, all of these methods have insufficient heating and heating, and in addition, a knit, a woven fabric, which is most suitable for an interlining, which exhibits effective heat storage and heat retention with the heat absorption of moisture / water absorption as a cut,
Non-woven fabrics, fleeces or resin moldings have not been proposed.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a moisture-absorbing / water-absorbing exothermic structure suitable for interlining, which is excellent in heat generation rate, heat generation temperature, and heat retention during moisture absorption or water absorption.

[0004]

The present invention has the following technical constitution for solving the above problems. That is, 1. A structure for moisture-absorbing / water-absorbing exothermic interlining, which is a structure to which highly hygroscopic fine particles are attached, and has a maximum temperature rise of 3 ° C. or more during moisture absorption and / or water absorption.

2. The heat-absorbing / water-absorbing exothermic interlining structure according to the first aspect, characterized in that heat generation during moisture absorption is maintained for 30 minutes or more and / or heat generation during water absorption is maintained for 1 minute or more.

3. 3. The moisture-absorbing / water-absorbing exothermic interlining structure according to item 1 or 2, wherein the maximum temperature rise during water absorption is 8 ° C. or higher.

4. The highly hygroscopic / water-absorbing exothermic interlining structure according to any one of the first to third aspects, wherein the highly hygroscopic fine particles are organic fine particles.

5. The highly hygroscopic organic fine particles are polystyrene-based, polyacrylonitrile-based, polyacrylic acid ester-based, or polymethacrylic acid ester-based vinyl polymers, and have sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, or their metals. The moisture-absorbing / water-absorbing exothermic interlining structure according to the fourth aspect, which is a cross-linked polymer having at least one hydrophilic group of a salt and cross-linked with either divinylbenzene, triallyl isocyanate or hydrazine.

6. Highly hygroscopic fine particles have an average particle size of 2 μm
The moisture-absorbing / water-absorbing exothermic interlining structure according to any one of the first to fifth features, wherein

7. 7. The moisture-absorbing / water-absorbing exothermic interlining structure according to any one of 1 to 6, wherein the highly hygroscopic fine particles are fixed to the structure through a hydrophilic resin.

8. The hygroscopic / water-absorbing exothermic interlining structure according to any one of items 1 to 7, wherein the mass ratio of the highly hygroscopic fine particles and the hydrophilic resin is 1/1 to 19/1.

9. The structure is a knitted fabric, a woven fabric, a non-woven fabric, a fleece, or a resin molded product composed of natural fibers, synthetic fibers, or a mixture of these fibers.
The moisture-absorbing / water-absorbing exothermic interlining structure according to any one of 1.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. The structure used in the present invention includes polyethylene terephthalate, polybutylene terephthalate,
Polyesters represented by polytetramethylene terephthalate, polyesters, polyamides represented by nylon 6, nylon 66, polyolefins represented by polyethylene, polypropylene, polyacrylonitriles, polyurethanes, polyphenylene sulfides, etc. Synthetic fibers, chemical fibers such as rayon and acetate, natural fibers such as cotton, hemp, silk, wool and feather, or knits, woven fabrics and non-woven fabrics made of mixed materials thereof,
It is a structure composed of a fleece or a resin molded body.

Highly hygroscopic fine particles of the present invention (hereinafter referred to as high moisture absorption /
Also referred to as water-absorbing exothermic particles. ) Is not particularly limited in terms of chemical structure as long as it is a fine particle that exhibits exothermicity when absorbing moisture or absorbing water. For example, inorganic type such as hygroscopic silica, or hygroscopic polyurethane type, polyamide type,
It is possible to apply various organic fine particles such as polyester-based and polyacrylate-based, but particularly high moisture-absorption / water-absorption exothermic organic fine particles are preferable, and examples thereof include polystyrene-based, polyacrylonitrile-based, polyacrylic ester-based, and polyacrylic ester-based. A methacrylic acid-based vinyl polymer having a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, or at least one hydrophilic group of metal salts thereof, and having divinylbenzene, triallyl isocyanate, or It is a crosslinked polymer fine particle crosslinked with any of hydrazine.

The particle size of the highly hygroscopic fine particles is preferably as small as possible from the viewpoint of moisture absorption / water absorption heat generation rate / heat generation efficiency, uniform adhesion, texture and abrasion resistance, and an average particle diameter of less than 2 μm is more preferable.

The method of applying the highly hygroscopic / water-absorbing exothermic fine particles of the present invention includes a method of directly kneading into a fiber, a film or a resin layer or a surface layer of a knitted fabric, a woven fabric, a non-woven fabric, a fleece, a string-like product, a film and a resin molded product. There is a method of attaching via a binder resin to
From the viewpoint of heat generation efficiency, the latter method of attaching via a binder resin is preferable.

As the binder resin, a usual impregnation method,
Examples include silicone-based, urethane-based, acrylic-based, polyester-based resins that can be applied to the padding method, coating method, and spray method, and are not particularly limited, but are excellent in hydrophilicity and moisture permeability, and have high moisture absorption / water absorption heat-generating fine particles. Those that do not impair hygroscopicity are preferred. Further, various crosslinking agents may be used in combination in the system of these highly hygroscopic / water-absorbing exothermic particles and the hydrophilic resin binder in order to improve durability.

The compounding ratio of the highly hygroscopic / water-absorbing exothermic fine particles and the hydrophilic resin and the amount of these adhering to each other greatly influence the hygroscopic / water-absorbing exothermicity. The compounding ratio of the highly hygroscopic / water-absorbing exothermic fine particles and the hydrophilic resin is slightly different depending on the hydrophilic level of the hydrophilic resin, but it is desirable to use the compounding ratio of 1/1 to 19/1, and particularly, the compounding ratio of the hydrophilic resin is small. The more excellent moisture absorption / water absorption exothermicity can be exhibited. However, when the hydrophilic resin is extremely small, or when the hydrophilic resin is not used in combination, the abrasion resistance of the highly hygroscopic / water-absorbing heat-generating fine particles adhered to the surface of the structure is deteriorated and the particles easily fall off.

The exothermicity of the moisture-absorbing / water-absorbing exothermic structure of the present invention is based on the heat of adsorption reaction generated when absorbing moisture or absorbing water, and the hygroscopic ability of the highly hygroscopic / water-absorbing fine particles contained in the structure. And / or depends on the water absorption capacity and the amount deposited.
That is, the higher the moisture absorption / water absorption fine particles, and the finer the particles, the greater the heat production due to the adsorbed moisture and the faster the heat generation rate. Of course, since such a moisture absorption / water absorption is possessed by the structure base material alone, in order to realize more effective moisture absorption / water absorption exothermicity, the hygroscopicity of the applied moisture absorption / water absorption exothermic fine particles is 25%.
The above is desirable, and more preferably 40% or more.
Therefore, in order to obtain effective moisture absorption / water absorption exothermicity, the moisture absorption / water absorption exothermic structure of the present invention should be stored with a moisture absorption rate as low as possible, and more preferably in a state close to a completely dry (absolute dry) state. Is essential. On the other hand, the structure that has adsorbed moisture at a saturated moisture absorption rate or higher and has completed heat generation is cooled by heat radiation and drops to the initial temperature, but if it is dried again to remove the adsorbed water, the original excellent moisture absorption / Water absorption and exothermicity reappear.

The moisture absorption exothermicity in the vapor phase heats up at an appropriate rate and maintains the exothermicity for a relatively long time, whereas the water absorption exothermicity in the liquid phase gives a rapid exothermicity, while the adsorbed water If the amount is too large, the remarkable heat generation effect may not be obtained, so it is important to control the amount of attached water.

According to the present invention, the type of the highly hygroscopic / water-absorbing exothermic fine particles and the amount of adhesion are optimized, and the structure adhered through an appropriate hydrophilic resin binder has a maximum temperature rise during moisture absorption and / or water absorption. 3 ° C. or higher, preferably 4 ° C. or higher, more preferably 5 ° C. or higher, further, the maximum temperature rise during water absorption is 8 ° C. or higher, and the heat generation during moisture absorption is 30 minutes or more, and the heat generation during water absorption is 30 Excellent moisture absorption / water absorption exothermicity is obtained, which is maintained for more than 2 seconds, more preferably for more than 1 minute.

The structure of the present invention has, in addition to these excellent high moisture absorption / water absorption exothermic properties, antibacterial / deodorant properties, antibacterial properties, deodorant properties,
Nonenal deodorant, pH buffering, antistatic, SR antifouling,
It is also possible to develop multifunctionality of acid rain resistance.

[0023]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. Below, what is described simply as part and% means on a mass basis. Moreover, the measurement and evaluation of the structure in this example were performed by the following methods.

<Absolute dry mass> After drying the sample at 110 ° C for 6 hours, the sample was placed in a desiccator containing silica gel and kept at 20 ° C for 6 hours.
After adjusting the temperature in a 5% RH environment, mass measurement was performed. <Hygroscopicity> The mass was measured after the temperature and humidity were adjusted for 24 hours in an environment of 20 ° C. and 65% RH, and calculated from the following formula. Moisture absorption rate (%) = {(moisture absorption mass-excess dry mass) / excess dry mass}
× 100

<Heat absorption by moisture absorption> After drying at 110 ° C. for 6 hours,
5c put in desiccator containing silica gel and dried
20 after mounting a temperature sensor (for example, manufactured by Anritsu Keiki Co., Ltd .; 540K MD-5 type) on a measurement sample measuring m × 5 cm.
Temperature recorder (for example, manufactured by Anritsu Keiki Co., Ltd .; DATA COLLECTOR A)
M-7052 type). <Water absorption exothermicity> After attaching a temperature sensor to the measurement sample of 5 cm x 5 cm in the absolutely dry state, ion-exchanged water equivalent to 50% of the sample mass for 3 to 5 seconds was placed in an environment of 20 ° C and 65% RH. After uniformly spraying in the meantime, the water absorption exothermicity was measured with a temperature recorder. The water absorption heat generation time and the water absorption heat generation retention time (minutes) above the maximum water absorption heat generation temperature and the sample temperature before water absorption were evaluated.

<Dew Condensation> A 5 cm × 5 cm sample was placed in a desiccator having an internal volume of 10 to 15 liters, and the lid was left open in a room at 20 ° C. and 80% to adjust the temperature and humidity. . After 24 hours, the desiccator lid is closed, and the desiccator is moved to the environment kept at 10 ° C. within 5 minutes. One hour after that, the lid was opened and the dew condensation state of the sample was confirmed.

Example 1 A flat woven fabric (weight per unit area = 80 g / m ² ) made of polyethylene terephthalate long-fiber processed yarn (34T / 24f) was usually subjected to relax scouring, dispersion dyeing,
After drying, it was used as a base fabric of the highly moisture-absorbing / water-absorbing exothermic structure for interlining of the present invention.

Next, highly hygroscopic / water-absorbing exothermic organic fine particles were produced by the following method. 350 parts of a water-soluble polymer of methacrylic acid / sodium p-styrenesulfonate = 70/30 and 35 parts of sodium sulfate were dissolved in 6500 parts of water and charged into a polymerization tank equipped with a paddle type stirrer. Next, 2,750 parts of methyl acrylate 2750 parts and divinylbenzene 330 parts were added.
-Azobis- (2,4-dimethylvaleronitrile) 15
Part was melted and charged into a polymerization tank, while stirring at 400 rpm,
Polymerization was carried out at 60 ° C. for 2 hours to obtain a copolymer having a polymerization rate of 88%. 100 parts of the polymer was dispersed in 900 parts of water, 110 parts of caustic soda was added thereto, and the reaction was carried out at 90 ° C. for 2.5 hours to hydrolyze the methyl ester part of methyl acrylate to obtain a carboxyl group. 4.6 meq / g
A crosslinked polymer having The obtained polymer was dispersed in water, washed, dehydrated, pulverized and classified to obtain highly hygroscopic / water-absorbing exothermic particles. The resulting highly hygroscopic / water-absorbing exothermic organic fine particles had a hygroscopicity of 50% at 20 ° C. and 65% RH and an average particle diameter of 0.8 μm.

As a hydrophilic resin binder, 95 parts of an aqueous dispersion containing 20% of such highly hygroscopic / water-absorbing exothermic fine particles was treated with T
F-3500 (Kao's hydrophilic silicone binder;
Solid content 40%) 4 parts and Aquaprene WS105 (Meissei Chemical Industry hydrophilic urethane binder; solid content 4)
0%) Immerse the base cloth in the processing padding liquid added with 1 part,
After squeezing with a mangle so that the wet pick-up rate of the working fluid was 100%, it was dried at 120 ° C. and dry-heat set at 180 ° C. for 1 minute to obtain a structure. The moisture absorption / water absorption exothermic properties of the obtained structure are shown in Table 1. Excellent heat absorption by moisture absorption / heat absorption by water absorption was obtained as compared with the unprocessed product.

[Example 2] The same base fabric as that used in Example 1 was used as the base fabric in Example 2.

The highly hygroscopic / water-absorbing exothermic organic fine particles used in Example 2 were produced by the following method. Acrylonitrile 4
50 parts, 40 parts of methyl acrylate, 16 parts of sodium p-styrenesulfonate and 118 parts of water were charged into an autoclave, and 0.5% of di-tert-butyl peroxide was added as a polymerization initiator to the whole monomer. After that, the mixture was sealed, and then the polymerization reaction was carried out at 150 ° C. for 20 minutes under stirring, followed by cooling to about 90 ° C. with stirring to obtain an average particle size of 1.
An aqueous dispersion of raw material fine particles of 4 μm (measured by a light scattering photometer) was obtained. Hydrazine was added to this aqueous dispersion so that the concentration in the bath was 35%, crosslinking treatment was performed at 102 ° C. for 2 hours, and then caustic soda was added so that the concentration in the bath was 10%.
After hydrolyzing at 02 ° C. for 5 hours, dialysis in running water, desalting, drying, pulverization, and classification were performed to obtain highly hygroscopic / water-absorbing exothermic organic fine particles. The resulting highly hygroscopic / water-absorbing exothermic organic fine particles had a hygroscopicity of 45% at 20 ° C. and 65% RH, and an average particle diameter of 0.9 μm.

As a hydrophilic resin binder, 95 parts of an aqueous dispersion containing 20% of such highly hygroscopic / water-absorbing exothermic fine particles was used as a hydrophilic resin binder.
F-3500 (Kao's hydrophilic silicone binder;
Dip the base cloth in the processing padding solution containing 5 parts of solid content (40%) and use the mangle to wet the processing solution with a pick-up rate of 1
Squeeze to 20%, dry at 120 ° C, then 170
The structure was obtained by dry heat setting at 1 ° C. for 1 minute. The moisture absorption / water absorption exothermic properties of the obtained structure are shown in Table 1. Excellent heat absorption by moisture absorption / heat absorption by water absorption was obtained as compared with the unprocessed product.

[Example 3] 2.2 decitex, fiber length
38mm cut hollow polyester staple fiber (mechanical crimp
After opening the card, after carding, the normal needle-punched nonwoven fabric
(Basis weight = 80 g / m ²) Got.

Next, 95 parts of an aqueous dispersion containing 20% of highly hygroscopic / water-absorbing exothermic organic fine particles obtained in Example 1 was added as a hydrophilic binder with TF-3500 (hydrophilic silicon-based binder manufactured by Kao Corporation; solid). After dipping the base cloth in the processing padding liquid added with 5 parts, and squeezing with a mangle so that the processing liquid wet pickup ratio is 100%,
After drying at 120 ° C., it was dry heat set at 170 ° C. for 1 minute to obtain a structure for interlining. The moisture absorption / water absorption exothermic properties of the obtained structure are shown in Table 1. Excellent heat absorption by moisture absorption / heat absorption by water absorption was obtained as compared with the unprocessed product.

[Example 4] A flat woven fabric made of 100% cotton spun yarn of 40 count was subjected to ordinary scouring, hydrogen peroxide bleaching,
A woven fabric dyed with a reactive dye, washed and dried after mercerizing was used as a structural base fabric.

Next, 90 parts of an aqueous dispersion containing 20% of highly hygroscopic / water-absorbing exothermic organic fine particles obtained in Example 1 was used as a hydrophilic binder, and TF-3500 (hydrophilic silicone binder manufactured by Kao Corporation; solid). 40%), 3.5 parts of fibrin-reactive type glyoxal resin (dimethylol hydroxyethylene urea; 80% of solid content), 0.5 parts of magnesium chloride-based acidic catalyst, and a base cloth to a processing padding solution. Immerse and pick up the processing liquid with mangle 1
After squeezing so that it becomes 00%, it is dried at 120 ° C and then 170
The structure for interlining was obtained by dry heat setting at 1 ° C. for 1 minute. The moisture absorption / water absorption exothermic properties of the obtained structure are shown in Table 1. Excellent heat absorption by moisture absorption / heat absorption by water absorption was obtained as compared with the unprocessed product.

[Comparative Example 1] Table 1 shows the results of the woven fabric using the polyester filament processed yarn described in Example 1 alone. As compared with Examples 1 and 2, no moisture absorption / water absorption exothermic effect was observed.

[Comparative Example 2] Table 1 shows the results of the needle punched nonwoven fabric made of the hollow polyester short fibers described in Example 3 alone. As compared with Example 3, no moisture absorption / water absorption exothermic effect was observed.

Comparative Example 3 The cotton spun yarn 1 described in Example 4
The results for the 00% flat fabric alone are shown in Table 1. Although some heat absorption due to moisture absorption / water absorption was observed, it was inferior to that of Example 4.

Comparative Example 4 Using the polyester woven fabric of Example 1, 5 parts of amino-modified silicone resin binder (solid content 40%) was added to 95 parts of an aqueous dispersion containing 20% of highly hygroscopic / water-absorbing exothermic fine particles. The base cloth was dipped in the working liquid, squeezed with a mangle so that the wet pick-up ratio of the working liquid was 100%, dried at 120 ° C., and then dried and set at 180 ° C. for 1 minute to obtain a structure. The moisture absorption / water absorption exothermic properties of the obtained structure are shown in Table 1. The exothermic heat of moisture absorption / exothermic heat of water absorption was inferior to those of the examples.

[0041]

[Table 1]

[0042]

EFFECTS OF THE INVENTION According to the present invention, highly hygroscopic exothermic particles are attached to a knitted fabric, a woven fabric, a nonwoven fabric, a fleece or a resin molded product through a small amount of a hydrophilic resin, and the external environment, human body or artificial moisture By absorbing (steam) and water (liquid) and quickly and stably generating heat, a moisture-absorbing / water-absorbing exothermic structure suitable for interlining can be obtained easily and stably.

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Claims (9)

[Claims] 1. A structure for moisture-absorbing / water-absorbing exothermic interlining, which is a structure to which highly hygroscopic fine particles are adhered, and has a maximum temperature rise of 3 ° C. or more during moisture absorption and / or water absorption. . 2. The moisture-absorbing / water-absorbing exothermic interlining structure according to claim 1, wherein the heat generated when absorbing moisture is maintained for 30 minutes or more and / or the heat generated when absorbing water is maintained for 1 minute or more. 3. The moisture-absorbing / water-absorbing exothermic interlining structure according to claim 1, wherein the maximum temperature rise during water absorption is 8 ° C. or higher. 4. The moisture absorbing / water absorbing exothermic interlining structure according to claim 1, wherein the highly hygroscopic fine particles are organic fine particles. 5. The highly hygroscopic organic fine particles are polystyrene-based,
Polyacrylonitrile-based, polyacrylic ester-based,
Polymethacrylic acid ester-based vinyl polymer having a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, or at least one hydrophilic group of metal salts thereof, and having divinylbenzene, triallyl isocyanate, or The moisture-absorbing / water-absorbing exothermic interlining structure according to claim 4, which is a cross-linked polymer cross-linked with any one of hydrazine. 6. The moisture-absorbing / water-absorbing exothermic interlining structure according to any one of claims 1 to 5, wherein the highly hygroscopic fine particles have an average particle diameter of less than 2 μm. 7. The highly hygroscopic fine particles are immobilized on the structure via a hydrophilic resin.
The moisture-absorbing / water-absorbing exothermic interlining structure according to any one of 1. 8. The mass ratio of the highly hygroscopic fine particles to the hydrophilic resin is 1/1 to 19/1.
The moisture-absorbing / water-absorbing exothermic interlining structure according to any one of 1. 9. The structure is a knitted fabric, a woven fabric, a nonwoven fabric, a fleece, a string-like body or a film, or a resin molded body, which is composed of natural fibers, synthetic fibers or mixed fibers thereof. 9. The moisture-absorbing / water-absorbing exothermic interlining structure according to any one of 8 above.