JP2003105657A - Internal material of shoe having hygroscopic and pyrogenic property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an internal material of shoe such as shoe side fabric, shoe insole member, etc., having improved heat retaining property and stuffy feeling, excellent comfortableness with nice heat retaining property and hygroscopicity especially in winter. SOLUTION: This internal material of shoe such as a shoe side fabric, a shoe insole, etc., is a structural body stuck with a highly hygroscopic fine particle and comprises at least 20 mass % of a hygroscopic and pyrogenic structural body having >=3 deg.C maximum temperature rise in moisture absorption. The internal material of shoe comprises a hygroscopic and pyrogenic structural body keeping heat generation in moisture absorption for >=30 deg.C minutes.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an inner shoe member. More specifically, the present invention relates to an inner shoe member such as a shoe side, a shoe insole, etc., which has improved heat retention and stuffiness and is excellent in comfort.

[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. However, as for the heat retention in the shoes, it is hardly proposed because it is difficult to secure a space for the heat insulation agent. Speaking of which, socks are often devised. In the olden days, padding such as cotton was used in the shoes to enhance the heat retaining effect. Another problem with shoes is that they tend to get stuffy. In order to avoid this, sandals or the like in which meshes and strings are combined are worn in the summer and the like, but it is not suitable when there is external landing such as rain. In addition, heat retention and ventilation are contradictory properties, and cannot be satisfied simultaneously by ordinary methods.

[0003]

DISCLOSURE OF THE INVENTION The present invention is a shoe such as a shoe side or shoe insole member having improved heat retention and stuffiness and having excellent heat retention and moisture absorption especially in winter. It is intended to provide an inner member.

[0004]

In order to solve the above problems, the present invention introduces a base cloth having the following technical construction as an inner member for shoes. That is, 1. A shoe inner member which is a fibrous structure to which highly hygroscopic fine particles are adhered, and which contains 20% by mass or more of a hygroscopic exothermic fiber structure having a maximum temperature rise of 3 ° C. or more when absorbing moisture.

2. The shoe inner member according to the first aspect, wherein heat generated when the structure absorbs moisture is retained for 30 minutes or more.

3. The shoe inner member according to the second aspect, wherein the highly hygroscopic fine particles attached to the structure are organic fine particles.

4. The structure is a highly hygroscopic organic fine particle is a polystyrene-based, polyacrylonitrile-based, polyacrylic acid ester-based, polymethacrylic acid ester-based vinyl polymer, sulfonic acid group, carboxylic acid group, phosphoric acid group or The shoe inner member according to the third aspect, which is a crosslinked polymer having at least one hydrophilic group of metal salts thereof and crosslinked with either divinylbenzenetriallyl isocyanate or hydrazine.

5. The shoe inner member according to any one of items 2 to 4, wherein the fine particles have an average particle diameter of less than 2 μm.

6. 6. The shoe inner member according to any one of 2 to 5, wherein the structure has a highly hygroscopic fine particle fixed to the structure via a hydrophilic resin.

7. 7. The shoe inner member according to any one of 2 to 6, wherein the mass ratio of the highly hygroscopic fine particles and the hydrophilic resin in the structure is 1/1 to 19/1.

8. The structure is a natural fiber, a knitted fabric, a woven fabric or a non-woven fabric composed of a compound fiber or a mixed fiber of these,
The shoe inner member according to any one of the second to seventh aspects.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. In the shoe inner member such as the shoe side material and the shoe insole member of the present invention, the moisture absorbing and heat generating fiber structure is used for at least a part of the constituent laminated materials. The moisture absorbing heat generating structure used in the present invention, polyester-based, polyamide-based, polyacrylonitrile-based, polyethylene-based, polypropylene-based, polybutylene terephthalate-based, polytetramethylene terephthalate-based, polyurethane-based, polyphenylene sulfide-based synthetic fibers, Knitted fabrics, woven fabrics, non-woven fabrics made of chemical fibers such as rayon and acetate, natural fibers such as cotton, hemp, silk, wool, and feathers, or mixed materials thereof.
It is composed of braids.

Highly hygroscopic fine particles (high moisture absorption /
Also referred to as water-absorbing and exothermic organic fine particles. ) Is not particularly limited in terms of chemical structure as long as it is a fine particle that exhibits exothermicity when absorbing moisture. For example, inorganic particles such as hygroscopic silica, or various organic particles such as hygroscopic polyurethane, polyamide, polyester and polyacrylate particles can be applied, but particularly high hygroscopic / water absorbing exothermic organic particles. Preferably, for example, polystyrene-based, polyacrylonitrile-based, polyacrylic acid ester-based, polymethacrylic acid ester-based vinyl polymer, sulfonic acid group, carboxylic acid group, phosphoric acid group or a metal salt thereof. Which is at least one kind of hydrophilic group and is crosslinked with divinylbenzene, triallyl isocyanate or hydrazine.

The particle size of the highly hygroscopic fine particles depends on the heat absorption rate of moisture absorption /
From the viewpoint of heat generation efficiency, uniform adhesion, texture and abrasion resistance, finer is preferable, and average particle diameter of less than 2 μm is more preferable.

The method of applying the highly hygroscopic fine particles used in the present invention is a method of directly kneading into a fiber, a film or a resin layer, or a binder on the surface layer of a knitted fabric, a woven fabric, a nonwoven fabric, a fleece, a string, a film or a resin molded product. A method of attaching via a resin is mentioned, but the latter method of attaching via a binder resin is preferable from the viewpoint of moisture absorption / water absorption heat generation rate / heat generation efficiency.

As the binder resin, a usual impregnation method,
Examples of the resin include silicone-based, urethane-based, acrylic-based, polyester-based, polyamide-based, and polyethylene oxide-based resins that can be applied to the padding method, coating method, and spray method, and are not particularly limited, but are hydrophilic, that is, hygroscopic, permeable. It is desirable to use a type that has excellent wettability, does not inhibit the excellent hygroscopicity and water absorption of the highly hygroscopic / water-absorbing exothermic fine particles, and has an excellent binder function that can effectively adhere and fix the highly hygroscopic / water-absorbing exothermic fine particles to the structure. . As a particularly preferable hydrophilic resin binder, as the hydrophilic segment, polyalkylene oxide addition type, sulfonate,
Hydrophilic silicone resin, hydrophilic urethane resin, hydrophilic polyamide resin, hydrophilic polyethylene oxide resin with polar hydrophilic group type such as carboxylate, modified amide, etc. Those that have high wettability and do not impair hygroscopicity can be mentioned. The moisture permeability of the resin as used herein means the moisture permeability in a non-porous film state. Even a resin having a high moisture permeability expressed by a microporous film, a binder resin having a low hygroscopicity of the resin itself masks and lowers the excellent moisture absorption heat generation or water absorption heat generation property of the high moisture absorption heat generation fine particles. In addition, in order to improve the durability, these high moisture absorption / water absorption exothermic fine particles and hydrophilic resin binder are combined with various crosslinking agents such as isocyanate type, methylol type, ethyleneimine type, polyfunctional aziridinyl type, and metal salt type. You may use together in the range which does not reduce the original hygroscopic property of fine particles.

The compounding ratio of the highly hygroscopic heat-generating particles and the hydrophilic resin and the amount of these adhering particles in the present invention have a great influence on the heat-moisture absorption. The compounding ratio of the highly hygroscopic heat-generating particles and the hydrophilic resin is slightly different depending on the hydrophilic level of the hydrophilic resin, but it is usually desirable to use the compounding ratio of 1/1 to 19/1, and preferably,
The compounding ratio of 10/1 to 19/1 is more preferably 1
Particularly, the smaller the compounding ratio of the hydrophilic resin, such as the compounding ratio of 5/1 to 19/1, is, the more excellent heat absorption by moisture absorption can be exhibited. However, when the hydrophilic resin is extremely small, or when the hydrophilic resin is not used together, the abrasion resistance of the highly hygroscopic and heat-generating fine particles adhered to the surface of the structure is lowered, and the particles easily fall off. On the contrary, when the mixing ratio of the hydrophilic resin is high, even in the case of the hydrophilic resin, there are many cases where the hygroscopicity originally possessed by the highly hygroscopic exothermic particles is obstructed. Extremely low. of course,
When the hygroscopicity of the hydrophilic resin is equal to or higher than that of the highly hygroscopic and heat-generating fine particles, the compounding ratio of the hydrophilic resin can be increased.

The exothermicity of the hygroscopic and exothermic structure used in the present invention is based on the heat of adsorption reaction generated when the substance absorbs moisture.
It depends on the hygroscopic ability and the amount of adhesion of the highly hygroscopic fine particles and the combined hydrophilic resin binder contained in the structure. That is, the higher the hygroscopic particles, the finer the hydrophilic resin binder having the higher hygroscopic level, the larger the heat production due to the adsorbed moisture, the faster the heat generation rate, and the longer the heat retention time.
Of course, since the structure substrate alone has such hygroscopicity, the moisture absorption rate (20 ° C., 65% RH) of the applied hygroscopic exothermic fine particles should be 25% or more in order to realize more effective hygroscopicity. Desirably, more preferably 40% or more. Further, the combined hydrophilic resin preferably has at least a moisture absorption rate (20 ° C., 65% RH) of 3 to 50% which does not impair the hygroscopicity / water absorptivity of the moisture absorption / water absorption exothermic fine particles as much as possible. That is, in order to obtain effective moisture absorption and heat generation, the structure having a high degree of moisture absorption and heat generation of the present invention is stored with a moisture absorption rate as low as possible, and more preferably in a state close to a completely dry (absolute dry) state. It is essential. On the other hand, the structure that has absorbed heat above the saturated moisture absorption rate and has completed heat generation is cooled by heat dissipation and drops to the initial temperature, but if it is dried again to remove the adsorbed water, the original excellent moisture absorption heat generation Gender reappears.

According to the present invention, the structure in which the kind and the amount of the highly hygroscopic heat-generating particles are optimized, and the particles are adhered via a proper hydrophilic resin binder, the maximum temperature rise during moisture absorption is 3 ° C. or more, It is preferably 4 ° C. or higher, more preferably 5 ° C. or higher, or the heat retention time when absorbing water is 30 seconds or longer, more preferably 1 minute or longer. In terms of heat generation performance, excellent heat absorption by moisture absorption that has never been obtained can be obtained.

In the shoe inner member of the present invention, in the case of the shoe ground, the high moisture absorption heat generating structure can be used alone, but can also be covered with a coarse mesh material for the purpose of reinforcement,
The outer surface of the high moisture absorption heat generating structure is covered with an outer skin for ensuring the shape retention and strength required for shoes. The mass of the highly hygroscopic heat generating structure in the shoe inner member is at least 20.
% Is required, and if it is less than 20%, neither heat retention nor moisture absorption performance can be felt. If necessary, it is also possible to form an elastic body on the entire shoe side by using a high-density fabric or the like and impregnate the entire body.

Further, in the case of the shoe insole member, it is preferable that the high moisture absorption heat generating structure is located near the sole side, but it is also possible to cover it with a coarse mesh material for the purpose of reinforcement, and the lower part of the high moisture absorption heat generating structure. It is more preferable to stack an elastic member having a high porosity for the purpose of cushioning and moisturizing. The absorbed moisture is stored as high-humidity air in the void and is discharged to the outside of the shoe by the repeated compression of the shoe insole member during walking. The mass of the high moisture absorption heat generating structure in the shoe insole member needs to be at least 20%, and if it is less than 20%, neither heat retention nor moisture absorption performance can be felt. If necessary, the entire shoe insole member may be made of a non-woven fabric or the like to form an elastic body and the whole body may be impregnated.

As the outer skin material in the present invention, it is preferable to use a material having a so-called moisture-permeable and waterproof function of repelling water and allowing moisture in the vapor phase to pass therethrough.

The shoe inner member of the present invention can exhibit multi-functionality such as antibacterial deodorant property, bacteriostatic property, deodorant property, and nonenal deodorant property, in addition to these excellent high moisture absorption and heat generation properties.

[0024]

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. The moisture absorption rate and the exothermic temperature were measured by the following measuring 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 put into 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% for temperature control and humidity control. . 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 later, the lid was opened and the state of dew condensation of the sample was visually judged.

<Antibacterial property> A quantitative antibacterial test method (unified test method) of a textile product was used according to the manual.
As the test bacterial species, Staphylococcus aureus Staph-yl
Using Occoccus aureus ATCC 6538P, the number was determined by the following method from the number of unprocessed cloth (standard cotton cloth) bacteria [B] and the number of evaluated sample bacteria [C]. Bacteriostatic activity value = logB-logC Products having a bacteriostatic activity value of 2.2 or more were considered to have antibacterial properties.

[Example 1] Polyethylene terephthalate type polyester long fiber needle punched nonwoven fabric (single yarn fineness; 5.5 decitex, basis weight; 100 g / m ² , thickness;
1.0 mm) was used as the base fabric of the highly hygroscopic and exothermic structure of the present invention.

Next, the highly hygroscopic and 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, methyl acrylate 27
15 parts of 2,2'-azobis- (2,4-dimethylvaleronitrile) was dissolved in 50 parts and 330 parts of divinylbenzene and charged into a polymerization tank, and stirred at 400 rpm at 60 ° C.
Polymerization was carried out 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. A cross-linked polymer having 4.6 meq / g was obtained. Disperse the obtained polymer in water,
After washing and dehydration, pulverization, classification or filtration was performed to obtain highly hygroscopic / water-absorbing exothermic particles. The high moisture absorption / water absorption exothermic organic fine particles thus obtained have a moisture absorption rate of 50% at 20 ° C. and 65% RH,
The average particle size was 0.8 μm.

TF-3 was added as a hydrophilic resin binder to 95 parts of an aqueous dispersion containing 20% of such highly hygroscopic and heat-generating fine particles.
500 parts (Kao Corporation hydrophilic silicone binder; solid content 40%) 4 parts and Aquaprene WS105 (Meisei Chemical Industry hydrophilic urethane binder; solid content 40%)
Immerse the base cloth in the processing padding liquid added with 1 part, squeeze the processing liquid wet pickup ratio to 100% with a mangle, dry it at 120 ° C, and set it at 180 ° C for 1 minute to dry heat and structure Got Table 1 shows the moisture absorption and exothermic properties of the obtained structure. As compared with the unprocessed product, it was possible to obtain the moisture absorption and heat generation properties, which were superior in heat generation rate, heat generation temperature, and heat generation retention time, and it was also possible to confirm antibacterial properties.

The processed cloth and a nylon processed thread mesh knitted fabric (33 decitex, using 6 filaments and a basis weight of 35 g / m ² ) for reinforcement were laminated to form an inner shoe member. A shoe in which the same fabric is placed on the inner side surface and the bottom surface of a shoe (a synthetic leather having a moisture-permeable and waterproof property is used as an outer skin) is prepared. The wearing feeling of the shoe when it was worn for 30 minutes in an environment of 10 ° C. and 40% RH by wearing nylon socks was compared with that of a shoe using the same kind of outer skin and not wearing the shoe interior material of the present invention. did. The person using the interior material of the present invention was warm and had less stuffiness. Also,
When the shoes not using the product of the present invention were worn, the soles of the socks were slightly moist.

Example 2 Polyethylene terephthalate-based polyester long-fiber processed yarn fabric (110 decitex, 2
A plain weave of 4 filaments having a basis weight of 88 g / m ² ) was used as a base fabric and treated in the same manner as in Example 1 to obtain a processed fabric. The results are shown in Table 1.

A shoe in which the processed shoe inner member and the unprocessed same cloth were respectively installed were prepared in the same manner as in Example 1. When evaluated in the same manner as in Example 1, it was confirmed that the processed cloth had heat retention, no stuffiness, and antibacterial properties as compared with the unprocessed cloth.

[Comparative Example 1] Polyethylene terephthalate-based polyester long-fiber processed yarn woven fabric (22 decitex,
A plain weave of 12 filaments having a basis weight of 23 g / m ² was used as a base fabric and treated in the same manner as in Example 1 to obtain a processed fabric. The results are shown in Table 1.

The processed cloth and a polyester filament processed yarn woven fabric (165 decitex, 48 filaments, basis weight: 185 g / m ² ) were laminated to each other to provide a shoe interior material. Evaluation was carried out by the same method as in Example 1. Neither the heat retaining effect nor the stuffiness preventing effect was felt, and no antibacterial property was observed. Further, a slight amount of water was felt on the soles of the socks by touch.

[0037]

[Table 1]

[Example 3] Polyethylene terephthalate polyester long fiber needle punched nonwoven fabric (single yarn fineness; 5.5 decitex, basis weight; 212 g / m ² , thickness; 2.1 m
m) was used as the base fabric of the highly hygroscopic and exothermic structure of the present invention.

Highly hygroscopic exothermic particles 20 described in Example 1
% In an aqueous dispersion containing 100% of TF-3500 (Kao's hydrophilic silicone binder; solid content 40%) 4 parts and Aquaprene WS10
5 (Meisei Chemical Industry Co., Ltd. hydrophilic urethane binder; solid content 40%) The base cloth is dipped in the processing padding liquid and 1 part of the processing liquid is wet picked up with a mangle.
Squeeze to 0%, dry at 120 ° C, then 180 ° C
After that, the structure was obtained by dry heat setting for 1 minute. Table 2 shows the moisture absorption and exothermic properties of the obtained structure. As compared with the unprocessed product, it was possible to obtain the moisture absorption and heat generation properties, which were superior in heat generation rate, heat generation temperature, and heat generation retention time, and it was also possible to confirm antibacterial properties.

The processed cloth and the unprocessed cloth are shaped into the shape of the right foot and the left foot respectively, inserted into ordinary leather shoes, and the socks made of nylon processed thread are worn, and the environment is kept at 10 ° C. and RH 40% for 30 minutes. As a result of comparing the feeling of wearing when walking, it was found that the person using the processed cloth as the shoe insole member had a warmer and less stuffy feeling than the one using the unprocessed cloth. Moreover, the sole of the sock in which the unprocessed cloth was worn was slightly moist.

[Example 4] Polyethylene terephthalate polyester long fiber needle punched nonwoven fabric (single yarn fineness; 5.5 decitex unit weight; 101 g / m ² , thickness; 1.0 m
m) was used as a base fabric and treated in the same manner as in Example 1 to obtain a processed fabric. The results are shown in Table 2.

The processed cloth and the unprocessed non-woven fabric were bonded together, and a plain weave of polyester filament (22 decitex monofilament) having a basis weight of 25 g / m ² was bonded to the surface of the processed cloth, shaped and sewn to form a shoe insole member. . When evaluated by the same method as in Example 1, it was confirmed that the processed cloth had heat retention, no stuffiness, and antibacterial properties as compared with the unprocessed cloth.

[Comparative Example 2] Polyethylene terephthalate polyester long fiber needle punched non-woven fabric (single yarn fineness; 5.5 decitex unit weight; 53 g / m ² , thickness; 0.6 m
m) was used as a base fabric and processed in the same manner as in Example 1 to obtain a high moisture absorption heat generating structure. The characteristics are shown in Table 2.

The processed cloth and polyethylene terephthalate-based polyester long fiber needle punched non-woven cloth unprocessed cloth (single yarn fineness; 3.3 decitex, basis weight; 305 g / m ² ) are laminated and shaped to form a shoe insole member. Evaluated by law. Neither the heat retaining effect nor the stuffiness preventing effect was felt, and no antibacterial property was observed. Further, a slight amount of water was felt on the soles of the socks by touch.

[0045]

[Table 2]

[0046]

EFFECTS OF THE INVENTION According to the present invention, due to its excellent hygroscopicity and the effect of generating heat due to this hygroscopicity, it can bring about a comfortable in-shoe climate which is excellent in heat retention and stuffiness prevention when worn in a cold environment. An inner shoe member such as a shoe interior material and a shoe insole member can be provided.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F050 AA01 AA06 BC01 BC03 BC07                       BD01 HA16 HA80 HA89                 4L033 AC07 AC15 CA11 CA13 CA18                 4L047 AA07 AA12 AA13 AA21 BA03                       CC16 DA00

Claims (8)

[Claims] 1. A shoe having a hygroscopic exothermic fiber structure having a maximum hygroscopic temperature increase of 3 ° C. or more, which is a fibrous structure to which highly hygroscopic fine particles are attached. Inner member. 2. The shoe inner member according to claim 1, wherein a structure is included in a heat-absorbing heat-generating property that retains heat generated during moisture absorption for 30 minutes or more. 3. The shoe inner member according to claim 1, wherein the highly hygroscopic fine particles are organic fine particles. 4. The highly hygroscopic organic fine particles are polystyrene-based,
Polyacrylonitrile-based, polyacrylic ester-based,
Any vinyl polymer of polymethacrylic acid ester type, having a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, or at least one hydrophilic group of metal salts thereof,
The shoe inner member according to claim 3, which is a crosslinked polymer crosslinked with either divinylbenzene, triallyl isocyanate or hydrazine. 5. The shoe inner member according to claim 3, wherein the highly hygroscopic fine particles have an average particle diameter of less than 2 μm. 6. The shoe inner member according to claim 1, wherein the hygroscopic fine particles are fixed to the structure through a hydrophilic resin. 7. A mass ratio of the highly hygroscopic fine particles and the hydrophilic resin is 1/1 to 19/1.
The shoe inner member according to any one of 1. 8. The shoe interior according to claim 1, wherein the structure is a knitted fabric, a woven fabric, a non-woven fabric or a braid composed of natural fibers, synthetic fibers or mixed fibers thereof. Material.