JPH06220775A - Cloth having moisture-premeability controllable by temperature - Google Patents

Abstract

PURPOSE:To obtain a cloth having moisture-permeability controllable by the change of temperature by coating a textile structure with a synthetic polymer containing a heat-responding polymer. CONSTITUTION:A woven, knit or nonwoven cloth made of natural fiber, synthetic fiber, etc., is coated with a formulated treating liquid containing a synthetic polymer (e.g. urethane resin, acrylic copolymer or silicone) containing a heat-responding polymer such as poly-N-isopropylacrylamide of formula I, polyacryloylpiperidine of formula II, polyacryloylpyrrolidone of formula III and poly-n-propylacrylamide of formula IV at a rate of 1-200g/m<2> to obtain the objective cloth having moisture-permeability controllable by the temperature change and capable of keeping the humidity in clothes to a low level at high temperature and to a high level at low temperature.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fabric whose moisture permeability is controlled by changing temperature.

[0002]

2. Description of the Related Art Conventionally, fabrics made of synthetic fibers and fabrics made of natural fibers are required to have water repellency, waterproofness, windproofness, heat retention,
Addition of performance such as flame retardancy, heat resistance, heat insulation, and color,
Various coating processes are carried out to impart surface changes such as gloss and touch.

More recently, there has been a strong demand for products having excellent moisture permeability in order to prevent the stuffy feeling of coated products. For example, porous fibrillated Teflon membranes on the surface of fabrics,
Those made by joining porous polyethylene with an adhesive, etc.,
Although a method of forming a wet regenerated film of urethane resin on a fiber structure has been proposed, only one with a small change in moisture permeability can be obtained, keeping the humidity inside the clothes low at high temperatures and keeping the humidity inside the clothes low. There was a problem that it was not possible to control it to keep it high, and its use was restricted at low temperatures.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and keeps the humidity inside clothes at a high temperature at a high temperature and keeps the humidity inside a clothes at a low temperature higher than that of a conventional coated cloth. An object of the present invention is to provide a fabric which can be kept, that is, whose moisture permeability can be controlled by changing the temperature.

[0005]

Means for Solving the Problems The above object is a fibrous structure made by coating a synthetic polymer containing a thermally responsive polymer, in that the coating weight of 1g / m ² ~200g / m ² It is achieved by a fabric whose moisture vapor transmission rate is controlled by the temperature.

In the present invention, the fibrous structure means a knitted fabric, a woven fabric, a non-woven fabric made of only natural fibers or synthetic fibers, or a mixed spun product made of two or more kinds of fibers, a mixed woven or mixed knitted fabric, leather,
A product containing paper and other fibers.

In the present invention, the thermoresponsive polymer means fine polymer particles (microspheres) which become hydrophilic or hydrophobic only by raising and lowering the temperature. As their thermoresponsive polymer, polyacrylamide derivatives

[Chemical 1] , Poly-N-isopropylacrylamide,
General formula

[Chemical 2] , Polyacryloylpiperidine, a general formula

[Chemical 3] , Polyacryloylpyrrolidine, a general formula

[Chemical 4] And poly-n-propyl acrylamide, etc.

[0008] In the case of hydrophilic polyacrylamide, since both amino groups have hydrogen atoms at their tips, the hydration power is strong and does not dehydrate even at high temperature (maintains hydrophilicity). However, if both or one of the ends of the amino group is made bulky and hydrophobic, such as poly (N-isopropylacrylamide), it warms even if it has water and hydration power at low temperature (provides thermal energy). ), The hydrogen bond is broken and dehydrated (becomes hydrophobic). This transition temperature is, for example, poly-N-
The temperature is around 32 ° C. for isopropylacrylamide, around 51 ° C. for polyacryloylpyrrolidine, around 5 ° C. for polyacryloylpiperidine, and around 22 ° C. for poly-n-propylacrylamide. Then, by mixing and copolymerizing these compounds, it becomes possible to prepare microspheres having a transition temperature according to the composition ratio. In addition, butyl vinyl ether, polyethylene glycol methacrylate and the like can be cited as the monomer which becomes a thermoresponsive polymer of this kind other than the acrylamide derivative.

If the hydration power of the polymer changes with temperature,
The material expands and contracts in water in response to temperature changes. If such a polymer is in the form of microspheres, its change can be easily measured by measuring the hydrodynamic particle size in water. An example is shown in FIG.

The particle size at a temperature below the transition point of the polymer is about 2.5 times the particle size at a temperature above the transition point, and if this is a manifestation of the result of taking in plenty of water, the polymer is its own. It is swollen with about 16 times the volume of water.

Examples of the synthetic polymer for adhering the thermoresponsive polymer to the fiber structure include urethane resin, acrylic copolymer, and a polymer substance containing silicon as a main component.

As the polyurethane resin, for example, an organic diisocyanate and a polyalkylene ether glycol, or a polyester having a hydroxy group at the terminal is reacted to prepare a prepolymer, and a chain extender such as diamine, diol, or polyol is used, and an appropriate known method is used. To produce a polyurethane elastomer. As the organic diisocyanate which is a component constituting these polyurethanes, aromatic, aliphatic, and alicyclic hydrocarbon diisocyanates or a mixture thereof, specifically, for example, toluylene-2,4-diisocyanate, toluylene-2,
6-diisocyanate, diphenylmethane-4,4 '
-Diisocyanate, 1,5-naphthylene diisocyanate, hexamethylene diisocyanate, paraxylene diisocyanate and the like.

Examples of the polyalkylene ether glycol include polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and mixtures and copolymers thereof, and polyesters include ethylene glycol, 1, Aliphatic polyalkylene glycols such as 4-butylene glycol, propylene glycol, tetramethylene glycol and hexamethylene glycol, alicyclic glycols such as cyclohexanediol, glycols such as aromatic glycols such as xylenediol and succinic acid, adipic acid, Polycondensates with organic acids such as sebacic acid and terephthalic acid are used as chain extenders such as ethylene glycol, 1,4-butylene glycol and hydra. Emissions, ethylenediamine, include methylene di -O- chloro aniline. If necessary, triethylamine, triethylenediamine, N-methylmorpholine, N-ethylmorpholine, dibutyltin dilaurate, cobalt naphthenate or the like is used as a polymerization reaction catalyst. The polyurethane thus obtained is usually applied to the present invention in the form of a solution. As the solvent for dissolving polyurethane, water or a water-soluble or water-miscible solvent that can be extracted with a water-miscible solvent is suitable, and examples thereof include N, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, tetramethylurea, and N. , N-dimethylacetamide, dioxane, butylcarbinol and the like are used alone or in combination. It is permissible to use ketones such as acetone and methyl ethyl ketone and water in these solvents in a range that does not solidify the polyurethane, for example, 20% or less.

As the acrylic copolymer used in the present invention, any of those generally used can be applied. For example, a hydroxyl group- or carboxyl group-containing ethylenically unsaturated monomer polymer and a crosslinking agent are ketones. A solution dissolved in an organic solvent such as benzene, xylene, toluene and halogenated hydrocarbons is mainly used.

The hydroxyl group- or carboxyl group-containing ethylenically unsaturated monomer polymer is represented by the general formula:

[Chemical 5] (In the formula, R ₇ is hydrogen or an alkyl group having 1 to 2 carbon atoms, R ₃
Is an alkyl group, an aryl group, a halogen-substituted alkyl group,
Halogen-substituted aryl group, nitrile group or 2 to 1 carbon atoms
9 represents an alkoxycarbonyl group. However, when R ₃ is a nitrile group, R ₇ is hydrogen. ) An ethylenically unsaturated monomer having neither a hydroxyl group nor a carboxyl group, represented by the general formula

[Chemical 6] (Wherein R ₂ represents hydrogen, an alkyl group or a carboxyalkyl group, R ₁₀ represents a hydrogen or a carboxyl group, R ₁₁ represents a hydrogen or a hydroxyalkyl group, and n represents 0 or a positive integer) or It can be obtained very easily by polymerizing an ethylenically unsaturated monomer having a carboxyl group by a known appropriate method. If an example of a specific example of the monomer represented by the general formula (1) is shown here, acrylonitrile, alkyl acrylate, alkyl methacrylate, styrene and the like are acrylic as the monomer represented by the general formula (2). Examples of the acid include ethylenically unsaturated acids such as methacrylic acid, itaconic acid, fumaric acid, and maleic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, 3-chloro-2-hydroxyalkyl methacrylate, and the like (1) or (2 It is needless to say that the monomers represented by the formula) may be used as two or more kinds of each of them in the polymerization to form a ternary or more multi-component polymer.

As the polymer substance containing silicon as a main component, a dehydrogenation reaction, dealcoholization reaction or addition reaction product of a silicon prepolymer having hydrogen, an alkyl group or a hydroxyl group at the terminal is generally used. It is a polymeric substance produced by the following formula and is industrially produced. (A) Dehydrogenation reaction type

[Chemical 7] (B) Dealcoholization reaction type

[Chemical 8] (C) Addition reaction type

[Chemical 9]

The silicon prepolymer is a halogenated hydrocarbon such as trichloroethylene, tetrachloroethylene, 1,1,1-trichloroethane, etc., or a single solvent of benzene or toluene or a mixed solvent thereof, and a solid content concentration of 5 to 40.
%, Viscosity adjusted to 3000 to 50000 cps, Pt,
By using a catalyst containing a metal such as Zn, Sn, or Pb together, a resin film containing silicon as a main component is formed on the fiber structure.

The coating amount of the fiber structure of the heat-responsive polymer and the synthetic polymer is ^{1g / m 2 ~200g / m 2} . If it is less than 1 g / m ² , the moisture permeability cannot be controlled by the temperature, and if it exceeds 200 g / m ² , the texture becomes too hard, so the above range is set. The ratio of the thermoresponsive polymer and the synthetic polymer used is 1: from the viewpoint of adhesiveness and effect.
About 0.5 to 1:50 is preferable.

In addition, synthetic polymers having a thermoresponsive polymer, fibroin and modified fibroin, silk powder, collagen, chitosan, gelatin, protein,
It is also possible to use natural proteins such as casein, cellulose powder, rayon powder, wool powder, and keratin, or inorganic particles such as silicon dioxide, titanium oxide, zirconium oxide, and aluminum oxide. By dispersing animal protein fibers such as protein powder and silk powder, which have an ultrafine powder size smaller than several hundreds of micron order, in the coating layer, dew condensation-preventing property and dry-touch texture can be imparted.
Examples of the application method include coating and laminating. The coating method may be either dry coating or wet coating, and a coating method such as a floating knife coater, a knife over roll coater, a reverse roll coater, a roll doctor coater, a gravure roll coater, or a kiss roll coater can be used. Further, the coating film may be made porous by a known method.

In the present invention, in addition to the coating process,
Of course, various treatments such as water repellency and softness may be applied. However, the water-repellent treatment can be performed either before or after coating, but if it is performed before coating, it is necessary to pay sufficient attention to the adhesive strength.

[0021]

The present invention is characterized by having a thermoresponsive polymer. When the temperature of the atmosphere is higher than the transition temperature of the thermoresponsive polymer, the particle size of the thermoresponsive polymer becomes small and the water vapor permeability becomes large. When the temperature of the atmosphere is lower than the transition temperature, the particle size of the thermoresponsive polymer becomes large and the water vapor permeability becomes small. That is, it is possible to control the moisture permeability by changing the temperature.

[0022]

EXAMPLES The present invention will be described in detail below based on examples. In the examples, "part" means "part by weight", moisture permeability is measured according to JIS-L-1099, and water resistance is JI.
It was measured by SL-1092 (method A).

Example 1 A plain woven fabric (warp density 98 yarns / inch, weft density 94 yarns / inch) using polyester filament yarns of 60d / 48f as warp yarns and weft yarns was prepared, and this woven fabric was scoured by a known method. , Heat set, dyeing, and water repellent finish with fluorine water repellent. Polyurethane resin (Dainippon Ink and Chemicals, Crisbon NYT-20
(Solid content 20%) 100 parts by weight of poly-N-isopropylacrylamide (particle size shown in FIG. 1) 7 parts was applied using a floating knife coater,
Immediately after drying at a temperature of 120 ° C. and heat treatment (170 ° C.), the product of Example 1 was obtained.

Comparative Example 1 A polyurethane resin (Krisbon NY, manufactured by Dainippon Ink and Chemicals, Inc.) was added to the water-repellent treated fabric used in Example 1.
T-20) alone was applied using a floating knife coater, immediately dried at a temperature of 120 ° C., and heat-treated (170 ° C.) to obtain a product of Comparative Example 1.

Example 2 To 100 parts of a porous urethane resin (Daimichi Seika Kogyo KK, Heimlen X-3040 (solid content 30%)) was added a mixed solvent of methyl ethyl ketone / toluene = 13 parts / 18 parts, and A mixture of 1 part of poly-N-isopropylacrylamide (particle size shown in FIG. 1) and 50 parts of water was gradually added dropwise to prepare a treatment liquid. And
The above treated liquid was applied to the water-repellent treated fabric used in Example 1 using a knife over roll coater, immediately dried at a temperature of 80 ° C., and heat treated (13
Then, the product of Example 2 was obtained.

Comparative Example 2 To 100 parts of a porous urethane resin (Heimren X-3040 manufactured by Dainichiseika Kogyo Co., Ltd.) was added a mixed solvent of methyl ethyl ketone / toluene = 13 parts / 18 parts, and water 5
Only 0 part was gradually dropped to prepare a preparation treatment liquid. Then, the above water-repellent treated fabric used in Example 1 was coated with the above treatment liquid using a knife over roll coater, immediately dried at a temperature of 80 ° C., and heat-treated (130 ° C.). .

Example 3 Polyurethane resin (Krisbon NY, manufactured by Dainippon Ink and Chemicals, Inc.) was added to the water-repellent treated fabric used in Example 1.
A treatment liquid prepared by mixing 4 parts of poly-N-isopropylacrylamide (particle size shown in FIG. 1) was applied to 100 parts of T-20). Then, the solvent is evaporated, and the solvent evaporation rate is 50%.
Then, hexane was poured as a non-solvent and the mixture was immersed for 1 hour and then dried to obtain the product of Example 3.

Comparative Example 3 The product of Comparative Example 3 was obtained by treating the water-repellent treated fabric used in Example 1 in the same manner as in Example 3 except that poly-N-isopropylacrylamide was not included. Obtained.

Table 1 shows the coating amount, moisture permeability, and water pressure resistance of the products obtained in Examples 1 to 3 and Comparative Examples 1 to 3.

[0030]

[Table 1]

As is apparent from Table 1, the products obtained in the examples have a rapid increase in moisture permeability when the temperature rises. Also, it can be seen that the water pressure resistance is the same as before.

[0032]

According to the present invention, it is possible to provide a cloth whose moisture permeability can be controlled by changing the temperature, and when the cloth is used for clothes or the like, it is more than the transition temperature of the thermoresponsive polymer. When the temperature is high, the water vapor transmission rate becomes large, and when the temperature is high, it does not become damp. On the other hand, when the temperature is lower than the transition temperature of the thermoresponsive polymer, the water vapor transmission rate becomes small and when the temperature is low The effect is that the humidity does not drop and it does not feel cold. Therefore, it is very useful because it can be applied to the sports field and the like which could not be used due to the problem of stuffiness.

[Brief description of drawings]

FIG. 1 is a diagram showing a relationship between temperature and particle diameter of a thermoresponsive polymer.

Claims (1)

[Claims] 1. A fiber structure coated with a synthetic polymer containing a thermoresponsive polymer, the coating amount of which is 1 g / m ^2.
A fabric whose moisture vapor transmission rate is controlled by the temperature, which is characterized by being -200 g / m ² .