JPH0696825B2 - Method for producing heat-retaining, moisture-permeable waterproof cloth - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention is a fabric excellent in waterproofness, moisture permeability, heat retention, flexibility and mechanical properties, which is suitable for applications such as sportswear, casual wear, rainwear, and shruffs. Related to the manufacture of.

<Prior Art> Many methods of manufacturing waterproof fabric have been proposed.

The first method is a method in which a resin porous membrane having water repellency such as polytetrafluoroethylene is attached to a cloth, and the waterproof and moisture-permeable cloth obtained by this method is surely excellent in waterproofness and moisture permeability. However, the texture is a little rough,
It has the drawback of poor stretchability. Further, in this method, the adhesion is difficult, and it is difficult to say that the adhesive force between the film and the cloth is sufficient (JP-A-46-7284 or JP-A-50-2281).
The second method is to apply the polyurethane solution directly to the fabric and then immerse the coated fabric in water to extract the solvent and form a porous film, or apply the polyurethane solution onto the release film. Then, there is a method in which a porous film formed by immersing in water is applied to a cloth and then processed to be water repellent. The moisture-permeable waterproof fabric obtained by these methods has excellent moisture permeability, but it is difficult to control the diameter of the fine pores. Therefore, there are drawbacks that the waterproof property is likely to vary and the abrasion resistance is low because of the porous urethane film. Further, since it is a wet method, the equipment cost is high and solvent recovery is required (JP-A-56-26076 and JP-A-57-205586).

In order to solve the above-mentioned drawbacks, various methods have been proposed as a third method, such as a method of forming a moisture-permeable polyurethane film by a dry method and then laminating it with a cloth, or a method of directly applying the cloth to the cloth (JP JP 59-53786, JP 59-7
No. 6973), a non-porous film is formed on a fabric, so that it has poor moisture permeability. A technique that satisfies all the characteristics such as moisture permeability, waterproofness, flexibility and adhesiveness to the base fabric is completed, such as waterproofness and adhesion to the base fabric deteriorates when trying to improve the moisture permeability. It has not been. In addition, a higher degree of heat retention is often required in applications such as shruff.

<Purpose of the invention> The present invention solves the above-mentioned drawbacks, has suitable drapeability and flexibility, and satisfies the functional aspects of heat retention, moisture permeability, and waterproofness, and further has adhesiveness with a cloth and abrasion of a film. It is an object of the present invention to provide a method for producing a cloth for clothing which also has mechanical properties such as strength by a dry method.

<Structure of the present invention> That is, the present invention is a method for producing a moisture-permeable waterproof fabric comprising a cloth coated with a resin mainly composed of a polyurethane polymer, wherein the one-part moisture-permeable polyurethane resin has a radiation ability value of 0.3 or less. The resin composition to which the metal-based fine powder is added is made into a thin film, and then the thin film is coated with a resin composition (A) consisting of a two-component polyether polyol-modified polyurethane resin, a melamine derivative, an organic polyosocyanate, and a crosslinking catalyst. A method for producing a heat-retaining, moisture-permeable and waterproof fabric, which comprises laminating a fabric via the composition (A).

As the fiber material used for the cloth, any of polyester-based, polyamide-based, polyolefin-based, polyurethane-based, etc. may be used, but polyester-based fibers are particularly preferable. The state of the cloth may be woven or knitted, sloppy cloth, or a combination thereof, but the cloth should be a high density cloth using fine denier of 2 denier or less, which is heat retention and moisture permeability. It is preferable in terms of waterproofness.

The metal-based fine powder to be mixed with the one-pack type moisture-permeable polyurethane resin has a radiation value (value described in the Chemical Engineering Handbook (Chemical Engineering Handbook, 4th revised edition), item 20) of 0.3 or less. If it exceeds 0.3, the absorption and radiation of heat rays increase and the heat shielding effect decreases. If the emissivity is 0.3 or less, the emissivity of the heat rays is low, so that the heat rays are less likely to absorb and radiate the heat and the heat shielding property is enhanced.

The metal-based fine powder may be any metal-based substance having a radioactivity of 0.3 or less, but it is easy to obtain and easy to handle, and therefore aluminum, copper, nickel, brass, iron, titanium and oxides thereof are used. It is desirable to use one or more kinds of fine metal powders selected from the group consisting of

From the viewpoint of lightness, aluminum is particularly preferable. The metal-based fine powder may be a metal powder, a metal compound fine powder, or a mixture of both. The shape of the metal-based fine powder may be any shape, but in view of the heat ray shielding effect, an aspherical shape, for example, a linear shape, a rod shape, a flaky shape or the like is preferable, and more preferably a long piece shape, a scale shape, a cloud shape, or the like. Is particularly preferable.

Here, as the one-pack type moisture-permeable polyurethane resin, a urethane prepolymer obtained by reacting a polyester polyol or polyether polyol containing a polyoxyalkylene glycol unit with a polyvalent isocyanate and a polyfunctional chain extender having active hydrogen, for example, a polyvalent Polyurethane obtained by reacting an amine or a polyhydric alcohol can be used.

The two-pack type polyether polyol-modified polyurethane resin means (a) polyoxyalkylene glycol having an average molecular weight of 500 to 5000, such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol,
5 to 60 parts by weight, preferably 10 to 40 parts by weight of polyoxyalkylene glycol such as ethylene oxide or propylene oxide adduct of glycerin or trimethylolpropane, or a mixture or copolymer thereof.
(B) Polyester having an average molecular weight of 500 to 5000, such as organic polybasic acids such as succinic acid, adipic acid, sebacic acid, maleic acid, and terephthalic acid, and ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, diethylene glycol, glycerin, etc. Polyester produced by polycondensation with an organic polyhydric alcohol, polyester produced by ring-opening polymerization of lactone acid, or a mixture thereof or a copolymer 95 to 40
Parts by weight, preferably 90 to 60 parts by weight, and (c) organic polyisocyanates such as diphenylmethane-4,4'-diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, dicyclohexylmethane-4,4-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, etc. Polyurethane resin obtained by reacting 5 to 25 parts by weight of the above isocyanate or a mixture thereof.

When the amount of polyoxyalkylene glycol is less than 5 parts by weight, the moisture permeability is poor, and when it is more than 60 parts by weight, the adhesive strength to the fabric is low and when it is wet with water, the polyurethane film becomes wet.

If the amount of organic polyisocyanate is less than 5 parts by weight, the mechanical properties of the polyurethane film will be insufficient, and if it is more than 20 parts by weight, the polyurethane film will be coarse and hard and the adhesive strength to the fabric will be reduced.

The melamine derivative is a compound represented by the following general formula.

However, in the formula, R _{1 to} R ₆ are -H, -CH ₂ OH, -CH ₂ OCnH.
_{2 n + 1} (where n is 1 to 16 _{integer), - CH 2 CH 2 OH} , -CO
It is a group selected from the group consisting of NH ₂ and —CONHCH ₂ OH. It includes an initial condensate of the compound represented by the above general formula or an acid colloid compound. The amount of these melamine derivatives used is preferably 2% by weight or more, and more preferably 5 to 20% by weight, based on the two-pack type polyether polyol-modified polyurethane resin. If it is less than 2% by weight, the adhesive strength will be insufficient, and if it exceeds 20% by weight, the feel of the film will be rough.

Examples of the organic polyisocyanate compound as the two-component polyurethane crosslinking agent include hexamethylene diisocyanate, o-, m- or p-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, and aromatic ring having hydrogen. Added 2,4- or 2,6-tolylene diisocyanate, diphenylmethane-4,4-diisocyanate, 3,3'-dimethyl-4,4-biphenylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate , Ω, ω ′
-Diisocyanate-4,4-dimethylbenzene, ω,
ω'-diisocyanate-1,3-dimethylbenzene and the like can be mentioned, and these can be used alone or in combination. The amount of organic polyisocyanate used is 2
It is preferable to use 3 to 20 parts by weight based on 100 parts by weight of the liquid polyether polyol-modified polyurethane resin and the melamine derivative.

The crosslinking catalyst comprises a melamine crosslinking catalyst and a urethane crosslinking catalyst, and an acid catalyst is used as the melamine crosslinking catalyst. For example, formic acid, aliphatic carboxylic acids such as acetic acid, olefin carboxylic acids such as acrylic acid, saturated dicarboxylic acids such as oxalic acid and succinic acid, oxycarboxylic acids such as malic acid and tartaric acid, aromatic dicarboxylic acids such as phthalic acid and the like. Ammonium salts, organic amine salts, sulfonic acids such as dodecylbenzenesulfonic acid, p-toluenesulfonic acid and their ammonium salts, sulfuric acid, hydrochloric acid, phosphoric acid,
Mention may be made of inorganic acids such as nitric acid and their ammonium salts. These catalysts are preferably used in the range of 0.1 to 20% by weight based on the melamine derivative.

As the urethane cross-linking agent, for example, an organic metal compound such as dibutyltin dilaurate, triethylenediamine, stannas octoate, and a tertiary amine such as N-methylmorpholine are used. The amount used is preferably in the range of 0.1 to 10% by weight based on the organic polyisocyanate.

Next, a method for producing the heat retaining / moisture permeable waterproof fabric will be described below.

Using an ordinary coating machine such as knife coater, comma coater, kiss roll coater, an organic solvent solution obtained by adding metal fine powder to a commercially available moisture-permeable 1-liquid type polyurethane as a skin layer on polypropylene-coated paper or silicon-coated paper. A solid moisture content of 3 to 20 g / m ² is applied and dried in a dryer at a temperature range of 70 to 120 ° C. to obtain a moisture permeable urethane film containing fine metal powder. Then, as an adhesive layer on the urethane film formed on the release paper
The organic solvent solution of (A) was used as a solid component in a coating machine and
It is applied at a rate of ~ 25 g / m ² and the organic solvent is semi-dried or completely dried in a temperature range of 60-100 ° C with a dryer. Next, it is laminated with the base cloth and thermocompression-bonded with a heat roll having a temperature of 100 to 130 ° C. and a pressure of 3 to 30 kg / cm ² . Then, the release paper is peeled off, and the obtained cloth is preferably impregnated with a silicon-based or fluorine-based water repellent solution and then dried to obtain a moisture-permeable waterproof cloth.

<Effects of the Invention> The heat-retaining and moisture-permeable waterproof fabric obtained by the above method has both heat-retaining property, flexibility, moisture-permeability and waterproof property, and also has excellent mechanical properties such as adhesiveness as a base fabric and film strength of polyurethane. It is a suitable material for sportswear, rainwear, and other applications that require various functions such as heat retention, moisture permeability, and waterproofness.

<Examples> The present invention will be specifically described below with reference to Examples.

In the examples, the moisture permeability, the water resistance, the film rubbing resistance, and the peel strength between the film and the base cloth are values determined as follows.

Moisture permeability (g / m ² / 24hr) According to the method of JIS K-6328 Water resistance (mmH ₂ O) According to the method of JIS L-1092 Water repellency (point) Peel strength (g / cm) according to the method of JIS L-1092 According to the method of JIS K-6328 Membrane Abrasion Resistance Using a dynamic vibration type friction fastness tester, overlay polyurethane surfaces and rub them 100 times with a load of 500g. Grade 5 if the polyurethane surface is not damaged at all, Grade 4 if the polyurethane surface is only partially damaged, Grade 3 if the polyurethane surface is damaged about 1/3, Grade 1 if the polyurethane surface is completely peeled off Is displayed.

The parts or% in the examples mean parts by weight or% by weight, respectively.

Example 1 One-part moisture-permeable polyurethane: Crisbon 3314 (manufactured by Dainippon Ink and Chemicals, Inc. 110 parts, aluminum paste 6170 (manufactured by Toyo Aluminum Co., Ltd.), 6 parts, yellow pigment Zxyelllow230 (manufactured by Mikuni pigment) A polyurethane solution prepared by mixing 8 parts was coated on polypropylene-coated paper using a comma coater so that the solid content would be 8 g / m ^2, and dried by heating at 100 ° C. for 2 minutes to form a skin layer.

Next, 20 parts by weight of polyethylene glycol having an average molecular weight of 1500 and polybutylene adipate diol having an average molecular weight of 2000.
80 parts by weight and 15 parts by weight of tolylene diisocyanate were reacted in 173 parts by weight of a mixed solvent of 105 parts by weight of toluene and 68 parts by weight of dimethylformamide to prepare a two-component polyether polyol-modified polyurethane resin solution having a resin concentration of 40% by weight. Obtained.

To this solution was added 10 parts by weight of trimethylolmelamine (80% by weight based on the two-component polyether polyol-modified polyurethane resin), and then hexamethylene diisocyanate was added.
15 parts by weight, p-toluenesulfonic acid 0.5 parts by weight, and dibutyltin dilaurate 0.5 parts by weight were added to obtain a two-pack type polyether polyol-modified polyurethane resin. The resin composition (A) was used as an adhesive and the adhesive solid content was 1
It was coated so as to be 8 g / m ² and dried at 60 ° C. for 30 seconds to obtain a resin thin film.

Next, a plain woven fabric using polyethylene terephthalate filament yarn (75 denier / 72 filaments) for the warp and weft is scoured and dyed by a conventional method with a disperse dye (CI No. Disperse Blue 139), and then a water repellent and Asahi Guard. A
A 5% aqueous solution of G710 (manufactured by Meisei Chemical Co., Ltd.) was used for water repellent finishing treatment by the impregnation method, and then calendering and cam fitting treatment. The obtained blue water-repellent plain weave (warp density 116 yarns /
2.54 cm, weft density 94 threads / 2.54 cm) and the resin thin film 120
The release paper was peeled off after being pasted through a heating roll at ℃ for 2 days. The obtained gold-colored laminated woven fabric was flexible, had excellent moisture permeability, waterproofness, and heat retention, and had a vivid color and rich fashionability. The main characteristic values were as follows.

Water pressure resistance 2000mm or more Water repellent 90 points Moisture permeability 3000g / m ² / 24hr Heat ray reflection skin rate 37% Peel strength 700g / cm Membrane operation resistance Grade 5

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Claims (1)

[Claims] 1. A method for producing a moisture-permeable waterproof fabric comprising a cloth mainly coated with a resin comprising a polyurethane polymer, wherein a one-component moisture-permeable polyurethane resin is mixed with a fine metal powder having a radiation value of 0.3 or less. The added resin composition is made into a thin film, and then the thin film is coated with a resin composition (A) comprising a two-component polyether polyol-modified polyurethane resin, a melamine derivative, an organic polyisocyanate, and a crosslinking catalyst.
A method for producing a heat-retaining, moisture-permeable and waterproof fabric, which comprises laminating a fabric via