JPH0157189B2 - - Google Patents

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is applicable to sportswear, casual wear,
This field relates to the production of fabrics with excellent waterproofness, moisture permeability, heat retention, flexibility, and mechanical properties that are suitable for uses such as rain gear and blankets.

<Prior Art> Many methods for manufacturing waterproof fabrics have been proposed.

The first method is to attach a water-repellent resin porous membrane such as polytetrafluoroethylene to a fabric, and the waterproof property obtained by this method,
Moisture-permeable fabrics certainly have excellent waterproofness and moisture permeability, but they have the drawbacks of being somewhat rough and hard in texture and lacking in stretchability. In addition, adhesion is difficult with this method, and it is difficult to say that the adhesive strength between the membrane and the fabric is sufficient (Unexamined Japanese Patent Publication No.
46-7284 or Japanese Patent Application Laid-open No. 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 to apply the polyurethane solution on a release film. After that, there is a method in which a porous film formed by immersing the fabric in water is laminated to the fabric and then treated to make it water repellent. Although the moisture permeable waterproof fabrics obtained by these methods have excellent moisture permeability, it is difficult to control the diameter of the micropores. Therefore, there are disadvantages in that the waterproof property tends to vary, and since it is a porous urethane film, the abrasion resistance is low. Moreover, since it is a wet method, equipment costs are high and solvent recovery is required (Japanese Patent Application Laid-Open No. 56-26076, JP-A No. 57-205586).

In order to overcome the above-mentioned drawbacks, various methods have been proposed as a third method, such as forming a moisture-permeable polyurethane film using a dry method and then bonding it to the fabric, or directly coating it on the fabric. Showa 59
(Japanese Patent Laid-Open No. 53786, Japanese Patent Application Laid-Open No. 59-76973), the non-porous film is formed on the fabric, so it has poor moisture permeability. If you try to improve moisture permeability, the waterproofness and adhesion to the base fabric will deteriorate, but the technology that satisfies all the characteristics such as moisture permeability, waterproofness, flexibility, and adhesion to the base fabric has not yet been completed. It has not been. In addition, even higher moisture retention properties are often required for applications such as shillaf.

<Object of the invention> The present invention solves the above-mentioned drawbacks, has suitable drapability and flexibility, satisfies the functional aspects of moisture retention, moisture permeability, and waterproofness, and also has good adhesion to fabrics and abrasion of the film. The object of the present invention is to provide a dry method for manufacturing clothing fabrics that also have mechanical properties such as strength.

<Structure of the present invention> That is, the present invention provides: (1) A method for producing a moisture-permeable waterproof fabric in which a fabric is coated with a resin mainly composed of a polyurethane polymer, in which the fabric is coated with a two-component polyether polyol-modified polyurethane resin; A heat-retaining transparent material characterized by coating a resin composition (A) consisting of a melamine derivative, an organic polyosocyanate, and a crosslinking catalyst with a resin composition (B) in which fine metal powder with a radioactivity value of 0.3 or less is added. Method for producing wet waterproof fabric.

(2) After forming the resin composition (B) into a thin film and then subjecting it to crosslinking treatment, the resin composition (A) is further applied to the crosslinked thin film.
2. The method for producing a heat-retaining, moisture-permeable, waterproof fabric according to claim 1, which comprises coating the fabric with the resin composition (A) and laminating the fabric through the resin composition (A).

(3) The method for producing a heat-retaining, moisture-permeable, waterproof fabric according to claim 1, which comprises applying the resin composition (B) to a high-density fabric and then heating and drying it.

The fiber material used for the fabric here may be any of polyester, polyamide, polyolefin, polyurethane, etc., but polyester fibers are particularly preferred. The fabric can be made of woven or knitted fabric, non-woven fabric, or a combination of these, but the fabric should be a high-density fabric using fine denier yarn of 2 deniers or less because it has good moisture retention, moisture permeability, This is preferable in terms of waterproofness and the like.

Resin composition based on polyurethane polymer (A)
The metal-based fine powder to be mixed with is one with a radioactivity value (value listed in Section 20 of the Chemical Engineering Handbook (revised 4th edition) edited by the Japan Society of Chemical Engineers) of 0.3 or less. If it exceeds 0.3, the absorption and radiation of heat rays will increase and the heat shielding effect will decrease. If the radioactivity is 0.3 or less, the radioactivity of the heat rays is low, so absorption and radiation of heat by the heat rays is difficult to occur, and the heat shielding properties are improved.

The metal-based fine powder may be any metal-based substance with a radioactivity of 0.3 or less, but aluminum, copper, nickel, brass, iron, titanium, and their oxides are used because they are easily available and easy to handle. One or more types of metal-based fine powder selected from the group consisting of:

In addition, aluminum is particularly preferable from the viewpoint of lightness. The metal-based fine powder may be a metal fine powder, a metal compound fine powder, or a mixture of both. The shape of the metal-based fine powder may be any shape, but from the viewpoint of the heat ray shielding effect, non-spherical shapes such as linear, rod-like, and flaky shapes are preferable, and shapes such as long flakes, scales, and cloud-like shapes are more preferable. is particularly preferred.

The two-component polyether polyol-modified polyurethane resin herein refers to (a) polyoxyalkylene glycol with an average molecular weight of 500 to 5,000, such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, glycerin, or ethylene oxide or propylene oxide of trimethylolpropane; 5 to 60 parts by weight, preferably 10 to 40 parts by weight, of polyoxyalkylene glycols such as adducts, or mixtures or copolymers thereof, and (b) polyesters with an average molecular weight of 500 to 5,000, such as succinic acid, adipic acid, and sebacic acid. , polyesters produced by polycondensation of organic polybasic acids such as maleic acid and terephthalic acid with organic polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, diethylene glycol, and glycerin, and lactonic acid. 95 to 40 parts by weight, preferably 90 to 60 parts by weight of a polyester or a mixture or copolymer thereof produced by ring-opening polymerization, and (c) an organic polyisocyanate such as diphenylmethane-4,4'-diisocyanate, tolylene diurethane. It refers to a polyurethane resin obtained by reacting 5 to 25 parts by weight of an isocyanate such as isocyanate, naphthalene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, or a mixture thereof.

If the amount of polyoxyalkylene glycol is less than 5 parts by weight, the moisture permeability will be poor, and if it is more than 60 parts by weight, the adhesion to the fabric will be low and the polyurethane film will become wet when wet with water.

If the amount of organic polyisocyanate is less than 5 parts by weight, the mechanical properties of the polyurethane film will be insufficient,
If the amount is more than 20 parts by weight, the polyurethane film becomes rough and hard and its adhesive strength with the fabric decreases.

Melamine derivatives are compounds represented by the following general formula.

However, in the formula, R ₁ to R ₆ are -H, -CH ₂ OH, -
CH ₂ OCnH _2o+1 (where n is an integer from 1 to 16), -
It is a group selected from the group consisting of CH ₂ CH ₂ OH, -CONH ₂ and -CONHCH ₂ OH. In addition, 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 to be used is preferably 2% by weight or more, preferably 5 to 20% by weight, based on the two-component 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 texture of the film will be rough and hard.

Examples of the organic polyisocyanate compound as a two-component polyurethane crosslinking agent include hexamethylene diisocyanate, o-, m- or p-
Phenyl diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate with hydrogenated aromatic ring, diphenylmethane-4,4'-
Diisocyanate, 3,3'-dimethyl-4,4'-
Examples include biphenylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, ω,ω'-diisocyanate-4,4-dimethylbenzene, and ω,ω'-diisocyanate-1,3-dimethylbenzene. These can be used alone or in combination. The amount of organic polyisocyanate used is preferably 3 to 20 parts by weight per 100 parts by weight of the two-component polyether polyol-modified polyurethane resin and melamine derivative.

The crosslinking catalyst consists of a melamine crosslinking catalyst and a urethane crosslinking catalyst, and an acidic catalyst is used as the melamine crosslinking catalyst. For example, aliphatic carboxylic acids such as formic acid and 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 their ammonium salts, organic amine salts, sulfonic acids and their ammonium salts such as dodecylbenzenesulfonic acid and p-toluenesulfonic acid, inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, Examples include ammonium salts thereof. These catalysts are preferably used in an amount of 0.1 to 20% by weight based on the melamine derivative.

As the urethane crosslinking agent, for example, organometallic compounds such as dibutyltin dilaurate, triethylenediamine, and stannath octoate, and tertiary amines such as N-methylmorpholine are used. The amount used is 0.1 to 10% by weight based on the organic polyisocyanate.
It is preferable to use the range of .

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

A resin composition (A) consisting of a two-component polyether polyol-modified polyurethane resin, a melamine derivative, an organic polyisocyanate, a crosslinking catalyst, and a metal fine powder added to the resin composition (A) as a skin layer on polypropylene coated paper or silicone coated paper. Apply the organic solvent solution of B) using a conventional coating machine such as a knife coater, comma coater, kiss roll coater, etc. to a solid content of 3 to 20 g/ ^m2 , and dry it at 120 to 160℃. Dry and crosslink at a temperature range to obtain a crosslinked film of the resin composition (B) containing fine metal powder. Next, on the crosslinked film of (B) formed on the release paper, an adhesive layer is further formed by applying the organic solvent solution of (A) as a solid content of 5 to 25 g/m ² using a coating machine.
The organic solvent is semi-dry or completely dried in a dryer at a temperature range of 60 to 100°C.
Next, the crosslinked film (B) and the base fabric are laminated together at a temperature of 100 to 130.
℃ and a pressure of 3 to 30 kg/cm ² using a hot roll. Then, the release paper is peeled off, and the resulting fabric is impregnated with a water repellent solution, preferably silicone-based or fluorine-based, and then dried to obtain a moisture-permeable waterproof fabric.

In addition, when using a high-density fabric without any traces of polyurethane resin as the base fabric, an organic solvent solution of the resin composition (B) is directly applied to the high-density fabric using a normal coating machine, and the solid content is 3 to 40 g/ ^m2. The fabric is coated and cross-linked by drying in a dryer at a temperature range of 120 to 160℃, and the resulting fabric is impregnated with a silicone-based or fluorine-based water repellent solution and dried to create a moisture-permeable waterproof fabric. You can also use it.

<Effects of the Invention> The heat-retaining, moisture-permeable, waterproof fabric obtained by this method is excellent in heat retention, flexibility, moisture permeability, and waterproofness, and has excellent mechanical properties such as adhesion to the base fabric and polyurethane film strength. This material is suitable for applications that require various functions such as heat retention, moisture permeability, and waterproofness, such as sportswear and rain gear.

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

In the Examples, the values of moisture permeability, water resistance, film abrasion resistance, and peeling strength between the film and the base fabric were determined as follows.

Moisture permeability (g/m ² /24hr) Water pressure resistance (mmH ₂ O) according to the method of JIS K-6328 Water repellency point (point) according to the method of JIS L-1092 Peel strength (g/cm according to the method of JIS L-1092) ) Membrane rubbing resistance according to JIS K-6328 method Using a Gakushin type friction fastness tester, overlap the polyurethane surfaces and rub together 100 times under a load of 500g. 5 if the polyurethane surface is completely undamaged.
Grade: 4 for cases where the polyurethane surface is slightly damaged.
Grade: 3 when the polyurethane surface is damaged by about 1/3
Grade 1 is indicated when the polyurethane surface is completely peeled off.

Note that parts and % in the examples represent parts by weight and % by weight, respectively.

Example 1 20 parts by weight of polyethylene glycol with an average molecular weight of 1500, 80 parts by weight of polybutylene adipate diol with an average molecular weight of 2000, and 15 parts by weight of tolylene diisocyanate were mixed with 173 parts by weight of a mixed solvent of 105 parts by weight of toluene and 68 parts by weight of dimethylformamide. A two-component polyether polyol-modified polyurethane resin solution with a resin concentration of 40% by weight was obtained.

To this solution was added 10 parts by weight of trimethylolmelamine (87% by weight based on the two-component polyether polyol-modified polyurethane resin), 15 parts by weight of hexamethylene diisocyanate, 0.5 parts by weight of p-toluenesulfonic acid, and dibutyltin dilaurate.
0.5 part by weight was added to obtain a two-component polyether polyol-modified polyurethane resin. The resin composition (A)
Aluminum Paste No.6170 (Toyo Aluminum Co., Ltd.)
6 parts by weight was added to obtain a resin composition (B). The obtained resin composition (B) was coated on a silicone coated release paper using a comma coater so that the solid content was 11 g/m ² , and was heated at 130° C. for 5 minutes to perform a dry crosslinking treatment. Next, on the crosslinked film of the resin composition (B) formed as a skin layer on the silicone coated paper, the resin composition (A) was coated as an adhesive layer using a comma coater so that the solid content was 15 g/m ² . The resin layer was heated at 60°C for 45 seconds to obtain a semi-dry resin layer with release paper. On the other hand, a plain woven fabric using polyethylene terephthalate woolly processed yarn (100 denier/48 filaments) for the warp and weft was refined by a conventional method, and then a red disperse dye (CI
After dyeing with No. Disperse Red 73), a fluorine-based water repellent, Asahi Guard AG710 (Meisei Chemical
Water-repellent treatment was carried out by impregnation using a 5% aqueous solution (manufactured by Co., Ltd.). The resulting water-repellent processed yarn fabric (weighing 103
g/m ² ) and the above-mentioned resin layer with release paper were pasted together through a heating roll at 120° C., and after aging for 2 days, the release paper was peeled off. The obtained laminate fabric was flexible, moisture permeable, waterproof, and had excellent heat retention properties.

The main characteristic values are as follows.

Water pressure resistance 2000mm or more Water repellency 100-90 points Moisture permeability 3000g/m ² /24hr Heat ray reflection ratio 53.8% Peel strength 900g/cm Membrane handling resistance Grade 5

Claims (1)

[Scope of Claims] 1. A method for producing a moisture-permeable waterproof fabric in which a fabric is coated with a resin mainly composed of a polyurethane polymer, in which the fabric is coated with a two-component polyether polyol-modified polyurethane resin, a melamine derivative, and an organic polyisocyanate. A method for producing a heat-retaining, moisture-permeable, waterproof fabric, which comprises coating a resin composition (A) comprising a cross-linked catalyst with a resin composition (B) in which fine metal powder having a radioactivity value of 0.3 or less is added. 2 The resin composition (B) is made into a thin film, then crosslinked, the crosslinked thin film is further coated with the resin composition (A), and a fabric is laminated via the resin composition (A). A method for producing a heat-retaining, moisture-permeable, waterproof fabric according to claim 1. 3. The method for producing a heat-retaining, moisture-permeable, waterproof fabric according to claim 1, which comprises applying the resin composition (B) to a high-density fabric and then heating and drying it.