JPH0121270B2 - - Google Patents

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is applicable to sportswear, casual wear,
This invention relates to a method for manufacturing fabrics with excellent waterproofness, moisture permeability, flexibility, and mechanical properties suitable for use in rain gear, snowflakes, etc.

<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 do have excellent waterproofness and moisture permeability, but they have the drawbacks of having a somewhat rough texture and poor elasticity. Furthermore, in this method, adhesion is difficult and the adhesive force between the membrane and the fabric is not said to be sufficient (Japanese Unexamined Patent Publication No. 46-7284 or 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.
Alternatively, there is a method in which a polyurethane solution is applied on a release film, and then a porous film is formed by immersing the film in water, and then a porous film is bonded to a 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. In addition, since it is a wet method, equipment costs are high and solvent recovery is necessary (Japanese Patent Application Laid-Open No. 56-26076, JP-A No. 57-205586).
Publication No.).

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.

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

<Structure of the present invention> That is, the present invention provides the following features: (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, melamine. Resin composition (A) consisting of a derivative, an organic polyisocyanate, and a crosslinking catalyst
1. A method for producing a moisture-permeable waterproof fabric, the fabric comprising:

(2) The resin composition (A) is formed into a thin film, and 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 moisture-permeable waterproof fabric according to claim 1.

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

It is.

The two-component polyether polyol-modified polyurethane resin herein refers to (a) polyoxyalkylene glycol with an average molecular weight of 500 to 3,000, such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, glycerin, or ethylene oxide or propylene oxide of trimethylolpropane; 5 to 60 parts by weight of polyoxyalkylene glycols such as adducts, or mixtures or copolymers thereof, preferably 10 to 40 parts by weight, and (b) polyesters with an average molecular weight of 500 to 5,000, such as succinic acid, adipic acid, 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 polymerization; and (c)
Organic polyisocyanates such as diphenylmethane-4,4'-diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate,
It refers to a polyurethane resin obtained by reacting 5 to 25 parts by weight of isocyanates such as isophorone diisocyanate and hexamethylene diisocyanate, or mixtures 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-
-phenylene 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,
Examples include 4'-biphenylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, ωω'-diisocyanate-4,4-dimethylbenzene, and ωω'-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 catalyst, for example, organic metal compounds such as dibutyltin dilaurate and stannath octoate, and organic amines such as triethylenediamine and N-methylmorpholine are used. The amount used is preferably 0.1 to 10% by weight based on the organic polyisocyanate.

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

A resin composition consisting of a two-component polyether polyol-modified polyurethane resin, a melamine derivative, an organic polyisocyanate, and a crosslinking catalyst as a skin layer on polypropylene coated paper or silicone coated paper.
Apply the organic solvent solution of (A) 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 in temperature range,
A crosslinked film of crosslinked material (A) is obtained. Next, on the crosslinked film (A) formed on the release paper, an organic solvent solution of (A) is further applied as an adhesive layer using a coating machine to a solid content of 5 to 25 g/m ² , and then dried in a dryer. in
Semi-dry or completely dry the organic solvent at a temperature range of 60-100°C. Next, the crosslinked film (A) and the base fabric are laminated together and thermocompressed using a hot roll at a temperature of 100 to 130°C and a pressure of 3 to 30 kg/cm ² . Then peel off the release paper,
The obtained 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 polyurethane resin as the base fabric, a solution of the resin composition (A) in an organic solvent is directly applied to the high-density fabric using an ordinary coating machine, and the solid content is 3 to 40 g/m2. ² , and dried and cross-linked in a dryer at a temperature range of 120 to 160°C. The resulting fabric is impregnated with a silicone-based or fluorine-based water repellent solution, and then dried to create a moisture-permeable waterproof fabric. get it.

<Effects of the invention> The moisture-permeable waterproof fabric obtained by this method is highly flexible, has both moisture permeability and waterproofness, and has excellent adhesion to the base fabric.
It also has excellent mechanical properties such as polyurethane film strength, making it a suitable material for applications that require both 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 (points) according to the method of JIS-L-1092 Peel strength (g/m 2 /24hr) according to the method of JIS-L-1092 cm) Membrane rubbing resistance according to the method of JIS K-6328 Using a Gakushin type friction fastness tester, overlap the polyurethane surfaces and rub together 100 times under a load of 500 g. Class 5 is when the polyurethane surface is completely undamaged, Class 4 is when the polyurethane surface is only partially damaged, Class 3 is when the polyurethane surface is damaged by about 1/3, and Class 1 is when the polyurethane surface is completely peeled off. is displayed.

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

Example 1 Polyethylene glycol 20 with an average molecular weight of 1500
part, 80 parts of polybutylene adipate diol with an average molecular weight of 2000 and 15 parts of tolylene diisocyanate in a mixed solvent of toluene and dimethylformamide.
A two-component polyether polyol-modified polyurethane resin solution with a resin concentration of 40% was obtained by reacting in 173 parts. Add 10 parts of trimethylolmelamine (2 parts) to this solution.
(8.7% based on liquid type polyether polyol modified polyurethane resin), and further added 15 parts of hexamethylene diisocyanate and p-toluenesulfonic acid.
Add 0.5 parts and 0.5 parts of dibutyltin dilaurate,
Liquid polyether polyol modified polyurethane resin, melamine derivative, organic polyisocyanate,
A solution (A-1) of a resin composition comprising a crosslinking catalyst was obtained. Solution A-1 was coated onto silicone-coated release paper using a comma coater so that the solid content was 10 g/m ² and heated at 130° C. for 5 minutes to effect drying and crosslinking at the same time. Solution A-1 was further coated as an adhesive layer on the crosslinked film of A-1 formed as a skin layer on silicon coated paper using a comma coater so that the solid content was 13 g/m ² and heated at 60°C. It was heated for 45 seconds and semi-dried to obtain a crosslinked film A'-1.
On the other hand, a polyethylene terephthalate knitted fabric obtained by knitting at 36 gauge using polyethylene terephthalate filament yarn (50 denier/36 filament) and performing scouring and dyeing treatment by a conventional method and the crosslinked film A'-1 were heated to 120°C. They were laminated through heated thermal rolls, aged for 2 days, and then the release paper was peeled off. The fabric made by laminating the thus obtained polyurethane resin and polyester knitted fabric is treated with a fluorine-based water repellent.
It was impregnated with a 3% aqueous solution of AG730 (manufactured by Meisei Kagaku Co., Ltd.), squeezed with a mangle, and then dried at 120°C for 5 minutes to obtain a moisture-permeable waterproof fabric. The obtained fabric was extremely flexible and stretchable, and its characteristic values were as follows.

Moisture permeability (g/m ² /24hr) 3700 Water pressure resistance (mmH ₂ O) >2000 Water repellency (points) 90 Peel strength (g/cm) 750 Membrane rubbing resistance (grade) 5 Example 2 Both warp and weft 70 Resin composition A-1 obtained in Example 1 was applied to nylon taffeta (high-density fabric) woven using denier 36 filaments at a warp density of 120 threads/inch and a weft density of 90 threads/inch at a solid content of 15 g/m ^{2 .} Coat it so that it looks like this, heat dry it at 80℃ for 1 minute,
Crosslinking was achieved by heating at 130°C for 3 minutes. The fabric was then impregnated with a 3% aqueous solution of a fluorine-based water repellent, squeezed with a mangle, and dried at 150°C for 2 minutes to obtain a moisture-permeable waterproof fabric. The obtained fabric was extremely flexible and had the following characteristic values.

Moisture permeability (g/m ² /24hr) 4500 Water pressure resistance (mmH ₂ O) 1500 Water repellency (points) 100 Peel strength (g/cm) Non-peelable film resistance to rubbing (grade) 5 Comparative example 1 In Example 1, trimethylol melamine 10
The fabric obtained in the same manner as in Example 1 except that a resin composition containing no 0.5 parts of p-toluenesulfonic acid was used was a fabric with high flexibility and stretchability, but the characteristic values were as follows. It was hot.

Moisture permeability (g/m ² /24hr) 1800 Water pressure resistance (mmH ₂ O) >2000 Water repellency (points) 90 Peel strength (g/cm) 250 Membrane abrasion resistance (grade) 1 Comparative example 2 Average in Example 1 The fabric obtained in the same manner as in Example 1 except that 100 parts of polybutylene adipate diol with an average molecular weight of 2000 was used instead of 20 parts of polyethylene glycol with a molecular weight of 1500 had flexibility,
The fabric was highly stretchable, and its characteristic values were as follows.

Moisture permeability (g/m ² /24hr) 600 Water pressure resistance (mmH ₂ O) >2000 Water repellency (points) 100 Peel strength (g/cm) 480 Membrane abrasion resistance (grade) 4 Example 3 Polypropylene with an average molecular weight of 2000 glycol 50
50 parts of polyethylene adipate diol with an average molecular weight of 1000 and 10 parts of 4,4'-diphenylmethane diisocyanate were reacted in 130 parts of a mixed solvent of toluene and dimethylformamide to give a resin concentration of 46%.
A two-component polyether polyol-modified polyurethane resin solution was obtained. Add 20 parts of trimethylolmelamine to this solution, further add 10 parts of hexamethylene diisocyanate, 0.5 part of p-toluenesulfonic acid,
0.5 part of dibutyltin dilaurate was added to obtain a solution (A-2) of a two-part resin composition comprising a polyether polyol-modified polyurethane resin, a melamine derivative, an organic polyisocyanate, and a crosslinking catalyst. Next, a moisture-permeable waterproof fabric was obtained in the same manner as in Example 1, except that resin composition A-2 was used instead of resin composition A-1.
The resulting fabric had a tendency for the polyurethane resin layer to swell slightly in water, but was a fabric with excellent flexibility and lateral stretchability, and its characteristic values were as follows.

Moisture permeability (g/m ²・24hr) 4800 Water pressure resistance (mmH ₂ O) 1700 Water repellency (points) 90 Peel strength (g/cm) 450 Membrane abrasion resistance (grade) 3 Comparative example 3 Trimethylol in Example 3 melamine 20
In a fabric obtained in the same manner as in Example 3 except for using a resin composition to which 0.5 parts of p-toluenesulfonic acid was not added, the polyurethane resin layer had a tendency to swell considerably in water. Its characteristic values were as follows.

Moisture permeability (g/m ²・24hr) 2700 Water pressure resistance (mmH ₂ O) 1100 Peel strength (g/cm) 250 Membrane abrasion resistance (grade) 1

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, wherein the fabric is coated with a two-component polyether polyol-modified polyurethane, a melamine derivative, an organic polyisocyanate, and a crosslinked polyurethane. 1. A method for producing a moisture-permeable waterproof fabric, comprising coating it with a resin composition (A) comprising a catalyst. 2 The resin composition (A) is made into a thin film, then subjected to crosslinking treatment, 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 moisture-permeable waterproof fabric according to claim 1. 3. The method for producing a moisture-permeable waterproof fabric according to claim 1, which comprises applying the resin composition (A) to a high-density fabric and then heating and drying it.