JPH01124687A - Production of humidity permeable waterproof fabric - Google Patents

Abstract

PURPOSE: To produce the subject fabric flexible and excellent in drape by forming a thin film of a single fluid type moisture-permeable polyurethane resin on a substrate and stick a fabric through a double fluid type resin composition comprising a specific modified polyurethane-melamine derivative, etc. CONSTITUTION: This production of moisture-permeable waterproof fabric comprises forming a thin film of a single fluid type moisture-permeable polyurethane resin on a substrate such as polypropylene-coated paper or the like, thereafter coating an organic solvent solution of a resin composition comprising a double fluid type polyether-polyol-modified polyurethane melamine derivative, an organic polyisocyanate (e.g. hexamethylene diisocyanate, etc.), and a cross- linking catalyst, sticking a fabric (e.g. one comprising polyester-based fiber woolly yarns) through the composition and treating the fabric with a water repellent to obtain the subject fabric excellent in adhesiveness to the fabric and abrasion resistance of the film.

Description

[Detailed description of the invention] <Industrial application field> The present invention is sportswear and casual wear.

Waterproof and breathable, suitable for use as rain gear, sleeping bags, etc.

This invention relates to a method for producing fabrics with excellent flexibility and mechanical properties.

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

The first method is to attach a porous resin membrane having 9 aqueous properties such as polytetrafluoroethylene to a fabric, and the waterproof property obtained by this method.

Moisture-permeable fabrics are certainly waterproof and breathable, but
It has the drawbacks of a somewhat rough and hard texture and poor elasticity. Furthermore, in this method, adhesion is difficult, and the adhesive force between the membrane and the fabric cannot be said to be 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 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 is a drawback 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 Laid-Open Nos. 56-26076 and 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. (Japanese Patent Application Laid-Open No. 59-53786, Japanese Patent Application Laid-Open No. 59-76973), the non-porous film is formed on the fabric, so it has poor moisture permeability. If an attempt is made to improve moisture permeability, waterproofness and adhesion to the base fabric will deteriorate. Therefore, a technology that satisfies all the characteristics such as moisture permeability, waterproofness, flexibility, and adhesion to the base fabric has not yet been completed.

<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 also has mechanical properties such as adhesion to fabric and abrasion strength of the film. The object of the present invention is to provide a method for manufacturing clothing fabrics using a dry method, which also has excellent properties.

Structure of the Invention In other words, the present invention provides 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 a one-component moisture-permeable polyurethane resin is formed into a thin film, and then the thin film is coated with a one-component moisture-permeable polyurethane resin. A transparent fabric characterized by coating a resin composition (A) consisting of a two-component polyether polyol-modified polyurethane, a melamine derivative, an organic polyisocyanate, and a crosslinking catalyst, and laminating a fabric through the resin composition (A). This is a method for producing a wet waterproof fabric.

The two-component polyether polyol-modified polyurethane resin herein refers to (a) 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 60 parts by weight
40 parts by weight and (b) a polyester having an average molecular weight of 500 to 5,000, such as succinic acid, adipic acid, sebacic acid,
Ring-opening polymerization of lactonic acid and polyester 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. 95 to 40 parts by weight, preferably 90 parts by weight of a polyester or a mixture or copolymer thereof produced by
~60 parts by weight and (c) an organic polyisocyanate such as diphenylmethane 4,4'-diisocyanate, tolylene diisocyanate, naphthalene diisocyanate,
Dicyclohexylmethane-4,4'-diisocyanate.

Isocyanates such as isophorone diisocyanate and hexamethylene diisocyanate, or mixtures thereof 5-
It refers to a polyurethane resin obtained by reacting with 25 parts by weight.

If the polyoxyalkylene glycol is less than 51 parts, the moisture permeability is poor, and if it is more than 60 parts, the adhesion to the fabric is low and the polyurethane film becomes wet when 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 25 parts by weight, the polyurethane film will become rough and hard and its adhesive strength with the fabric will decrease.

Melamine derivatives are compounds represented by the following general formula.

RI N-R2 Ma However, in the formula, R1 to R6 are -H, -〇　820　H.

-CH20Cn H2n + + (where n is 1 to
16 integer), -CH2CH20H, -CONH2.

-CONHGHZOH is a group selected from the group consisting of -CONHGHZOH. In addition, the initial condensate of the compound represented by the above general formula or an acid colloid compound is also included. The amount of these melamine derivatives used is preferably 2 to 20 weight percent, preferably 5 to 20 weight percent, 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, and hydrogenated aromatic rings. 2,4- or 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 3.3'
-dimethyl-4,4'-biphenylene diisocyanate, dicyclohexylmethane-4,41-diisocyanate, isophorone diisocyanate, ωω'-diisocyanate 4,4-dimethylbenzene, ωω'-diisocyanate 1,3-dimethylbenzene, etc. These can be used alone or in combination. The amount of organic polyisocyanate to be 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, olefinic carboxylic acids such as acrylic acid, saturated dicarboxylic acids such as oxalic acid and succinic acid, and 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 have a 0.
It is preferable to use it in a range of 1 to 20% by weight.

Examples of urethane crosslinking catalysts include organometallic compounds such as dibutyltin dilaurate and stannath octoate;
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.

One-component moisture permeable polyurethane resins include polyester polyols containing polyoxyalkylene glycol units, urethane prepolymers obtained by reacting polyether polyols with polyvalent isocyanates, and polyfunctional chain extenders containing active hydrogen, such as polyvalent amines, Polyurethane obtained by reacting with a polyhydric alcohol can be used.

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

Commercially available moisture-permeable one-component polyurethane is coated as a skin layer on polypropylene coated paper or silicone coated paper using an ordinary coating machine such as a knife coater, comma coater, kiss roll coater, etc., and the solid content is 3 to 20 g/TIt.
It is coated and dried in a dryer at a temperature range of 80 to 120°C. Next, on the one-component moisture-permeable polyurethane film formed on the template paper, a resin composition <A) consisting of a two-component polyether polyol-modified polyurethane resin, a melamine derivative, an organic polyisocyanate, and a crosslinking catalyst is further applied as an adhesive layer. The organic solvent solution is coated using a coating machine so that the solid content is 5 to 25 g/TIt, and the organic solvent is semi-dried or completely dried using a dryer in a temperature range of 60 to 100°C. Next, the crosslinked film (A) and the base fabric are laminated together at a temperature of 100 to 130°C and a pressure of 3 to 30 kg.
/ 'Cti heat roll to bond. The release paper is then 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.

<Effects of the Invention> The moisture permeable waterproof fabric obtained by this method is highly flexible, has both moisture permeability and waterproof properties, and has good 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 (9/go/24hr) Water pressure resistance (ms+Hzo) according to the method of JIS K-6328 Water repellency (points) according to the method of JIS-L-1092 Peeling image a according to the method of JIS-L-1092 (9/ C11) Membrane rubbing resistance according to the method of JIS K-8328 Using a Gakushin type friction fastness tester, the polyurethane surfaces are overlapped and rubbed 100 times under a load of 500 g.

No damage to the polyurethane surface If the case is grade 5, please use polyurethane surface. Grade 4, Poly The urethane surface was damaged about 3 times in 1 part. The case is grade 3, the polyurethane surface is complete. If completely peeled off, it is indicated as grade 1. Ru.

In addition, parts and % in the examples represent heavy parts or weight %, respectively.

Example 1 Polyethylene glycol 20 with average molecular weight 1i11500
Department.

80 parts of polybutylene adipate diol with an average molecular weight of 2000 and 15 parts of tolylene diisocyanate were reacted in 173 parts of a mixed solvent of toluene and dimethylformamide to obtain a two-part polyether polyol-modified polyurethane resin solution with a vIA11B concentration of 40%. . To this solution was added 10 parts of trimethylolmelamine (8.7% based on the two-component polyether polyol-modified polyurethane resin), and further 15 parts of hexamethylene diisocyanate.
0.5 part of p-toluenesulfonic acid.

0.5 part of dibutyltin dilaurate was added to obtain a solution (A-1) of a resin composition consisting of a two-component polyether polyol-modified polyurethane resin, a melamine derivative, an organic polyisocyanate, and a crosslinking catalyst.

One-component moisture-permeable polyurethane; CRIBON 3314 (manufactured by Dainippon Ink & Chemicals) was coated on polypropylene-coated paper using a comma coater so that the solid content was 87%, and then heated and dried at 100°C for 2 minutes. The above-mentioned resin composition A-1 was applied on the formed skin layer to a solid content of 189.
The coated film was coated so as to be at the base of the film and dried by heating at 65° C. for 1 minute and 30 seconds to obtain a coating A'-1. On the other hand, a fabric woven, scoured, and dyed using polyethylene terephthalate filament woolly yarn with a warp and weft of 50 denier and 24 filaments at a warp density of 140 pieces/inch and a weft density of 80 pieces/inch and the coating A'-1 were heated at 120°C. The pattern paper was peeled off after being pasted through a heated roll for 2 days and aged for 2 days. The thus obtained fabric made by laminating the polyurethane resin and polyester fabric is impregnated with a 3% aqueous solution consisting of a mixture of a fluorine-based water repellent and a silicone-based water repellent, squeezed with a mangle, and dried at 120°C for 5 minutes to make it moisture permeable. A waterproof fabric was obtained. The obtained fabric was extremely flexible and highly elastic in the lateral direction, and its characteristic values were as follows.

Moisture permeability (9/Td/24hr) 3500 Water pressure resistance (mH20) > 2000 Water repellency (point) 100 Peel strength (g/σ) 650 Membrane rubbing resistance (grade) 5 Example 2 Polyethylene terephthalate filament yarn ( The fabric obtained in the same manner as in Example 1 except that a polyethylene terephthalate motsukuroday knitted fabric obtained by knitting at 36 gauge using 50 denier/36 filament and performing scouring and dyeing treatment by a conventional method was used. It has excellent elasticity and elasticity, and its characteristic values are as follows.

Moisture permeability ('J/rd, /24hr)
3600 water pressure resistance (a+lIH20) > 2
000 Water repellency (point) 100 Peel strength (g/σ) 750 Membrane abrasion resistance (grade) 5 Comparative example 1 In Example 1, 10 parts of trimethylolmelamine,
The fabric obtained in the same manner as in Example 1 except that a resin composition without 0.5 part of p-toluenesulfonic acid was used was a fabric with high flexibility and stretchability, but the characteristic values were as follows. there were.

Moisture permeability (g/rd/24hr) 170
0 Water pressure resistance (#IIH20) >2000 Water repellency (points) 90 Peel strength ('j/an) 250
Membrane abrasion resistance (grade) 1 Comparative Example 2 Same as Example 1 except that in Example 1, 20 parts of polyethylene glycol with an average molecular weight of 1,500 was not used and 100 parts of polybutylene adipate diol with an average molecular weight of 2,000 was used. The fabric obtained by this method is flexible.

Although the fabric was highly stretchable, its characteristic values were as follows.

Moisture permeability (g/TIt/24hr) 500
Water pressure resistance (#IIH20) >2000 Old aqueous (point) 100 Peel strength (g/am) 480 Membrane abrasion resistance (grade) 4 Example 3 50 parts of polypropylene glycol with an average molecular weight of 12000, polyethylene adipate diol with an average molecular weight of 111000 50 1 part and 10 parts of 4'-diphenylmethane diisocyanate in toluene and dimethylformamide,
A two-component polyether polyol-modified polyurethane resin solution with a resin concentration of 46% was obtained by reacting in 130 parts of a mixed solvent with 100% polyurethane. Add 20 parts of trimethylolmelamine to this solution, further add 10 parts of hexamethylene diisocyanate,
0.5 part of p-toluenesulfonic acid.

0.5 parts 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 polyurethane resin layer of the obtained fabric had a tendency to swell slightly in water, but the fabric was highly flexible and lateral stretchable, and its characteristic values were as follows.

Moisture permeability (g/rd -24hr) 4500
Water pressure resistance (MHz O) 1800 water repellency (
point) 90 peel strength <9/
am > 450 membrane abrasion resistance (grade)
3 Comparative Example 3 In Example 3, 20 parts of trimethylolmelamine.

In a fabric obtained in the same manner as in Example 3 except for using a resin composition without adding 5 parts of p-toluenesulfone lid O, the polyurethane resin layer had a tendency to swell considerably in water. Its characteristic values were as follows.

Moisture permeability (g/rd, -24hr) 250
0 Water pressure resistance (#IH20)' 1300 Peel strength NJ/α) 250

Claims (1)

[Claims] In a method for producing a moisture-permeable waterproof fabric in which a fabric is coated with a resin mainly composed of a polyurethane polymer, a one-component moisture-permeable polyurethane resin is formed into a thin film, and then a two-component polyether polyol-modified polyurethane or a melamine derivative is coated on the thin film. A method for producing a moisture-permeable waterproof fabric, which comprises coating the fabric with a resin composition (A) consisting of an organic polyisocyanate, and a crosslinking catalyst, and laminating the fabric through the resin composition (A).