JPH04146275A - Moisture permeable waterproofing cloth having excellent waterproofing performance - Google Patents

Abstract

PURPOSE:To obtain moisture permeable waterproofing cloth having excellent waterproofing performances and improved washing durability by forming a porous moisture permeable film of a fluorine modified polyurethane resin on fiber cloth and further making a porous moisture permeable film of water-soluble polyurethane resin on the film. CONSTITUTION:Firstly, cloth made of synthetic fiber or semisynthetic fiber is preferably subjected to water repelling treatment, then coated with a solution of a fluorine modified polyurethane resin and coagulated by a wet method to form a porous moisture permeable film, on which a porous moisture permeable film of a water-soluble or emulsion-based polyurethane is further made successively by dry method to give moisture permeable cloth showing excellent water pressure resistance, excellent water vapor absorbing performances and washing durability. The fluorine modified resin is obtained by copolymerizing a polyurethane with a fluorine-containing polymer (e.g. polyvinyl fluoride).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a moisture-permeable waterproof fabric used for various types of clothing such as raincoats, outerwear, and sports clothing.

(Prior Art) Conventionally, moisture-permeable waterproof fabrics obtained by dry or wet coating methods have been known to have non-porous resin layers and those with porous resin layers.

Especially moisture permeable waterproof fabrics with porous resin layers.

It is known to have high moisture permeability because it forms countless continuous fine pores that allow water vapor to escape in the resin layer during dry or wet coating processing.

(Problem to be Solved by the Invention) However, the above-mentioned moisture-permeable waterproof fabric has pores with a pore diameter of 1 to 3 μm on the surface of the resin layer, so the waterproof performance is insufficient when used for a rain hat for fishing. In addition, contaminants such as sweat and oil when worn and detergent during washing are adsorbed, causing the porous resin layer to become hydrophilic, resulting in a significant decrease in waterproof performance.

There were problems such as the waterproof performance retention rate after 10 home washings was 60% or less.

The present invention solves the above problems.

The object of the present invention is to provide a moisture-permeable waterproof fabric that has excellent moisture permeability, waterproof performance, and excellent washing durability.

(Means for Solving the Problems) The present invention achieves the above object and has the following configuration.

That is, 1 the present invention has a porous moisture-permeable membrane made of a synthetic polymer mainly composed of a fluorine-modified polyurethane resin on a fiber fabric, and a porous moisture-permeable membrane made of a synthetic polymer mainly composed of a water-soluble or emulsion polyurethane resin on the moisture-permeable membrane. The gist of this invention is to provide a moisture-permeable waterproof fabric with excellent waterproof performance, which is characterized by having a porous moisture-permeable membrane.

Two aspects of the present invention will be described in detail below.

The fiber fabrics used in the present invention include polyamide synthetic fibers such as nylon 6 and nylon 66, polyester synthetic fibers such as polyethylene terephthalate, polyacrylonitrile synthetic fibers, polyvinyl alcohol synthetic fibers, and triacetate synthetic fibers. Examples include woven fabrics, nonwoven fabrics, etc. made of synthetic fibers or mixed fibers such as nylon 6/cotton, polyethylene terephthalate/cotton, etc.

In the present invention, the above-mentioned fiber fabric may be treated with a water repellent agent, and this is one means for preventing the resin solution from penetrating into the fabric. The water repellent used may be a known one such as a paraffin water repellent, a polysiloxane water repellent, or a fluorine water repellent, and the treatment can be carried out by the commonly used padding method, spray method, etc. This can be done by any known method. If particularly good water repellency is required, use a fluorine-based water repellent1, such as Asahi Guard 730.
(Fluorine water repellent emulsion, manufactured by Asahi Glass) at 5%
After padding with an aqueous dispersion (squeezing ratio 35%), 160℃
This may be carried out by a method of performing heat treatment for 1 minute at .

In the moisture-permeable waterproof fabric of the present invention, a porous moisture-permeable membrane made of a synthetic polymer mainly composed of a fluorine-modified polyurethane resin is first formed on the above-mentioned fiber fabric.

The synthetic polymer mainly composed of fluorine-modified polyurethane resin as used herein refers to one containing 60 to 100% of fluorine-modified polyurethane resin as one synthetic polymer.

Other synthetic polymers such as polyacrylic acid,
It may contain less than 40% of polyvinyl chloride, polystyrene, polybutadiene, polyamino acids, and copolymers thereof.

Examples of fluorine-modified polyurethane resins include those obtained by copolymerizing polyurethane and a fluorine-containing synthetic polymer through a polymer reaction, or by introducing a functional group into polyurethane in advance and causing it to undergo a chemical reaction with a fluorine compound. can. The fluorine content of the fluorine-modified polyurethane resin may be appropriately selected depending on the intended use, but is usually preferably 10 to 50%.

Here, as the polyurethane resin, aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates may be used alone or in mixtures thereof as isocyanate components.1For example, tolylene 2,4-diisocyanate, 4,4''-diphenylmethane diisocyanate,
1,6-hexane diisocyanate, 1,4-cyclohexane diisocyanate, etc. are used as the polyol component.

Polyether polyols and polyester polyols are used. Polyether polyols are made of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., and polyester polyols are made of diols such as ethylene glycol and propylene glycol and dibases such as adipic acid and cepatic acid. A reaction product with an acid or a ring-opening polymer such as caprolactone is used.

In addition, fluorine-containing synthetic polymers include polyvinyl fluoride, polyvinylidene fluoride, polyhexafluoropropylene,
Polytrifluoroethylene, polytetrafluoroethylene, polyfluorinated acrylic acid.

Polyfluorinated amino acids and polyether polyols.

A fluorine-modified product of polyester polyol is used.

As a method for copolymerizing a polyurethane resin and a fluorine-containing synthetic polymer9, for example, when reacting the isocyanate group (-NGO) of a polyurethane resin with a fluorine-containing synthetic polymer, active hydrogen is added to the terminal of the fluorine-containing synthetic polymer. What is necessary is to introduce a functional group having a hydroxyl group, an amino group, a carboxyl group, etc. as the functional group.

In the present invention, in order to form a porous moisture-permeable membrane on a fiber fabric, a solution of the synthetic polymer mainly composed of the above-mentioned fluorine-modified polyurethane resin is coated using a conventional coating method 1, such as a knife coater or a comma coater.

After coating on the fiber fabric using a coating method such as a reverse coater, wet coagulation or applying a solution of a fluorine-modified urethane resin that has been modified in advance to a system that is easy to mechanically foam, There are methods of drying.

In the present invention, for the purpose of improving the peeling resistance between the resin layer and the fiber fabric, a compound having high affinity with the resin or the fiber fabric may be used in combination.

It is preferable to use an isocyanate compound in combination as the compound.

Examples of the incyanate compound include 2.4-) lylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene isocyanate, or 3 moles of these diisocyanates and 1 mole of a compound containing active hydrogen (for example, trimethylolpropane, glycerin, etc.). Triisocyanates obtained by addition reaction with can be used. The above incyanates can be stabilized even if they have free isocyanate groups, or by adding phenol, methyl ethyl ketoxime, etc.

Even if the block is dissociated by subsequent heat treatment, any type can be used, and it may be used appropriately depending on workability, usage, etc.

The amount used when using isocyanate compounds is as follows:
For fluorine-modified polyurethane resin.

It is desirable to use it in a proportion of 0.1 to 10% by weight.

If the amount used is less than 0.1%, the adhesive strength of the resin layer to the fabric will be low, and if it exceeds 10%.

This is because the texture tends to harden.

Undesirable.

In the present invention, in order to improve waterproof performance without impairing moisture permeability, water-soluble or emulsion polyurethane is further added to the porous moisture permeable membrane made of the synthetic polymer mainly composed of fluorine-modified polyurethane resin. Forms a porous moisture-permeable membrane made of resin-based synthetic polymer.

Water-soluble polyurethane resins and emulsion-based polyurethane resins include reaction products of incyanate components and polyol components, similar to the aforementioned polyurethane resins, but among these, water-soluble polyurethane resins generally contain known hydrophilic ions. Any polyurethane resin that has many groups and has the property of being soluble in water may be used.For example, Elastron CT-10 (manufactured by Daiichi Kogyo Seiyaku), HYDRAN
HW-3'01 (manufactured by Dainippon Ink & Chemicals) can be mentioned. In addition, emulsion-based polyurethane resins include W10 emulsion (water-in-oil emulsion) and 0/W emulsion (oil-in-water emulsion).
However, generally known polyurethane resins in which fine particles are uniformly dispersed with an emulsifier etc. may be used.For example, V
ONDIC1640 (manufactured by Dainippon Ink & Chemicals) and Heimlen X-3038 (manufactured by Dainippon Ink & Chemicals & Chemicals) can be mentioned. These water-soluble urethane resins and emulsion polyurethane resins may be used alone or in combination.

Here, the synthetic polymer mainly consisting of water-soluble or emulsion polyurethane resin refers to one containing 60 to 100% water-soluble or emulsion polyurethane resin as one synthetic polymer, and other synthetic polymers include water-soluble or emulsion polyurethane resin. It may contain less than 40% of polyacrylic acid, polyvinyl acetate, etc., or copolymers thereof.

Moreover, in order to improve the peeling resistance of the resin film, the above-mentioned incyanate compound may be used in combination.

The above-mentioned synthetic polymer solution is coated on a porous moisture-permeable membrane made of a synthetic polymer mainly composed of fluorine-modified polyurethane resin formed on a fiber fabric using a conventional coating method such as a knife coater, a comma coater, or a reverse coater. Coat with a coater etc.

dry. A moisture-permeable film is formed using a so-called dry coating method. At this time, while considering drying conditions and mechanical conditions,
Forms a porous moisture permeable membrane.

The total coating amount of the synthetic polymer based on fluorine-modified polyurethane resin and the synthetic polymer based on water-soluble or emulsion polyurethane resin is determined by the thickness of the resin film to be obtained.
What is necessary is just to determine suitably according to 100 micrometers.

In the present invention, for the purpose of further improving waterproof performance,
A porous moisture-permeable membrane made of a synthetic polymer mainly composed of fluorine-modified polyurethane resin is once subjected to water-repellent treatment, and then a porous moisture-permeable membrane made of a synthetic polymer mainly composed of water-soluble or emulsion polyurethane resin is formed. , a method of performing water repellent treatment again may be adopted. For the water repellent treatment, a commonly used known water repellent treatment method may be employed.

The present invention has one or more configurations.

(Function) The moisture permeable waterproof fabric of the present invention has excellent moisture permeability and high waterproof performance, and its waterproof performance has a retention rate of 60% or more after repeated home washing 30 times. Excellent washing durability. The reason why this moisture-permeable waterproof fabric has high waterproof performance and washing durability is as follows.
Although it is not necessarily clear, it can be thought of as follows.

Moisture-permeable waterproof fabric, which has a porous resin layer made of polyurethane resin or polyamino acid urethane resin formed on a conventional fiber fabric, maintains a contact angle of 90° or more between the porous resin layer and water, and has waterproof performance. Even if the product has a waterproof property, it becomes hydrophilic by adsorbing contaminants such as sweat and oil when worn, and by adsorbing surfactants in detergent when washed, reducing the contact angle and significantly improving waterproof performance. descend. On the other hand, the moisture-permeable waterproof fabric of the present invention has a porous resin layer mainly made of fluorine-modified polyurethane resin, so it has water and oil repellency and is free from pollutants and surfactants. At the same time, adsorption of agents, etc. is suppressed.

Furthermore, since a porous moisture-permeable membrane made of a synthetic polymer mainly composed of water-soluble or emulsion polyurethane resin with good adhesion is formed on the moisture-permeable membrane, the contact angle with water is always maintained inside the resin. The angle is maintained at 90° or more, thus improving waterproof performance.

The effect is that there is little deterioration in waterproof performance even after repeated washing.

In addition, synthetic polymers mainly based on water-soluble or emulsion polyurethane resins can be formed without damaging the porous moisture permeable membrane form made of synthetic polymers mainly based on fluorine-modified polyurethane resins, so they have high moisture permeability. Performance can also be maintained.

(Example) Hereinafter, the manufacturing method of the moisture-permeable waterproof fabric of the present invention will be specifically explained with reference to Examples. The performance of the fabric according to the Examples was measured and evaluated using the following method.

(1) Water pressure resistance According to JIS L-1092 (high water pressure method).

The water pressure resistance of the sample was measured before and after the washing durability test described in item (5) below.

In addition, the waterproof performance retention rate was calculated|required by the quadratic formula.

(2) Water retention l5 (3) Moisture permeability (spray method) JIS Z-0208 (4) Peeling strength JIS K-6328 (5) Washing durability test Washed repeatedly according to JIS L-0844 (A-2 method) 30 times Do it twice.

Example 1 First, fluorine-modified polyurethane resin (hereinafter F-P
It is called U resin. ) was produced by the following method.

Polytetramethylene glycol (OH value 56.9) 19
70g and 1,6-hexamethylene diisocyanate) 50
4g was reacted at 90°C for 5 hours to obtain a urethane prepolymer having isocyanate groups at the terminals (NGO equivalent: 23
40) was obtained. 85 g of this urethane prepolymer and 21 g of a vinyl fluoride polymer with a hydroxyl group introduced at the end were dissolved in 415 g of a mixed solvent of dimethylformamide/dioxane (weight ratio = 7/3), and 47 g of a 2% dimethylamine solution was added while stirring. The reaction was carried out at 30°C for 5 hours to obtain a yellow-brown F-PU resin solution with good fluidity and a viscosity of 39.0OOcps (25°C).

Next, using nylon multifilament 70 denier/34 filament for both warp and weft as the base fabric,
A plain weave (taffeta) with a warp density of 120 threads/inch and a weft thread density of 90 threads/inch is woven.

This is followed by scouring and acid dye Diacid in the usual manner.
After red staining with Fast Red 3BL (Mitsubishi Kasei ■), padding (squeezing ratio 35%) with a 5% aqueous solution of Asahi Guard 710 (manufactured by Asahi Glass Acupuncture), a fluorine-based water repellent emulsion, was performed at 160°C for 1 minute. heat treatment was performed.

Subsequently, calendering was performed using a calendering machine with mirror-finished rolls at a temperature of 160° C., a pressure of 30 kg/cnf, and a speed of 20 m/min.

Furthermore, after applying a synthetic polymer solution having the composition shown in Formulation 1 below and having a solid content concentration of 20% using a knife-over roll coater at a coating amount of 100 g/m', immediately
The resin was solidified by immersion in water at 0.degree. C. for 1 minute.

[Formulation 1] F-PU resin 00B N-N-dimethylformamide 18 parts After this, 50
A porous moisture-permeable membrane was formed on the fabric by washing for 10 minutes in warm water at ℃ and drying.

Next, a resin solution shown in Formulation 2 below was applied onto the moisture permeable membrane using a comma coater so that the weight of the dry film was 5 g/m', and then dried at 80°C for 3 minutes.

[Formulation 2] Methyl ethyl ketone toluene water 15 parts 15 parts Up to 30 parts 9 Padded with a 5% aqueous solution of fluorine-based water repellent emulsion Asahi Guard 710 (manufactured by Asahi Glass ■) (squeezing ratio 30%) and dried at 160°C. A heat treatment was performed for 1 minute to obtain a moisture permeable waterproof fabric of the present invention.

For comparison with the present invention, a comparative moisture-permeable waterproof fabric (Comparative Example 1) was obtained in exactly the same manner as in this Example, except that the following Formulation 3 was used in place of Formulation 1. .

[Formulation 3] N-N-dimethylformamide 10 parts The performance of the present invention and comparative moisture-permeable waterproof fabrics were measured and evaluated, and the results are shown in Table 1.

As is clear from Table 1, the moisture-permeable waterproof fabric of the present invention had excellent water pressure resistance and washing durability, and had very good water repellency, moisture permeability, and peel strength. .

Example 2 A moisture-permeable waterproof fabric of the present invention was obtained in exactly the same manner as in Example 1, except that the following formulation 4 was used in place of formulation 2 in Example 1.

[Prescription 4] In Example 2 for comparison with the present invention.

A comparative moisture-permeable waterproof fabric (Comparative Example 2) was obtained in exactly the same manner as in Example 2, except that Formulation 3 was used in place of Formulation 1 of Example 1, which was applied mutatis mutandis in the same Example.

The performance of the moisture-permeable waterproof fabric of the present invention and the comparative waterproof fabric was measured and evaluated, and the results are shown in Table 2.

Table 2 As is clear from Table 2, the moisture permeable waterproof fabric of the present invention had excellent water pressure resistance and washing durability, and had very good water repellency, moisture permeability, and peel strength. .

(Effects of the Invention) According to the present invention, it is possible to obtain a moisture permeable waterproof fabric that has excellent water pressure resistance and washing durability, and also has good moisture permeability. Due to such excellent performance, the moisture permeable waterproof fabric of the present invention can be used as raincoats and sports clothing.

It can be used for various other clothing, and is particularly suitable for raincoats that require high water pressure resistance.

Claims (1)

[Claims] (1) A porous moisture-permeable membrane made of a synthetic polymer mainly composed of a fluorine-modified polyurethane resin on a fiber fabric, and a porous membrane made of a synthetic polymer mainly composed of a water-soluble or emulsion polyurethane resin on the moisture-permeable membrane. A moisture-permeable waterproof fabric with excellent waterproof performance, characterized by having a moisture-permeable membrane.