JPH01246477A - Antifungal, moisture-permeable and waterproof cloth - Google Patents

Abstract

PURPOSE:To obtain the title cloth with a combination of antifungal nature excellent in washing durability with two functions of both water-proofness and moisture permeability, by incorporating an antifungal substance into a specified number of fine pores formed on the resin film on a cloth. CONSTITUTION:When a cloth made up of synthetic or semi-synthetic fiber is to be coated with a resin solution, such a solution as to be prepared by incorporating said resin solution (e.g., for the purpose of the film strength, pref. polyamino acid polyurethane resin solution) with an antifungal substance is applied on said cloth followed by e.g., underwater coagulation to effect incorporation of said antifungal substance into the resultant finely porous resin film formed so as to be 20-70% in the porosity determined by the relationship [P is porosity (%); W is weight (g) of the resin film; S is area (cm<2>) of the resin film; d is thickness (cm) of the resin film; rho is density (g/cm<3>) of the resin], thus obtaining the objective cloth. To form said finely porous film, wet or dry coagulation process may be used. Said antifungal substance is e.g., 2- naphthyl-N-methyl-N-(3-tolyl)thiocarbonate.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an antibacterial, moisture-permeable waterproof fabric that has dual functions of waterproofness and moisture permeability, and which also has antibacterial properties. It is something.

(Prior Art) In recent years, moisture-permeable waterproof fabrics that have both waterproofness and moisture permeability have been used for sports clothing, cold-proof clothing, etc., and are particularly used in the field of sports clothing where sweating is significant due to strenuous exercise. In this sports field where the amount of sweat is significant,
BACKGROUND ART Microorganisms such as bacteria multiply on clothing that has sweat on it, causing problems such as emitting a bad odor and causing discoloration and brittleness of the fabric.

In response to this current situation, conventional methods include coating or spraying antibacterial substances on fabrics made of natural fibers or synthetic fibers, or impregnating fabrics with an aqueous solution of antibacterial substances. This gives antibacterial properties to fabrics such as socks.

It was used in the fields of shoe insoles, linings, futons, etc. However, the fabric obtained by this method has the disadvantage that its antibacterial properties do not last long, and in particular, the substances with antibacterial properties attached to it easily fall off when washed, etc., and the fabric has excellent washing durability. There has been a strong demand for a moisture-permeable, waterproof fabric for sports clothing that has antibacterial properties.

(Problems to be Solved by the Invention) The present invention was made in view of the current situation, and provides a moisture-permeable waterproof fabric that has excellent moisture permeability and waterproof properties, and has antibacterial properties that have excellent washing durability. The purpose is to obtain.

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

That is, the present invention provides the following (I) formed on the surface of the fabric.
) The gist of this article is an antibacterial, moisture-permeable, waterproof fabric characterized by containing an antibacterial substance in a microporous resin film with a porosity calculated from the formula 20 to 70%. .

ρ (where, P is the porosity (%), W is the weight of the resin film (g)
, S is the area of the resin film (cni), d is the thickness of the resin film (C11), and ρ is the density of the resin (g/cd). ) The present invention will be explained in detail below.

Examples of substances having antibacterial properties used in the present invention include:

Naphthiomate antibacterial agents such as 2-naphthyl-N-methyl-N-(3-1-lyl)thiocarbamate.

Benzimidazole antibacterial agents such as 2-(4-thiazolyl)benzimidazole, halogenated phenyl antibacterial agents such as bis-(halachlorophenyldiguanide)hexane dihydrochloride, N, N-didecyl-N-methyl- Examples include quaternary ammonium salt compounds such as 3-trimethoxypropylammonium chloride, organic tin compounds such as triphenyltin chloride, and bromine compounds such as α-bromcinnamaldehyde, which have the desired antibacterial properties. Other antibacterial agents may also be used.

The amount of these antibacterial substances used is not particularly limited, but is preferably in the range of 0.01 to 50% by weight based on the weight of the resin film. If the amount used is less than 0.01% by weight, there is no effect on antibacterial properties.

Moreover, if the amount used exceeds 50% by weight, it is not preferable because the physical properties of the resin used generally deteriorate.

In the present invention, the resin film containing an antibacterial substance formed on the surface of the fabric has a porosity of 20 to 70 expressed by the following formula (I).
%, but considering antibacterial properties and moisture permeability, this porosity is within the range of .

A range of 40 to 70% is even more preferable.

ρ (where, P is the porosity (%), W is the weight of the resin film (g)
, S is the area of the resin film (ci), and d is the thickness of the resin film (
cm), ρ is the density of the resin (g/cnO). If the porosity is less than 20%, the antibacterial substance contained in the resin may be contaminated with bacteria or mold.

Since the surface area that comes into contact with yeast etc. is reduced, a sufficient antibacterial effect cannot be expected, and if the porosity exceeds 70%, the physical properties of the resin will deteriorate significantly and it will no longer be suitable for practical use.

The film resin used in the present invention is a resin that can form a microporous film, and specifically, polyurethane resin obtained by reacting polyisocyanate and polyol, γ-alkyl glutamate -N - Polyamino acid urethane resins made of polyamino acids obtained from carboxylic acid anhydrides and polyurethane, acrylic acid resins such as acrylic esters, etc. can be used alone or in combination, but may form a microporous film. If it's resin.

Any other resin can also be used.

The method of incorporating an antibacterial substance into the resin film is to add a predetermined amount of the antibacterial substance when preparing the resin solution to be used, mix thoroughly with a stirrer that matches the viscosity of the resin solution, etc. , coating, and film forming methods may be employed.

The moisture permeable waterproof fabric of the present invention can be manufactured by one of a variety of methods. The methods include wet film forming method using direct coating, dry foam film forming method, wet film forming method using lamination, dry foam film forming method, etc.
It may be selected appropriately depending on the purpose.

In the present invention, the above-mentioned resin and substance having antibacterial properties are mixed with various solvents, and a microporous resin film is obtained by the method described below.

First, in the wet method, a resin solution is diluted and mixed with a polar organic solvent, the resin solution is applied to the surface of the fabric or the release fabric, and then the resin is immersed in water to solidify the resin. Obtain a resin film.

In this case, the porosity of the microporous resin film is controlled by the dilution rate with the polar organic solvent (solid content concentration of the resin), the addition of a surfactant, the temperature of the water that is the solid liquid, and the like.

The polar organic solvents used here include dimethylformamide, dimethylacetamide, dimethylsulfoxide, N
-Methylpyrrolidone, hexamethylenephosphonamide, etc.

There are various methods for forming a microporous film using a dry method, but two typical methods include mixing an emulsion resin, a volatile solvent, and water, uniformly emulsifying the mixture, and then coating the fabric surface or Applying a resin solution onto a release paper, first evaporating the volatile solvent under temperature conditions that allow only the volatile solvent to evaporate but not water, and then evaporating water under temperature conditions that allow water to evaporate. A microporous film is obtained.

In this case, the porosity of the microporous resin film is controlled to an arbitrary porosity by the amount of volatile solvent and water added to the resin.

Volatile solvents used here include ketone solvents and aromatic hydrocarbon solvents. Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and aromatic hydrocarbon solvents. can include toluene, xylene, etc.

In the present invention, in order to improve the peeling resistance between the resin film and the fabric, in the direct coating method, in the resin solution,
In the lamination method, an isocyanate compound is used as a binder. As the isocyanate compound, 2,4-tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene isocyanate, etc. are used.

To apply a resin solution to the surface of a fabric or a release fabric by direct coating, 2. Ordinary coating method 1. For example, a coating method using a knife coater, comma coater, etc. may be used. After forming a film on the surface of a release fabric,
In the wet film forming lamination method, the fabric may be laminated with a polyurethane adhesive after wet film forming.

In addition, in the dry foam film forming lamination method, a resin solution may be coated on a release paper using a knife over roll coater or the like, and after dry film forming, the resin solution may be laminated onto a fiber fabric using a polyurethane adhesive.

As described above, in the present invention, a microporous resin coating may be obtained using any resin and any manufacturing method;
In order to obtain a microporous resin film having a high porosity of 0% and excellent film strength, a wet film forming method using a polyamino acid urethane resin is preferably used.

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. Synthetic fiber or nylon 6/cotton, polyethylene terephthalate/
Examples include two-knit woven fabrics, non-woven fabrics, etc. made of blended fibers such as cotton.

In the present invention, water repellent treatment is performed as post-processing.

The 1Ω liquid agent used here may be a known one such as a paraffin-based tθ liquid agent, a polysiloxane-based 1θ liquid agent, or a fluorine thread ■8 liquid agent, and Iθ water treatment may be performed using a padding method, spray method, coating method, etc. as appropriate. That's fine.

The present invention has the above configuration.

(Effects) The antibacterial mechanism of antibacterial substances is thought to be as follows.

(11. Substances with antibacterial properties penetrate the cell membranes and cell walls of microorganisms such as bacteria, blocking their function and destroying them.

(2) When the antibacterial substance does not penetrate into cells and microorganisms come into contact with the processed cloth, they destroy cell membranes and cell walls and inhibit their growth.

Based on the above, the present inventors believe that in order to make antibacterial properties efficient and sustainable, it is possible to make antibacterial properties efficient and sustainable if the area in which a substance with antibacterial properties comes into contact with bacteria and other microorganisms is widened. I had a feeling it would be something sexual. Additionally, in order to improve washing resistance, forming a resin film containing antibacterial substances on the surface of the fabric will prevent the antibacterial substances from leaching or falling off during washing. Therefore, it was inferred that the washing resistance would be improved.

The antibacterial moisture-permeable waterproof fabric of the present invention contains an antibacterial substance in the microporous resin film with a porosity of 20 to 70% formed on the surface of the fabric. This increases the area in which the resin comes into contact with microorganisms such as bacteria, and the microporous resin film contains substances that have antibacterial properties.

It becomes an antibacterial, moisture-permeable, waterproof fabric with excellent antibacterial durability and washing resistance.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples. The performance of the fabrics in the Examples was measured by the following method.

(1) Porosity: Cut the fabric having a microporous film into a square of 20cm x 20cm, peel the microporous film from the fiber base fabric, and after drying, calculate the thickness d (cm) and weight W (g) of the microporous film. The porosity P (%) is calculated by substituting this, the area S (400 cJ), and the density ρ (g/cut) of the resin, which is known in advance, into the above formula (I).

(2) Antibacterial properties Based on the shake flask method (bacterial count reduction rate test).

<Test strain> Staphylococcus aur.
EUS FDA 209P) Test method> A buffer suspension of test bacteria was poured into sterilized non-antibacterial treated cloth and antibacterial treated cloth, and the test was carried out 150 times/in a sealed container.
After shaking for 1 hour, the number of viable bacteria was measured, and the reduction rate (%) of the number of bacteria in the suspension added to the antibacterial-treated cloth compared to the number of bacteria in the suspension added to the non-antibacterial treated cloth. I asked for

Using the above method, the antibacterial properties of the samples before and after the washing durability test in item (3) above were measured.

(3) Washing durability test JIS t, '-0217
Repeat washing using the 103 method 30 times.

(4) Moisture permeability (moisture permeability): JIS L-1099
(A-1 method) (5) Waterproofness (water pressure resistance): JIS L
-1096 (Low Water Pressure Resistance Method) Example 1 First, as a base fabric, nylon 70 denier/24 filament was used for the warp, nylon 70 denier/34 filament was used for the weft, the warp density was 120/inch, and the weft density was 90.
Prepare a plain woven fabric (taffeta), scouring it in the usual way and dyeing it with an acid dye.
Calendering was carried out under conditions of a pressure of 30 kg/cm and a speed of 20 m/min.

Next, as a substance with antibacterial properties, Sanitize 1977
(Silicone quaternary ammonium salt antibacterial agent 9 Nippon Sanitize ■ product), apply a polyurethane resin solution with a resin solids concentration of 30% as shown in Formulation 1 below to a coating amount of 100 g/m using a knife over roll coater. After coating, the resin was immersed in a water bath with a bath temperature of 20° C. to solidify the resin, and then washed in warm water of 60° C. for 10 minutes and dried.

[Formulation 1] 20 parts of dimethylformamide 3 parts of Saskiz 1977 After this, apply fluorine thread to the above fabric! The antibacterial, moisture-permeable and waterproof fabric of the present invention was prepared by padding (squeezing ratio: 30%) with a 5% aqueous solution of Asahi Guard 710 (a product of Asahi Glass Co., Ltd.), an aqueous emulsion, and then heat treatment at 160°C for 1 minute. I got it.

For comparison with the present invention, a comparative moisture-permeable and waterproof fabric (referred to as Comparative Example 1) was prepared in the same manner as in the second example, except that the addition of the antibacterial substance Sanitize 1977 was omitted. I got it.

For comparison with the present invention, 1 except that the addition of the surfactant and dimethylformamide used in this example ↓) was omitted.
A comparative moisture-permeable waterproof fabric (referred to as Comparative Example 2) was obtained in exactly the same manner as in this example.

The present invention and Comparative Example I obtained as described above.

The performance of the moisture-permeable waterproof fabric No. 2 was measured, and the results are also shown in Table 1.

As is clear from Table 1, the antibacterial, moisture permeable and waterproof fabric of the present invention exhibits excellent durability and antibacterial properties as well as good permeability compared to the fabric of the comparative example. was.

Example 2 First, a polyamino acid urethane resin (hereinafter referred to as PAU resin) used in this example was manufactured by the following method.

Polytetramethylene glycol (014 value 56.9) 1
970g and 1,6-hexamethylene diisocyanate 5
04g was reacted at 90°C for 5 hours to form a urethane prepolymer having an isocyanate group at the end (NCO equivalent ff1).
2340) was obtained. 85 g of this urethane prepolymer and 35 g of γ-methyl-L-glutamate NCA were dissolved in 666 g of a mixed solvent of dimethylformamide/dioxane (weight ratio 7/3), and while stirring, 50 g of 2% triethylamine solution was added and reacted at 30°C for 5 hours. When you do .

A yellowish brown emulsion-like PAU resin solution with good fluidity and a viscosity of 65,000 cps (25°C) was obtained. This PAU
The resin is the one used in Formulation 2, which will be described later.

An antibacterial, moisture-permeable, waterproof fabric of the present invention was produced using the above-mentioned PAU resin by the first method.

First, a plain woven fabric was calendered in exactly the same manner as in Example 1.

Next, α-bromocinnamaldehyde (Tokyo Kasei Kogyo ■ product) was used as a substance with antibacterial properties.

A resin solution with a resin solid content concentration of 23% shown in Formulation 2 below,
Coated using knife over roll coater W110g
/m, the resin component was coagulated in a water bath at 20°C, followed by washing in warm water at 60°C for 10 minutes and drying.

[Formulation 2] PAU resin 100 parts Kuribon AW-7H 10 parts Dimethylformamide 10 parts α-Bromcinnamaldehyde 2 parts After this, apply 5% Asahi Guard 710 (a product of Asahi Glass Co., Ltd.), a fluorine-based water repellent emulsion, to the above fabric. Padding with aqueous solution (squeezing ratio 3
0%) treatment, and then heat treatment at 160° C. for 1 minute to obtain an antibacterial, moisture-permeable, waterproof fabric of the present invention.

For comparison with the present invention, 2 except that the surfactant and dimethylformamide used in this example were omitted.
A comparative moisture-permeable waterproof fabric (referred to as Comparative Example 3) was obtained in exactly the same manner as in this example. The performance of the moisture-permeable and waterproof fabrics of the present invention and Comparative Example 3 obtained as described above was measured, and the results are shown in Table 2.

As is clear from Table 2, the antibacterial waterproof fabric of the present invention exhibits excellent durability and good antibacterial properties, as well as good moisture permeability, compared to the fabric of the comparative example. was.

Example 3 First, polyethylene terephthalate 50 denier/24 filament was used as the base fabric for both the front yarn and the bank yarn, and the number of courses was 52/inch.

A tricot half with a wale count of 40 wood/inch was prepared and subjected to scouring and dyeing with a disperse dye in a conventional manner.

Next, using Sanitize 1977, which is the same as in Example 1, as an antibacterial substance, a polyurethane resin solution with a resin solid content concentration of 16% shown in Formulation 3 below was coated on release paper using a knife-over-roll coater. Coating it 100
After coating at 60°C for 3 minutes, dry again at 120°C for 12 minutes to form a microporous resin film. Apply the polyurethane adhesive solution shown in Formulation 4 below using a knife-over roll coater in an amount of 60.
After applying at g/g, drying at 50°C for 3 minutes,
A base fabric was attached to this and thermocompression bonding was performed at 90°C and 3 kg/cJ.

[Formulation 3] Methyl ethyl ketone/toluene (=13/18)
3 1 part water/methyl ethyl ketone (=5015) 5 5
Part [Formulation 4] Dimethylformamide 10 parts Toluene 40 parts Subsequently, the release paper was peeled off, and the resulting laminated fabric was coated with Asahi Guard 710 (a product of Asahi Glass Co., Ltd.), a fluorine-based tθ water emulsion.
% aqueous solution (squeezing ratio: 30%) and then heat treatment at 160° C. for 1 minute to obtain an antibacterial, moisture-permeable, waterproof fabric of the present invention.

2 for comparison with the present invention 1 Antibacterial moisture-permeable material for comparison was prepared in exactly the same manner as in this example, except that 55 parts of water/methyl ethyl ketone (=5015) of [Formulation 2] used in this example was removed. A waterproof fabric (Comparative Example 4) was obtained. The performance of the antibacterial, moisture-permeable, and waterproof fabrics of the present invention and Comparative Example 4 obtained as described above was measured, and the results are shown in Table 3.

Table 3 As is clear from Table 3, the antibacterial, moisture permeable and waterproof fabric of the present invention exhibits superior durability and antibacterial properties as well as good moisture permeability compared to the fabric of the comparative example. was also shown.

(Effects of the Invention) The antibacterial, moisture-permeable, waterproof fabric of the present invention contains a substance having antibacterial properties in the microporous resin film with a porosity of 20 to 70%, so it has excellent antibacterial properties and is durable. It has excellent moisture permeability and waterproof properties.

The antibacterial, moisture-permeable, waterproof fabric of the present invention is a material particularly suitable for sports clothing.

Patent applicant: Uni-Tei Riki Co., Ltd.

Claims (1)

[Claims] (1) A microporous resin film formed on the surface of the fabric and having a porosity of 20 to 70% calculated from the following formula (I) contains a substance having antibacterial properties. Antibacterial, breathable and waterproof fabric. P=(1-[W/S・d]/ρ)×100...(I
) (However, P is the porosity (%), W is the weight of the resin film (g)
, S is the area of the resin film (cm^2), d is the thickness of the resin film (cm), and ρ is the density of the resin (g/cm^3). )