JPH084524B2 - Adhesive composition for adhering water / oil repellent material and method for producing cloth shoes having water / oil repellency using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to an adhesive composition for adhering a water / oil repellent material and a method for producing a water / oil repellent cloth shoe using the same.

Conventional technology and its problems In recent years, the demand for added value of shoes has increased, and shoes with good functions for foot health, especially all-weather type that can be worn even on rainy days, are resistant to dirt on mud, and can be washed repeatedly. There is a strong demand for shoes that retain their original water and oil repellency, have good breathability, and prevent stuffiness. Normally, in order to exert the above-mentioned functions, the shoe cover material has a water repellency of 100 (according to JIS K-6328) and an oil repellency of 6 (AAT).
CC) and after 5 washes (JIS-L0217
It is necessary to use a base material that can maintain the water / oil repellency.

In order to satisfy the above-mentioned demand, for example, 1) a method in which a covering material such as cotton cloth is treated in advance with a fluorine-based water and oil repellent, and then molded into a shoe, 2) a device such as a spray is used. By spraying a solvent-type water and oil repellent agent on the formed shoes, and 3) coating a base material such as cotton cloth with urethane resin in advance to form an ultra-thin coating film, and forming this base material. There has been proposed a method of making shoes having waterproofness. However, the above methods are not preferable because they have the following drawbacks. That is, in the method of 1), when using a frosted material having a high degree of water / oil repellency (water repellency 100, oil repellency 6, maintaining the water repellency even after 5 times of washing) However, it is extremely difficult to attach the shoe covering material, the shoe rubber sole, the rubber tape, etc., with an adhesive. Therefore, as a material for shoes, use a cotton cloth that has a water and oil repellency of 80 to 90, 4 oil repellency, and 60 to 70 water repellency per wash. As the glue, for example, natural rubber glue or the like, to which tris-4-phenylisocyanate thiophosphate marketed under the trade name “Desmodur RF” [manufactured by Bayer GmbH, West Germany] is added, and a latex adhesive is fluorine-containing Attempts have been made to increase the adhesiveness by using those containing a system penetrant. However, the adhesiveness is still not satisfactory, and naturally, the water and oil repellency is not sufficient. The method 2) has drawbacks such as uneven coating, reduced water repellency, and complicated manufacturing process. According to the method 3), the water and oil repellency effect and the air permeability of the obtained cloth shoes are insufficient, and moreover, the texture becomes hard, which is not preferable.

Means for Solving the Problems The present inventor has conducted extensive studies in view of the above problems of the prior art, and as a result, when an adhesive containing a specific polyisocyanate compound and a rubber-based solvent paste is used, , A highly durable water and oil repellency (water repellency 100, oil repellency 6, maintains the water repellency even after 5 times of washing) and shoe rubber soles, rubber tape, etc. The present invention has been completed by finding that it can be adhered to.

That is, the present invention provides the following adhesive composition for adhering a water- and oil-repellent material and a method for producing a water- and oil-repellent cloth shoe using the same.

An adhesive composition for adhering a water- and oil-repellent material, which comprises isophorone diisocyanate prepolymer and a rubber-based solvent paste.

Water- and oil-repellency in which a shoe cover and a shoe rubber sole or a shoe cover, a shoe rubber sole and a rubber tape, which use a fiber cloth having water and oil repellency as a base material, are bonded together by a bonding paste A method for producing a cloth shoe having water and oil repellency, which is characterized in that an adhesive composition containing isophorone diisocyanate prepolymer and a rubber solvent glue is used as the pasting glue.

The adhesive composition of the present invention is used for adhesion for water and oil repellent materials. This adhesive composition achieves the intended effect of the present invention for the first time only when isophorone diisocyanate prepolymer is used as the polyisocyanate compound. Even if another polyisocyanate compound is used, the same effect is not exhibited.

Isophorone diisocyanate prepolymer is a known polyisocyanate compound. In the present invention, as the polymer, the NCO content is usually about 10 to 16% and the molecular weight is 440 to
Any of about 700 can be used. The isophorone diisocyanate prepolymer may be used after diluting it with a suitable solvent. Suitable solvents include, for example, cellosolve acetate, xylene, solvesso and the like.

As the rubber-based solvent paste, any known one can be used, and examples thereof include a natural rubber compound, a natural rubber / MMA copolymer, a synthetic rubber compound, and a natural rubber / synthetic rubber compound. Specific examples thereof include natural rubber, natural rubber MMA copolymer (MG25), SBR, isoprene rubber, synthetic rubber such as chloroprene rubber, natural rubber and NBR.
Rubber such as a mixture with a synthetic rubber such as sulfur, mercaptobenzothiazole, dibenzothiazole disulfide, tetramethylthiuram monosulfide, zinc white,
Examples include stearic acid, rosin resin, light calcium carbonate, magnesium carbonate, preservatives, pigments, and other additives to which additives commonly used in rubber-based solvent pastes are added.
The amount of the above-mentioned additive added is not particularly limited, and the amount usually used may be added. In the present invention, the rubber-based solvent paste may be diluted with an appropriate solvent before use. Examples of the solvent include toluene, methyl ethyl ketone, n-hexane,
Examples thereof include ethyl acetate and rubber volatile oil.

The mixing ratio of the isophorone diisocyanate prepolymer and the rubber-based solvent paste is not particularly limited and may be appropriately selected. Usually, 7 to 70 parts by weight of the isophorone diisocyanate prepolymer is added to 100 parts by weight of the rubber-based solvent paste in terms of solid content. It may be blended to some extent.

The adhesive composition for adhering the water / oil repellent material of the present invention is produced by mixing the above components by a known method. The adhesive thus obtained can be extremely strongly adhered to a material having water and oil repellency, and is not only used as a bonding paste in the method for manufacturing a cloth shoe having water and oil repellency described below, It can be widely used for adhering materials having water and oil repellency, for example, laminating the front and back cloths of shoes, rubberized cloth and other various industrial products,
It can also be used for applications such as carpet materials.

In the manufacturing method of the present invention, as the base material for shoe lace, any fiber cloth having water and oil repellency can be used.
Those having a water / oil repellency capable of maintaining the above water / oil repellency even after 0, oil repellency of 6, and washing 5 times or more are particularly preferably used. As a specific example thereof, for example, a fiber cloth is impregnated with a solution obtained by diluting a water- and oil-repellent agent containing a fluororesin having a perfluoroalkyl group as a main component and an acrylic resin, a silicone resin or the like as a binder with trichlene. 16
What was baked at about 0 ° C. for about 2 to 5 minutes may be used. As the fiber cloth used at this time, any known cloth can be used, and examples thereof include natural cloth such as cotton cloth, vinylon, soup, rayon and hemp, synthetic fiber or artificial fiber. Further, a commercially available water-repellent and oil-repellent processed substrate may be adopted, and specific examples thereof include, for example,
Cotton thread Of twill weave fabric extruded [Shikishima Spinning Co., Ltd.
Manufactured] and the like.

When the water-repellent and oil-repellent material-adhesive adhesive composition of the present invention is used to produce a water-repellent and oil-repellent cloth shoe, for example, it may be carried out as follows. That is, a shoe coat using a water-repellent and oil-repellent fiber cloth as a base material and a shoe rubber sole or a shoe rubber sole and a rubber tape are adhered to each other via the adhesive of the present invention, and then a molding combination according to a conventional method. After that, the fabric shoes having a high degree of water and oil repellency can be manufactured by subjecting this to hot air vulcanization treatment in a vulcanization can as required. The application amount of the adhesive of the present invention is not particularly limited, but it is usually 3 to 6 g (about 1.5 g in terms of solid content) in wet amount per pair. The application of the adhesive may be performed according to a conventional method. Also, the hot air vulcanization treatment is usually 120 to 130.
It may be carried out for about 40 to 90 minutes in a pressurized atmosphere of about 2 ° C / cm ² at ℃.

The shoe of the present invention thus obtained can be used as shoes for all purposes, but is particularly suitable for all-weather school shoes, casual shoes and the like.

Effects of the Invention According to the present invention, the following excellent effects are achieved.

(1) According to the method of the present invention, by using an adhesive containing an isophorone diisocyanate prepolymer and a rubber-based solvent paste, a shoe lace material having a high degree of water and oil repellency, a shoe rubber sole, a rubber tape, etc. Can bond extremely strongly.
In this case, it goes without saying that the shoe covering material is not limited to the one using the fiber cloth, and is widely applicable to a wide range of general covering materials such as natural leather and synthetic leather covering material.

(2) According to the method of the present invention, a cloth shoe having a high degree of water / oil repellency, washing resistance and breathability and having excellent durability can be manufactured easily at low cost. In addition, there are no coating unevenness, deterioration in durability, etc. as seen when spray-coating a solvent-based water and oil repellent.

(3) Compared to a cotton cloth or the like coated with a urethane resin, the texture does not become hard, the soft texture of the cotton cloth or the like can be maintained, and a well-balanced shoe can be obtained.

(4) The adhesive composition for adhering a water / oil repellent material of the present invention can extremely strongly adhere to a material having a water / oil repellency, and is only used as a bonding paste in the above production method. Instead, it can be widely used for bonding materials having water and oil repellency.

Examples The following examples and comparative examples will further clarify the present invention.

Example 1 of cotton yarn The twill weave fabric is made of an extrinsic base material (manufactured by Shikishima Spinning Co., Ltd.) that has been treated with a fluororesin that maintains water repellency of 100, oil repellency of 6, and the water repellency of 5 times or more after washing. Used as a shoe coat. A book containing 100 parts by weight of a natural rubber solvent glue solution having the following composition and 10 parts by weight of isophorone diisocyanate prepolymer (trade name: Desmodur Z4370, manufactured by Bayer GmbH, West Germany) with the shoe cover, the shoe rubber sole and the rubber tape. The invention adhesive was applied and attached. The applied amount was about 6 g / foot. After molding and assembling this, use a vulcanizer at 130 ℃, 2Kg / cm
The shoe of the present invention was manufactured by hot air vulcanization for 60 minutes under the pressure of ² .

Natural rubber Solvent paste solution Natural rubber 100 parts by weight Sulfur 2.5 parts by weight Mercaptobenzothiazole 0.3 parts by weight Dibenzothiazole disulfide 0.3 parts by weight Tetramethylthiuram monosulfide 0.1 parts by weight Zinc Hua No. 1 8.0 parts by weight Stearic acid 1.0 parts by weight Light Calcium carbonate 52 parts by weight Styrenated phenol (anti-aging agent) 1.0 parts by weight The above components were kneaded and dissolved in toluene to prepare a natural rubber solvent paste solution having a concentration of 30%.

The obtained shoes were subjected to a normal state adhesive strength test and a water resistant adhesive strength test (measurement of adhesive strength after immersing the sample in water for 24 hours) specified in JIS K6301. The results are shown in Table 1.

Comparative Example 1 A shoe was manufactured in the same manner as in Example 1 except that the isophorone diisocyanate prepolymer was not used.

Comparative Example 2 A hexamethylene diisocyanate polymer [trade name: Duranate AD-70, manufactured by Asahi Kasei Co., Ltd.] was used in place of the isophorone diisocyanate prepolymer.
A shoe was manufactured in the same manner as in Example 1.

Comparative Example 3 A shoe was manufactured in the same manner as in Example 1 except that diphenylmethane diisocyanate polymer [trade name: Nipporan 3030, manufactured by Nippon Urethane Co., Ltd.] was used in place of the isophorone diisocyanate prepolymer.

Comparative Example 4 A shoe was manufactured in the same manner as in Example 1 except that tolylene diisocyanate polymer [trade name: Desmodur E-14, manufactured by Bayer AG, West Germany] was used instead of the isophorone diisocyanate prepolymer.

Comparative Example 5 A shoe was manufactured in the same manner as in Example 1 except that tris-4-phenyldiisocyanate polymer [trade name: Desmodur RF, manufactured by Bayer GmbH, West Germany] was used in place of the isophorone diisocyanate prepolymer.

The shoes obtained in Comparative Examples 1 to 5 were subjected to the same performance test as in Example 1. The results are shown in Table 1.

It can be seen from Table 1 that excellent adhesive strength is exhibited when the adhesive of the present invention is used, and that the adhesive strength is sufficient even when a polyisocyanate compound other than the isophorone diisocyanate prepolymer used in the present invention is used. It turns out that not.

To test the durability of the shoes obtained in Example 1 (hereinafter referred to as the product of the present invention) and the shoes obtained in Comparative Examples 1 to 5 (hereinafter referred to as the comparative product), Tokuyama Factory, the world head. Smelting section Rubber kneading worker (standing work, transportation, walking work, 7 ~ per day
After 9 hours of work, the test shoes were worn for 2 months (the number of times of washing during the test shoes was 1 to 3 times). After the test, the condition of the shoe was observed, and it was found that the bent portion and the peripheral adhesive portion of the shoe of the present invention were completely adhered to each other, showed good water repellency and breathability, and were resistant to dirt. On the other hand, in the comparative product, the bent portion was peeled off on the first day, and the surrounding area was enlarged and peeled off after 7 days.

Example 2 A normal temperature glue solution having the following composition was used in place of the natural rubber solvent glue solution, and hot air vulcanization was not performed, except that
The shoe of the present invention was manufactured in the same manner as in Example 1. The obtained shoes had extremely excellent durability, good water repellency and breathability, and were resistant to mud stains.

Room temperature glue solution Chloroprene AD90 [trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.] 90
Parts by weight chloroprene MMA copolymer 10 parts by weight zinc white 5 parts by weight magnesium oxide 4 parts by weight rosin resin 2 parts by weight ditertiarybutyl paracresol (anti-aging agent) 1 part by weight 25 parts by weight of the above-mentioned components are mixed with toluene It was dissolved in 75 parts by weight to prepare a 25% room temperature glue solution.

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Claims (2)

[Claims] 1. An adhesive composition for adhering a water / oil repellent material, which comprises an isophorone diisocyanate prepolymer and a rubber-based solvent paste. 2. A molding combination in which a shoe cover and a shoe rubber sole, or a shoe cover, a shoe rubber sole, and a rubber tape, which use a water-repellent and oil-repellent fiber cloth as a base material, are adhered with a bonding paste. In the method for producing a water- and oil-repellent cloth shoe, the adhesive composition containing an isophorone diisocyanate prepolymer and a rubber-based solvent paste is used as the pasting glue, and the water- and oil-repellent cloth is obtained. How to make shoes.