JPS599669B2 - Adhesion treatment method for polyamide synthetic fibers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improvement in a method for adhering polyamide-based synthetic fibers and polyvinyl chloride-based resins.

Conventionally, various adhesives such as polyurethane-isocyanate, epoxy, RFL, and urea/melamine-formalin initial condensate have been known as adhesives between polyamide synthetic fibers and polyvinyl chloride resin, but none of them have adhesive strength. is insufficient, and a satisfactory vinyl chloride coated product has not been obtained. Furthermore, since organic solvents are used, there are also problems in terms of pollution, such as in the working environment. The reasons why polyamide synthetic fibers and vinyl chloride resin are difficult to adhere to are (1) poor compatibility between polyamide synthetic fibers and vinyl chloride, and both being inert in terms of adhesion; (2) vinyl chloride resin (3) The low-molecular-weight plasticizer contained tends to transfer to the adhesive layer, reducing adhesive strength; and (3) the active groups of the adhesive are not activated sufficiently due to the short time it takes to bond due to coating, etc. Can be mentioned.

As a result of fundamental analysis and consideration of this cause, the present inventors found that there is a limit to bonding through a chemical reaction using active groups as with conventional adhesives, and that it is particularly important to increase compatibility. It was discovered that a satisfactory adhesive force could be obtained only by the combination, and this led to the completion of the present invention.

The gist of the present invention is that when bonding a polyamide synthetic fiber and a polyvinyl chloride resin, as a first stage treatment, the synthetic fiber is treated with an aqueous solution of 2 to 10 parts by weight (solid content) of methylol group-containing melamine. ) and 100 to 40 parts by weight (solid content) of an aqueous dispersion of vinyl chloride or its copolymer. , a method for adhesion treatment of polyamide synthetic fibers, characterized by impregnating the adhesive composition B consisting of 20 to 40 parts by weight (solid content) of an aqueous dispersion of vinyl chloride or its copolymer, and drying and then drying. be.

That is, in the present invention, the polyamide synthetic fiber and the adhesive composition A are firmly bonded in the first stage treatment, and then the adhesive composition is bonded to the adhesive composition B while maintaining the thermoplasticity of the adhesive composition B in the second stage treatment. It is glued to A.

Therefore, since the adhesive layer has thermoplasticity, its compatibility with the polyvinyl chloride resin increases, and satisfactory adhesive strength can be obtained even in short-term bonding. The polyamide synthetic fibers used in the present invention include nylon 6, nylon 66
, nylon 610, nylon 12, etc. are used.

The present invention will be explained in more detail below.

In the present invention, the methylol group-containing melamine includes trimethylol melamine, trimethylated methylol melamine, etc., and those commercially available under commercial names such as Sumitekus Resin M-3 are generally used.

In addition, the aqueous dispersion of vinyl chloride or its copolymer includes vinyl chloride monomer, vinyl chloride acrylonitrile butadiene copolymer, vinyl chloride-acrylic acid ester copolymer, and vinyl chloride mono-reactive acrylic acid ester copolymer. Union,
It is an aqueous dispersion of vinyl chloride monovinyl acetate copolymer, etc.
It is generally commercially available as vinyl chloride latex.

In the present invention, adhesive composition A for the first stage treatment consists of 2 to 10 parts by weight (solid content) of a methylol group-containing melamine aqueous solution and 100 to 40 parts by weight (solid content) of an aqueous dispersion of vinyl chloride or its copolymer. ) is used. If the methylol group-containing melamine is less than 2 parts by weight, it will have poor reactivity with fibers, resulting in less formation of three-dimensional networks, resulting in poor adhesion and water resistance, and if it is more than 10 parts by weight, the formation of three-dimensional networks will be promoted. The second stage 5
The compatibility with adhesive composition B in the treatment decreases, resulting in poor adhesive strength. Furthermore, if vinyl chloride or a copolymer thereof exceeds 100 parts by weight, adhesion with fibers will be inhibited, and if it exceeds 40 parts by weight, compatibility with adhesive composition B will become poor, which is not preferable.

In the present invention, as a first stage treatment, fibers are impregnated with the adhesive composition A, and after drying, the adhesive composition A is preferably cured at 160 to 2
Cure for 1-3 minutes at 00°C.

If the curing conditions are lower than this temperature or time, the reactivity with the fibers will be poor, resulting in poor adhesion and water resistance, and if the temperature or time is higher than this, the compatibility with adhesive B will be poor. As it gets worse, the adhesive strength decreases. Note that the amount of adhesion after curing is 5 to 10% by weight based on the fiber. In the present invention, the first-stage treated synthetic fiber is further impregnated with an adhesive composition B consisting of 20 to 40 parts by weight (solid content) of an aqueous dispersion of vinyl chloride or its copolymer,
After drying, cure preferably at 140-200°C for 30 seconds or more.
It is cured for 2 minutes.

If the solid content is less than 20 parts by weight, the compatibility with the polyvinyl chloride resin that is the adherend will be lowered, resulting in a decrease in adhesive strength, and if it is more than 40 parts by weight, the viscosity will be high, making it difficult to use. Sexuality decreases. Furthermore, if the curing conditions are lower than this temperature or time, the water resistance and durability will deteriorate, and if the temperature or time is higher than this, the compatibility with the polyvinyl chloride resin that is the adherend will be poor. This will cause the adhesive strength to deteriorate. Second
The amount of adhesion due to the stage treatment is set to be 5 to 20% by weight based on the fiber. The polyamide synthetic fiber that has been adhesively treated in this manner is coated with a polyvinyl chloride resin by an appropriate method such as lamination or coating.

As described above, according to the present invention, strong adhesion can be achieved even during short-time adhesion, and the adhesion is highly durable and water resistant.

Furthermore, since the adhesive compositions used are both water-soluble, they can be adjusted very easily, and there is an advantage that the treated fibers are not colored. The present invention will be explained in more detail with reference to Examples below.

Example 1 Nylon 66 fabric (840d, 28 strands/inches x 28 strands/inches) was impregnated with various combinations of adhesive compositions A and B below, and after drying, the first stage Cure 180'CX 2 minutes, the second stage Cure Adhesion treatment was performed at 180°C for 1 minute.

The dry adhesion amount was 9% in the first stage and 13% in the second stage. A plasticized polyvinyl chloride sheet with a thickness of 1.5 mm was bonded to the adhesive-treated nylon 66 fabric at 18° C. and 10 k9/Cd for 10 seconds to obtain a vinyl chloride resin-coated product.

After the product was left in a constant temperature atmosphere for a day and night, it was tested with a constant speed elongation tensile tester (Shimadzu Autograph S-500) under the following conditions: 10CT in the vertical direction! Table 1 shows the results of measuring the peeling strength when peeled off.

(Peeling conditions) Burn: ↓i}X'. ! ．． ．． ;i=;::τ冑? As shown in Table 1, according to the present invention, coated products with extremely high adhesive strength can be obtained.

Example 2 In Example 1, vinyl chloride was prepared in the same manner as in Example 1, except that the first stage cure temperature was changed as shown in Table 2 when performing the adhesive treatment by combining Adhesive Washer 3 and /F6.8. A coated product was prepared and the peel strength was measured. The results are shown in Table 2.

As shown in Table 2, it can be seen that the first stage curing temperature is preferably 160 to 200°C.

Example 3 Table 3 shows the results of the same procedure as in Example 1 except that the second stage cure temperature was changed as shown in Table 3.

As shown in Table 3, it can be seen that the second stage curing temperature is preferably 140 to 200°C.

Comparative Example Adhesive in Example 1. S. 3 and adhesive waterfall 8, a coated product (comparative example 1), and further using conventionally known polyurethane-isocyanate adhesive compositions (Comparative Example 2) and RFL (Comparative Example 3) having the following compositions.
Table 4 shows the results of measuring the peel strength of coated products that were subjected to step adhesion treatment and prepared in the same manner as in Example 1.

(Polyurethane-isocyanate system) As is clear from the above examples, the present invention achieves remarkable adhesiveness compared to conventional methods by skillfully combining chemical reaction by active groups and improving compatibility. It is possible to obtain a vinyl chloride coated product having the following characteristics, and its value is extremely great.

Claims (1)

[Scope of Claims] 1. When bonding polyamide synthetic fibers and polyvinyl chloride resin, the synthetic fibers are treated with 2 to 10 parts by weight (solid content) of an aqueous solution of methylol group-containing melamine as a first stage treatment; Aqueous dispersion of vinyl chloride or its copolymer 10
The adhesive composition obtained by mixing 0 to 40 parts by weight (solid content) is impregnated, dried and cured, and as a second stage treatment, an aqueous dispersion of vinyl chloride or its copolymer 20
1. A method for adhesion treatment of polyamide-based synthetic fibers, which comprises impregnating with an adhesive composition consisting of ~40 parts by weight (solid content), drying, and then curing. 2. The method for adhesion treatment of polyamide synthetic fibers according to claim 1, characterized in that in the first stage treatment, curing is carried out at 160 to 200°C. 3. The method for adhesion treatment of polyamide synthetic fibers according to claim 1, characterized in that curing is carried out at 140 to 200° C. in the second stage treatment.