JPS60233140A - Vinyl chloride based resin composition - Google Patents

Abstract

PURPOSE:The titled composition, obtained by incorporating vinyl chloride resin with a mercaptobenzothiazole based compound or its salt, and having extremely improved resistance to discoloration caused by amines. CONSTITUTION:A vinyl chloride based resin compositon obtained by incorporating (B) 0.1-2pts.wt., preferably 0.5-1.5pts.wt. mercaptobenzothiazole based compound or its salt, preferably 2-mercaptobenzothiazole, dibenzothiazyl disulfide, zinc mercaptobenzothiazole or diphenylguanidine mercaptobenzothiazole with (A) 100pts.wt. vinylchloride resin (in case of elastomeric polyvinylchloride, 20- 200pts.wt. plasticizer and 0.3-5pts.wt. stabilizer are usually added). The discoloration can be prevented even when the composition is laminated on polyurethane containing, for example, a diamine based compound to form a composite material, and the composition can be suitably used.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vinyl chloride resin composition that has significantly improved resistance to discoloration and deterioration caused by amines.

It is known that vinyl chloride resins are colored by dehydrochlorination by heat, ultraviolet rays, etc. For this reason, various stabilizers have traditionally been added when processing vinyl chloride resins.
Efforts are made to prevent quality deterioration due to such coloring. However, the vinyl chloride resin is colored or discolored not only by heat and ultraviolet rays as described above, but also when the vinyl chloride resin comes into contact with polyurethane. For example, when an adhesive material between a vinyl chloride resin sheet and polyurethane is kept in a sealed state for a long period of time, the vinyl chloride resin will discolor and deteriorate. In particular, this tendency becomes more pronounced as the environmental temperature increases. More specifically, for example, shoe covers made by thermally bonding foamed polyurethane to the back side of so-called leather made of vinyl chloride resin, and polyurethane cast soles bonded to shoe covers made of vinyl chloride resin leather. When shoes made of the same material are kept sealed at relatively high temperatures for a long period of time, the vinyl chloride resin changes color to yellow or yellowish purple. In addition, composite materials made by bonding vinyl chloride resin to wood or steel plates using an adhesive such as an epoxy resin adhesive containing an amine compound as a 4-curing agent can also be used as described above. Discoloration occurs.

Such discoloration of vinyl chloride resin occurs when polyurethane contains a diamine compound as a chain extender.
It also occurs when vinyl chloride resin comes into contact with amine gas, so amines are thought to be the cause.

Therefore, in order to prevent the above-mentioned discoloration of vinyl chloride resins due to amine contamination, there has been a known method of adding large amounts of fatty acid zinc salts such as titanium dioxide or zinc stearate to vinyl chloride resins. There is. However, according to the former method, although the discoloration of the vinyl chloride resin is reduced to some extent, the desirable physical properties of the vinyl chloride resin deteriorate, and the manufacturing cost becomes high. In addition, according to the latter method, although the discoloration of vinyl chloride resin is considerably improved by adding a large amount of fatty acid zinc salt, the heat resistance is significantly deteriorated, and the resin rapidly deteriorates due to heat during rolling. It may be decomposed into

The present inventors conducted extensive research to prevent the discoloration of vinyl chloride resin that occurs when vinyl chloride resin and polyurethane come into contact with each other as described above. The present invention was achieved based on the discovery that the discoloration described above can be effectively prevented by containing a small amount of a salt thereof.

That is, the vinyl chloride resin according to the present invention is characterized by containing a mercaptobenzothiazole compound or a salt thereof.

In the present invention, the vinyl chloride resin includes not only a homopolymer of vinyl chloride but also a copolymer of vinyl chloride, and such copolymers include, for example, vinyl chloride and ethylene,
Copolymers with one or more monomers such as vinyl acetate, vinyl ether, maleic ester, vinylidene chloride, and acrylic ester can be mentioned. Also,
A mixture of these vinyl chloride resins and other resins may be used. Furthermore, the vinyl chloride resin composition according to the present invention includes a mercaptobenzothiazole compound or a salt thereof;
Along with the vinyl chloride resin, it may contain various additives normally contained in the vinyl chloride resin, such as plasticizers, stabilizers, pigments, fillers, ultraviolet absorbers, antioxidants, antistatic agents, etc. . Further, fatty acid metal salts such as zinc salts and titanium oxide may be contained as long as they do not impair the preferable properties of the vinyl chloride resin.

The resin composition of the present invention can be applied to both so-called soft and hard vinyl chloride early resins, but in the case of soft vinyl chloride resins, such vinyl chloride resins are usually used for polyvinyl chloride or vinyl chloride copolymerization-terminated resins. For 00 parts by weight, plasticizer 2
0 to 200 parts by weight and 0.3 to 5 parts by weight of stabilizer.

As the mercaptobenzothiazole compound or its salt used in the present invention, various compounds having a thiazole group can be used, but preferably 2-mercaptobenzothiazole, dibenzothiazyl disulfide, mercaptobenzothiazole zinc salt, mercaptobenzothiazole Examples include thiazole diphenylguanidine salt, mercaptobenzothiazole phthalate, and cupric mercaptobenzothiazole salt. These may be added to the vinyl chloride resin alone or as a mixture of two or more.

The amount of the above-mentioned mercaptobenzothiazole compound or its salt added to the vinyl chloride resin depends on the resin used and its composition, for example, if plasticizers or fillers are included, their types and amounts. However, usually vinyl chloride resin 1
The range of 0.1 to 2 parts by weight relative to 0.00 parts by weight is preferred, and the range of 0.5 to 1.5 parts by weight is particularly preferred.

As described above, vinyl chloride resins containing mercaptobenzothiazole compounds or salts thereof are effectively prevented from discoloring due to amines, and also have excellent heat resistance.

The amount added is based on 100 parts by weight of vinyl chloride resin,
When the amount is less than 0.1 part by weight, the effect of suppressing discoloration is small; on the other hand, even if the amount exceeds 2 parts by weight, the effect of suppressing coloration is saturated, and the heat resistance decreases. Disorders such as bloom may occur.

As described above, the vinyl chloride resin composition of the present invention contains a mercaptobenzothiazole compound or a salt thereof and effectively prevents discoloration caused by amines, and therefore contains, for example, a diamine compound as a chain extender. Composite materials can be made by laminating them with polyurethane, or by bonding vinyl chloride resin sheets to plywood, steel plates, or other base materials using an adhesive made of such polyurethane or an epoxy resin adhesive that uses amine as a hardening agent. Even when
Discoloration of vinyl chloride resin can be effectively prevented.

Therefore, the vinyl chloride resin according to the present invention includes a shoe cover made by adhering a foamed sheet made of polyurethane to vinyl chloride resin leather, a shoe sole made of polyurethane, and a vinyl chloride resin leather cover. It can be suitably used for shoes, sheets and various molded products made of composite materials of vinyl chloride resin and polyurethane, vinyl chloride resins bonded using amine hardeners, and the like.

The present invention will be explained in detail below using Examples, but the present invention is not limited to these Examples.

Example 1 As shown in Table 1, polyvinyl chloride was mixed with plasticizers, stabilizers, etc., and heated to 160° with a 10-inch test roll.
Knead for 5 minutes at C and process into a sheet with a thickness of 0.2.
Inventive products 1 to 6 and comparative products 1 to 3 were obtained.

(1) Effect of preventing discoloration caused by amines Each invention product and comparative product were cut into 5 cm square pieces.
It was used as a test piece. After immersing each of the above test pieces in a 20% solution of pentaethyldiethylenetriamine dissolved in dioctyl phthalic acid at room temperature for 3 hours, the surface was wiped and exposed for a predetermined time in a gear oven at 120°C to examine the degree of discoloration. . The results are shown in Table 2. Here, the evaluation was based on the following.

That is, 1 indicates a faint yellow or purple coloration, 5 indicates a marked yellow or purple coloration, and the degree of discoloration is 1.
Evaluation was made on a scale of 5 to 5.

Table 2 (2) Heat Resistance Next, each test piece was exposed to a gear oven at 180° C. for 1 hour, and its black discoloration was examined. The results are shown in Table 2. In the table, O indicates that the color remained brown, Δ indicates that the color changed to blackish brown, and × indicates that the color changed completely to black.

As is clear from the above, by adding a mercaptobenzothiazole compound or a salt thereof to the vinyl chloride resin, discoloration due to amine contamination in the vinyl chloride resin can be effectively suppressed.

In particular, the effect is remarkable in the zinc salt of mercaptobenzothiazole and the diphenylguanidine salt of mercaptobenzothiazole, and the vinyl chloride resin also has excellent heat resistance.

Example 2 Inventive product 2 and comparative product 1 obtained in Example 1 were each laminated with a base fabric to produce shoe covers.

A polyurethane cast sole made of polyol as a crosslinking agent using ethylenediamine as a chain extender is adhered to the above-mentioned shoe cover to produce shoes, and this is sealed in a polyethylene bag.
Heated at 0°C for 48 hours. As a result, the vinyl chloride resin portion of the shoes produced using Comparative Product 1 exhibited a yellowish color, but no discoloration was observed in the shoes produced using Invention Product 3.

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Claims (2)

[Claims] (1) A vinyl chloride resin composition containing a mercaptobenzothiazole compound or a salt thereof. (2) The mercaptobenzothiazole compound or its salt is 2-mercaptobenzothiazole, dibenzothiazyl disulfide, mercaptohenzo□thiazole zinc salt, mercaptohenzothiazole diphenylguanidine salt, mercaptobenzothiazole phthalate, mercaptobenzothiazole secondary At least one selected from copper salts
The vinyl chloride resin composition according to claim 1, which is a seed. (3) Mercaptobenzothiazole compound or its salt is vinyl chloride resin 1
The vinyl chloride resin composition according to claim 1 or 2, wherein the vinyl chloride resin composition is contained in an amount of 0.1 to 2 parts by weight per 00 parts by weight.