JP2000129059A - Polyvinylchloride-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which shows excellent high speed tensile properties without sacrificing advantages of a hard polyvinylchloride-based resin by mixing a specific amount of a partially crosslinked acrylonitrile- butadiene copolymer and a thermoplastic polyurethane elastomer with the polyvinylchloride-based resin. SOLUTION: 1-40 pts.wt. of a partially crosslinked acrylonitrile-butadiene copolymer (B) and 1-50 pts.wt. of a thermoplastic polyurethane elastomer (C) are mixed with 100 pts.wt. of a polyvinylchloride-based resin. A polymerization degree of the component A to be used is 700-2,000, preferably 700-1,500. The component B to be used contains 20-40% of acrylonitrile and Mooney viscosity of 30-80 ML1+4 (100 deg.C). The component C is a polyester-based polyurethane preferably having shore hardness of 70-90.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a vinyl chloride resin composition containing a vinyl chloride resin and three components of a partially crosslinked acrylonitrile-butadiene copolymer (hereinafter abbreviated as NBR) and a thermoplastic polyurethane elastomer. More specifically, the present invention relates to a vinyl chloride resin composition having excellent high-speed tensile strength and elongation, excellent impact resistance, and good workability.

[0002]

2. Description of the Related Art In order to improve the high-speed tensile properties of a vinyl chloride resin, a predetermined amount of a plasticizer is blended into a soft vinyl chloride resin composition, or a thermoplastic monomer is copolymerized with a vinyl chloride monomer. This has been dealt with by using a resin that has been used. However, a soft vinyl chloride resin composition using a plasticizer cannot be used in applications such as an environment in which the plasticizer is eluted due to migration and the deterioration is severe. Further, even in the case of compositions using various vinyl chloride copolymer resins,
The amount of the thermoplastic monomer component used for the copolymerization is generally smaller than the amount of the vinyl chloride monomer component, and the use of these vinyl chloride copolymer resin compositions alone improves the high-speed tensile properties. In many cases, it is not possible to use a small amount of plasticizer. Even in this case, the usage is limited as in the case of the soft vinyl chloride resin composition. Furthermore, when a soft vinyl chloride resin composition obtained by blending a plasticizer with a vinyl chloride resin is evaluated for high-speed tensile properties in accordance with JIS K-6723, the tensile strength is considerably lower than 11.8 MPa. Rigidity cannot be given to molded products. In the case of a vinyl chloride copolymer resin composition, the tensile strength may be equal to or higher than that of the hard vinyl chloride resin composition in the high-speed tensile evaluation shown in JIS K-6723, but the elongation is a softness in which a plasticizer is blended. It is considerably lower than the vinyl chloride resin composition. Further, a two-component blend of a vinyl chloride resin and NBR or a two-component blend of a vinyl chloride resin composition and a thermoplastic polyurethane elastomer exhibits either high strength or high elongation of high-speed tensile properties. But you can't make them both big. Although knowledge about such a composition of a blend of a vinyl chloride resin and a thermoplastic polymer has been known, methods for evaluating tensile properties differ depending on the application to be used, and thus a device for improving both tensile strength and elongation has been devised. I didn't.

[0003]

As a result of intensive studies in view of the above circumstances, a vinyl chloride resin composition containing no plasticizer, which is the object of the present invention, is used in the production of soft vinyl chloride using a plasticizer. The purpose of the present invention is to obtain a vinyl chloride resin composition having a high-speed tensile elongation equivalent to that of a resin composition and a high-speed tensile strength having a tensile strength equivalent to that of a hard to semi-rigid vinyl chloride resin composition. An object of the present invention is to provide a three-component blend of a vinyl chloride resin, a partially crosslinked NBR, and a thermoplastic polyurethane elastomer.

[0004]

That is, according to the present invention, a partially crosslinked acrylonitrile-butadiene copolymer is used in an amount of 1 to 40 parts by weight, preferably 15 to 30 parts by weight, based on 100 parts by weight of a vinyl chloride resin. The present invention relates to a vinyl chloride resin composition comprising a plastic polyurethane elastomer in an amount of 1 to 50 parts by weight, preferably 10 to 30 parts by weight.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

Although the degree of polymerization of the vinyl chloride resin used in the present invention can be in the range of 400 to 2,000, improvement of high-speed tensile properties can be expected by using a substance having a high degree of polymerization. Since the processing using the method of kneading and molding the vinyl chloride resin composition is difficult, the polymerization degree is preferably in the range of about 700 to 1500.

[0007] The vinyl chloride resin mentioned herein includes not only a vinyl chloride homopolymer but also a copolymer of a monomer copolymerizable with vinyl chloride and a vinyl chloride monomer, and is not particularly limited. Examples of monomers copolymerizable with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene and propylene;
(Meth) acrylates such as methyl acrylate,
Maleic anhydride, acrylonitrile, styrene, vinylidene chloride and the like can be mentioned. These can be used alone or in combination of two or more.

The partially crosslinked NBR has an acrylonitrile content of 20 to 40% and a Mooney viscosity of 30 to 80 ML.
_{1 + 4} (100 ° C.), preferably partially crosslinked N having an acrylonitrile content of 25% to 35% and a Mooney viscosity of 50 to 65 ML _{1 + 4} (100 ° C.).
BR is preferred. The Mooney viscosity referred to here is JI
It is a value measured according to SK-6300.

When the acrylonitrile content is out of the range of 20 to 40%, the compatibility with the vinyl chloride resin decreases, resulting in poor dispersion, and the desired physical properties cannot be obtained.

The Mooney viscosity is 30 ML _{1 + 4} (10
When the temperature is less than 0 ° C., the initial elastic modulus decreases and the same behavior as that of the soft vinyl chloride resin composition containing a plasticizer is exhibited.
Conversely, if the Mooney viscosity is greater than 80 ML _{1 + 4} (100 ° C.), there is a problem that the processability deteriorates. The thermoplastic polyurethane elastomer is preferably a polyester-based polyurethane having a Shore A hardness of 70 to 90, preferably 75 to 85. If the Shore A hardness is less than 70, there is a problem that the initial elastic modulus is reduced. Conversely, if the Shore A hardness is more than 85, dispersion in the resin phase becomes poor, and desired physical properties cannot be obtained. Here, the Shore A hardness is a measured value based on a test method of JIS B-7727. In order to obtain the above-mentioned vinyl chloride-based resin composition, a kneaded and pelletized product obtained by the same compounding method as for a normal vinyl chloride-based resin is again extruded into a desired molded product by a molding machine such as an extruder or an injection molding machine. Can be molded. The above-mentioned kneading method for pelletizing is performed by kneading at 150 ° C. to 180 ° C. using a kneader such as a pressure kneader, a coal, or a Banbury mixer. The process for producing pellets of the vinyl chloride resin composition in the present invention is the same as a conventionally known process, and the compounding agent is a conventionally known compounding agent such as a heat stabilizer, a processing aid, a filler, an ultraviolet absorber, A coloring agent, a lubricant and the like are used without any particular limitation. The heat stabilizer is used in an amount of 1 to 7 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. Specifically, for example, commonly used heat stabilizers such as Ba-Zn-based stabilizer, Ca-Zn-based stabilizer, Sn-based stabilizer, Pb-based stabilizer, Mg-Al stabilizer, and hydrotalcite-based stabilizer are used. May be used alone or in combination of two or more. The processing aid is added in an amount of 0 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. Specific examples include commonly used processing aids such as an MMA-based processing aid containing methyl methacrylate as a main component, and a polyester-based processing aid containing adipic acid as a main component.
More than one species may be used in combination. The filler is 0 to 20 parts by weight, preferably 1 to 1 part by weight, based on 100 parts by weight of the vinyl chloride resin.
0 parts by weight are blended. Specific examples include commonly used fillers such as calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, and talc, which may be used alone or in combination of two or more. The UV absorber is used in an amount of 0 to 6 parts by weight, preferably 0 to 3 parts by weight, based on 100 parts by weight of the vinyl chloride resin. Specifically, for example, a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, and a cyanoacrylic-based ultraviolet absorber may be mentioned, and these may be used alone or in combination of two or more. The lubricant is used in an amount of 0 to 10 parts by weight, preferably 0 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. Specific examples include commonly used lubricants such as higher fatty acid metal salts such as calcium stearate, higher alcohols, and polyethylene waxes. These may be used alone or in combination of two or more. Further, a colorant or other thermoplastic resin may be blended, and the type and the amount of addition may be appropriately selected and used depending on the purpose within a range that does not impair the purpose of the present invention.

[0011]

EXAMPLES Examples of the three-component vinyl chloride resin composition of the present invention comprising a vinyl chloride resin, partially crosslinked NBR, and a thermoplastic polyurethane elastomer are shown below, but the present invention is limited to only these examples. It is not something to be done.

(Examples 1 to 5) Partly crosslinked NBR (acrylonitrile content = 3) with respect to 100 parts by weight of vinyl chloride resin
5%, Mooney viscosity = 60 ML _{1 + 4} (100 ° C.) 10-30 parts by weight and thermoplastic polyurethane elastomer (Shore A hardness = 75) 30-30 parts by weight (Examples 1-5) The resin temperature is 18 with a pressure kneader
The mixture was kneaded to 0 ° C. and then rolled at 180 ° C. for about 3 minutes to prepare a roll sheet, which was finely cut with a sheet cutter and pelletized.

The other composition at this time is as follows. Sn stabilizer 5 per 100 parts by weight of vinyl chloride resin
Parts by weight, a total of 1.2 parts by weight of two types of polyethylene wax, 0.3 parts by weight of calcium stearate, and 2 parts by weight of an MMA-based processing aid. The pellets were subjected to injection molding to prepare a 3 mm thick JIS K-7113 No. 1 dumbbell and a 5 mm thick JISK-7111 Charpy test sample bar.

(Comparative Examples 1 to 5) Vinyl chloride resin 100
A soft vinyl chloride resin composition containing 30 and 50 parts by weight of a plasticizer DOP with respect to parts by weight (Comparative Examples 1 and 2) was kneaded to a resin temperature of 150 ° C. by a pressure kneader, and then pelletized through a granulator. Was. Also, vinyl chloride resin 100
Those obtained by mixing 0 to 30 parts by weight of MBS as an impact modifier with respect to parts by weight (Comparative Examples 3 to 5) were extruded and pelletized.

At this time, the other composition was the same as that of the embodiment. In these comparative examples, injection molding was performed in the same manner as in the above-described examples to prepare No. 1 dumbbells and Charpy test sample bars. The injection conditions were appropriately changed according to each material, and a molded article was obtained in an optimal state. Next, the above Examples 1 to 5 and Comparative Example 1
The test samples prepared in Nos. To 5 were evaluated according to the following methods.

[Evaluation of High-Speed Tensile Test] Using a dumbbell prepared by the above-mentioned injection molding, the test was performed according to JIS K-6723.
A tensile test was performed at a tensile speed of 200 mm / min in an environment of ° C. to obtain a 1% modulus (1% M: Kg / cm ² ), a yield stress (σy: Kg / cm ² ), and an elongation (%).

[Charpy test] A sample bar having a V-notch with a depth of 1 mm on one side was used in accordance with JIS K-7111. The test temperature was 23 ° C and 0 ° C. Table 1 shows the evaluation results of Examples 1 to 5 and Comparative Examples 1 to 5.

[0018]

[Table 1]

[0019]

As shown in Examples 1 to 5, according to the present invention, without impairing the advantages of hard vinyl chloride resin,
A molded article of a rigid vinyl chloride resin composition having excellent high-speed tensile properties can be provided.

Claims (4)

[Claims] 1. A partially crosslinked acrylonitrile-butadiene copolymer 1 to 40 with respect to 100 parts by weight of a vinyl chloride resin.
Parts by weight, and a thermoplastic polyurethane elastomer 1 to 5
A vinyl chloride resin composition comprising 0 parts by weight. 2. The polymerization degree of the vinyl chloride resin is 400 to 2
The vinyl chloride-based resin composition according to claim 1, wherein the molecular weight is in the range of 000. 3. The partially crosslinked acrylonitrile-butadiene copolymer has an acrylonitrile content of 20 to 40% and a Mooney viscosity of 30 to 80 ML _{1 + 4} (100 ° C.). The vinyl chloride resin composition as described in the above. 4. The thermoplastic polyurethane elastomer is a polyester-based polyurethane, and has a Shore A hardness in the range of 70 to 90.
4. The vinyl chloride resin composition according to any one of 3.