JPS6410012B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a vinyl chloride resin composition that provides excellent matte molded products. (Prior Art) Conventionally, in order to obtain a matte soft vinyl chloride resin molded product, a method of lowering the molding temperature has been adopted. However, with this method, the resin is not sufficiently melted and kneaded in a molding machine such as an extruder, resulting in the resulting molded product having poor mechanical properties.In addition, the low die temperature causes the resin and mold to interact. The disadvantage is that the frictional resistance is large and uneven surface roughness of the molded product becomes noticeable. (Structure of the Invention) The present invention relates to a vinyl chloride resin composition that provides a vinyl chloride resin molded article having an excellent matte appearance without the disadvantages of the conventional ones. 100 parts by weight of resin,
(b) Polyethylene with an average molecular weight of 500 to 6000 0.4 to 2.0
(iii) 0.4 to 3.0 parts by weight of polyethylene oxide having an average molecular weight of 500 to 3,000, and a necessary amount of a plasticizer. The resin composition of the present invention has moldability equivalent to that of ordinary vinyl chloride resin compounds, and can be molded at a molding temperature at which the inherent mechanical properties of vinyl chloride resin are fully expressed. A molded article with a remarkable matte surface effect is obtained, which also has the advantage of being a molded article with excellent mechanical strength. To explain this, in order for the vinyl chloride resin composition of the present invention to exhibit its excellent matting effect, components (b) and (c) are extremely important, and if either one is absent, However, it is not possible to obtain a high degree of matte effect. The polyethylene as component (b) and the polyethylene oxide as component (c) are each required to have a molecular weight within the above-mentioned range. If the molecular weight is too small, the matting effect is difficult to appear, and if the amount added is increased to compensate for this, the mechanical properties of the molded product will be greatly deteriorated.On the other hand, if the molecular weight is too large, the vinyl chloride resin This is because, in this case as well, the mechanical properties of the molded article deteriorate as the compatibility with the molded article deteriorates, and the surface of the molded article becomes rough. As the above-mentioned (b) polyethylene, commercially available polyethylene wax (terminal hydroxyl group, molecular weight 500-6000)
Of course, any polyethylene with a molecular weight in the range of 500 to 6,000 obtained by polymerizing ethylene at a low degree of polymerization can be used. However, those having a molecular weight preferably in the range of 800 to 2,500, more preferably 1,000 to 2,500 are preferred. The oxidized polyethylene as the component (c) is an oxidized product of low molecular weight polyethylene, which is conventionally known as a floor polishing wax or fiber treatment agent, and has a molecular weight in the range of 500 to 3000. If available, either fully oxidized or incompletely oxidized polyethylene may be used. However, those having a molecular weight preferably in the range of 800 to 2,500, more preferably 1,000 to 2,500 are preferred. Commercially available polyethylene oxide products include polyethylene oxide 629A and 6A manufactured by Allied Chemical Co., Ltd.
etc., and can be used in the present invention. The mixing ratio of component (b) and component (c) to (a) vinyl chloride resin is 0.4 to 2.0 parts by weight (preferably 0.5 to 1.5 parts by weight of component (b) per 100 parts by weight of vinyl chloride resin).
parts by weight), component (c) is 0.4 to 3.0 parts by weight (preferably
(0.5 to 2.0 parts by weight). If either component (B) or component (C) is too small, the matting effect will be poor and the objective will not be achieved.On the other hand, if either component (B) or component (C) is too large, slippage will be large. As a result, sufficient melting and gelation is not achieved during kneading of the resin in a molding machine such as an extruder, resulting in molded articles having poor appearance and poor mechanical properties. By adding and blending components (B) and (C) to vinyl chloride resin in this way, it is possible to obtain a molded product with a remarkable matte effect, but this effect is limited by the molding temperature. It is fully demonstrated even when the temperature is set to a sufficiently high temperature, for example, 180°C, and the resulting molded product also has the advantage of having excellent mechanical properties. Also, this
The matting effect can be further promoted by adding (d) a crosslinking agent along with components (b) and (c), but this addition is optional. The crosslinking agent added for this purpose is 6-R-1,3,5
-triazine-2,4-dithiol, 6-dibutylamino-1,3,5-triazine-2,4-dithiol, 2-R-4,6-dimercapto-S-
Examples include triazine. The amount of the crosslinking agent added is preferably 0.1 to 0.4 parts by weight per 100 parts by weight of vinyl chloride resin,
If this amount is too large, the mechanical properties of the molded product will deteriorate, so care must be taken. In addition, when using the above crosslinking agent, it is desirable to use a metal activator such as magnesium oxide (MgO) or barium oxide (BaO) in combination, and the amount of this addition is
The amount is approximately 2 to 7 parts by weight per 100 parts by weight. A molded article formed by adding the above-mentioned crosslinking agent has the advantage that it has an even better matte effect and also has improved surface smoothness. The vinyl chloride resins targeted by the present invention include vinyl chloride homopolymers and copolymers mainly composed of vinyl chloride, and examples of comonomers copolymerized with vinyl chloride include vinyl esters such as vinyl acetate, and acrylic acid. or esters thereof, styrene, maleic anhydride, acrylonitrile, olefins such as ethylene and propylene, and vinylidene chloride. On the other hand, plasticizers include dioctyl phthalate (DOP), dibutyl phthalate (DBP), and tricresyl phosphate (TCP), as well as epoxy plasticizers, polyester plasticizers, adipic acid plasticizers, and trimeritz. Examples include acid plasticizers. These plasticizers are added in appropriate amounts depending on the softness of the intended molded product (soft molded product), and may be the same as conventional ones. In addition, if necessary, stabilizers such as basic lead sulfate, calcium stearate, barium stearate, and other complex salts, fillers such as titanium white, calcined clay, and calcium carbonate, pigments such as carbon black, and acrylonitrile-butadiene-styrene. Similarly to the conventional method, modified resins such as resins, urethane resins, ethylene-vinyl acetate resins, and chlorinated polyethylenes may be blended. The resin composition of the present invention can be obtained by uniformly mixing the above-mentioned essential components and each component added as necessary by a conventionally known method using a Henschel mixer, a ribbon blender, or the like. In order to obtain a molded article from this, various conventionally known molding methods can be employed. For example, the compounded composition is kneaded using a mixer such as an extruder, roll kneader, or Banbury mixer; After pelletizing, it can be molded according to the desired product, and the molded product thus obtained has an excellent matte surface effect and good mechanical properties, so it can be used for general sheets, synthetic leather, synthetic resin tiles, and electric wire sheaths. and other various products. Next, specific examples of the present invention will be given. Example 1 (Experiment Nos. 1 to 11) Vinyl chloride resin TK-1300 (trade name manufactured by Shin-Etsu Chemical Co., Ltd.), dioctyl phthalate (DOP), calcium carbonate, tribasic lead sulfate, lead stearate, polyethylene (Note 1) ), and polyethylene oxide (Note 2) in the proportions shown in Table 1, and heated at 140°C.
It was extruded into pellets. This pellet is extruded using an extrusion molding machine equipped with a T-die with a thickness of 1 mm at a processing temperature (resin temperature at the exit of the die) of 150°C or 180°C to a thickness of approximately 1 mm.
When a sheet of 2 mm thick was obtained, its surface matte state, surface smoothness, tensile strength (Kg/cm ² ), and elongation (%) were as shown in Table 1. (Note 1) Polyethylene: Polyethylene with an average molecular weight of approximately 2000, manufactured by Allied Chemical Company AC6 (Note 2) Oxidized polyethylene: incompletely oxidized polyethylene with an average molecular weight approximately 2000, manufactured by Allied Chemical Company AC 629A Matte state: relative to the sheet surface After a comparative study, the degree of matting effect was judged in the following four stages. A: Great matte effect B: Average matte effect C: Slightly matte effect D: No matte effect Surface smoothness: Comparatively examine the sheet surface,
The degree of smoothness effect was evaluated in the following four stages. A: Very smooth B: Good C: Slightly rough D: Considerably rough Tensile strength (Kg/cm ² ) } Elongation (%) according to JIS K 6723

【table】

[Table] Example 2 (Experiment Nos. 12 to 15) Vinyl chloride resin TK-1300, dioctyl phthalate (DOP), calcium carbonate, tribasic lead sulfate,
polyethylene, oxidized polyethylene, 6-R-1,
3,5-triazine-2,4-dithiol (crosslinking agent) and magnesium oxide were blended in the proportions shown in Table 2, and the mixture was extruded at 130°C to form pellets.
However, the same polyethylene and polyethylene oxide as in the previous example were used. This pellet was extruded using an extrusion molding machine equipped with a T-die having a thickness of 1 mm at a processing temperature (resin temperature at the exit of the die) of 180°C to obtain a sheet having a thickness of about 1 mm. The matte state and surface smoothness of this product were determined in the same manner as in the previous example, and the results were as shown in Table 2.

【table】

[Table] Example 3 (Experiment No. 16 to 19) Vinyl chloride resin TK-1300, tribasic lead sulfate,
Epoxidized soybean oil, barium-zinc stabilizer (stabilizer), polyethylene, polyethylene oxide, the same crosslinking agent as in Example 2, magnesium oxide, and a plasticizer were mixed in the proportions shown in Table 3, and the mixture was heated to 130°C.
It was extruded into pellets. However, the same polyethylene and polyethylene oxide as in the previous example were used. This pellet was extrusion molded in the same manner as in Example 2 to obtain a sheet with a thickness of about 1 mm. The matte state and surface smoothness of this product were determined in the same manner as in the previous example, and the results were as shown in Table 3.

【table】

Claims (1)

[Scope of Claims] 1. (a) 100 parts by weight of vinyl chloride resin, (b) 0.4 to 0.4 parts of polyethylene with an average molecular weight of 500 to 6,000.
(c) 0.4 to 3.0 parts by weight of polyethylene oxide having an average molecular weight of 500 to 3000, and a required amount of a plasticizer.