JPS6348891B2 - - Google Patents

Description

[Detailed description of the invention]

BACKGROUND AND OBJECTS OF THE INVENTION The present invention relates to improvements in polymer compositions containing a mixture of polyurethane and polyvinyl chloride resin or a urethane-vinyl chloride graft copolymer as a polymer component. Conventionally, what is commonly called soft vinyl has a content of 30 to 100 parts by weight per 100 parts by weight of polyvinyl chloride resin.
100 parts by weight of a liquid substance called a plasticizer such as phthalate ester, adibate ester, trimellitic acid ester, polyester, etc. has been added to impart flexibility, cold resistance, elongation, etc. As a result, the field of application of polyvinyl chloride resin has expanded significantly, but the major drawback is that as the initial amount of plasticizer changes due to diffusion, migration, extraction, etc. of the plasticizer, related properties change significantly. or contaminate other contact materials such as air, water, oil, solvents, lacquers, varnishes, paints, plastics, rubber, etc. by diffusion, migration, extraction, etc.
Deterioration or change in quality. In order to eliminate these drawbacks, it is possible to create new products by, for example, blending polymers with large molecular weights that are compatible with polyvinyl chloride resin, or copolymerizing or graft copolymerizing vinyl chloride with these polymers. Attempts have been made to improve flexibility, cold resistance, elongation, and other properties. Typical examples include those that are a blend of polyurethane and polyvinyl chloride resin, or those that are obtained by dissolving polyurethane in a vinyl chloride monomer and performing graft copolymerization. Polyurethane is rich in elasticity, cold resistance, strength, and oil resistance.Although the blend or graft copolymers mentioned above have excellent mechanical properties, they have poor heat resistance and are heat resistant. Decrease in tensile properties, discoloration, or decomposition due to deterioration may occur.
This significantly narrows the practical range. Furthermore, it is a major drawback that hydrolytic deterioration occurs and the urethane portion has a lower molecular weight. In general, lead-based stabilizers and organotin-based stabilizers have outstanding effects in thermally stabilizing polyvinyl chloride resins, and these are generally used except for special purposes. However, lead-based stabilizers cannot be used in polymer systems containing urethane because they promote hydrolysis of the urethane part due to their high basicity.
Organotin stabilizers cannot be used because of their large deterioration. The present invention has been made based on the above, and has an object to improve the hydrolysis resistance and heat resistance of a polymer composition containing a mixture of polyurethane and polyvinyl chloride resin or a urethane-vinyl chloride graft copolymer as a polymer component. The purpose is to [Summary of the Invention] The polymer composition of the present invention comprises a polymer component consisting of a mixture of polyurethane and polyvinyl chloride resin or a urethane-vinyl chloride graft copolymer, which has polar groups added to the pores of porous metal silicate particles. It is characterized by being formed by blending a substance filled with a material having In the present invention, the content ratio of urethane and vinyl chloride in the polymer component consisting of a mixture of polyurethane and polyvinyl chloride resin or a urethane-vinyl chloride graft copolymer is determined depending on the intended use, and a hard material is required. When a soft material is required, the amount of vinyl chloride component may be increased, and when a soft material is required, the amount of urethane component may be increased. Examples of the porous metal silicate particles include porous particles of calcium silicate, barium silicate, zinc silicate, magnesium silicate, strontium silicate, and the like. These porous particles have a greater stabilizing effect as they have more pores on their surface, but have the disadvantage that they tend to absorb moisture and carbon dioxide gas. Therefore, in the present invention, the pores of porous grains are filled with a material having a polar group. As the filling material having a polar group, organic hydroxy compounds are suitable, and specifically, polyhydric alcohols such as polyethylene glycol, higher fatty acid alcohols such as tridecyl alcohol, and 2,6-di-t-butyl-p- Examples include phenols such as phenylphenol, which also have high boiling points and high decomposition properties. A representative example of a substance in which the pores of porous metal silicate particles are filled with a material having a polar group is the product name Stabinex NW, which is commercially available from Mizusawa Chemical Industry Co., Ltd. The amount of the substance that fills the pores of the metal silicate porous particles with a material having a polar group is not particularly limited, but naturally the larger the amount, the better the hydrolysis resistance and heat resistance, but Considering processability, the preferable range is 3 to 30 parts by weight per 100 parts by weight of the polymer component. In the present invention, in addition to the above components, nitrogen compounds such as urea, phosphorus compounds such as tris(nonylphenyl) phosphite, sulfur compounds such as dilaurylthiopropionate, di-n-octyltin maleate salts, etc. One type or two or more types selected from organic tin compounds and metal soaps such as stearic acid and oleic acid may be used in combination. Further, plasticizers such as dioctyl phthalate, diisodecyl adipate, epoxidized soybean oil, polyester adipic acid, and chlorinated paraffin, and furthermore, lubricants such as paraffin may be used in combination. [Examples of the Invention] As shown in each example in Table 1, various ingredients were kneaded in predetermined amounts with a roll, and then formed into a sheet with a thickness of 1 mm using a press. This sheet was evaluated on three items: thermal stability, moist heat resistance, and heat aging resistance, and the results are shown in Table 2. The evaluation was based on the following. Thermal stability: The sheet was placed in a constant temperature bath at 190°C and 200°C, and after a predetermined period of time, it was taken out and its appearance was observed. Humidity and heat properties: The sheet was suspended in a temperature of 80°C and 98% RH, and after a predetermined period of time, it was taken out and its appearance was observed. Heat aging properties: Changes in appearance were observed after being left in a hot air aging tester at 120°C for a predetermined period of time.

【table】

[Table] As is clear from the evaluation results in Table 2, Examples 1 to 3 within the scope of the present invention are excellent in all of thermal stability, moist heat resistance, and heat aging resistance. In contrast, Comparative Examples 1 to 4 using conventional stabilizers
The test failed in all test items. [Effects of the Invention] As explained above, the present invention provides a mixture of polyurethane and polyvinyl chloride resin or a urethane-polyvinyl chloride resin.
It is made by blending a polymer component made of a vinyl chloride graft copolymer with a substance in which the pores of porous metal silicate particles are filled with a material having a polar group,
It becomes possible to significantly improve the heat resistance and hydrolysis resistance of vinyl resin.

Claims (1)

[Claims] 1. A polymer component consisting of a mixture of polyurethane and polyvinyl chloride resin or a urethane-vinyl chloride graft copolymer is blended with a substance in which the pores of metal silicate porous particles are filled with a material having a polar group. Characterized polymer compositions.