JPH0113416B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to the prevention of aging of chlorine-containing resins adhered to or in contact with polyurethane foams at low temperatures. In general, molded products of chlorine-containing resin that are adhered to or in contact with polyurethane foam are heated to temperatures above 70℃ and 140℃.
If left in the following atmosphere for a long time, the layer made of chlorine-containing resin will deteriorate significantly over time, resulting in a decrease in mechanical properties and discoloration (hereinafter, this phenomenon is referred to as low-temperature aging). ). The object of this invention is to develop a new method for protecting chlorine-containing resins that are adhered to or in contact with polyurethane foams from low-temperature aging and maintaining them in a stable state for long periods of time. Depending on the purpose of use, chlorine-containing resins that adhere to or come into contact with polyurethane foam may exceed 70°C or 140°C.
It has long been desired to develop a method to prevent low-temperature aging, as products are often used in environments at temperatures below 0.9°C. Therefore, if a chlorine-containing resin impregnated with a diluted solution of an amine compound is left in an atmosphere at 120°C for a long time, the chlorine-containing resin will easily discolor and its elongation in a tensile test will drop significantly. One of the causes is presumed to be that trace amounts of amine compounds remaining in the polyurethane foam migrate to the chlorine-containing resin layer and have the effect of accelerating low-temperature aging of the chlorine-containing resin. Therefore, it is thought that low-temperature aging can be prevented by incorporating a substance that absorbs the action of this amine compound and renders it harmless. In view of the above, the present inventors have developed a method for preventing the low-temperature aging of chlorine-containing resins that adhere to or come into contact with polyurethane foam by reacting each metal such as alkali metals and alkaline earth metals in the periodic table with amine compounds. As a result of conducting research on the properties and selecting substances that meet the above objectives, and conducting intensive research on the mutual effects of these substances, we found that the combination shown below can prevent low-temperature aging. It has been found that the performance of chlorine-containing resins can be maintained well even after long-term use. The present invention provides at least one selected from the group of organic acid salts of zinc and inorganic compounds of zinc, and also at least one selected from the group of inorganic compounds of alkaline earth metals.
Selected seeds are combined and added as a low-temperature anti-aging agent to a chlorine-containing resin that is adhered to or in contact with polyurethane foam. It has been found that a low-temperature anti-aging agent made of a combination of these substances can maintain the mechanical strength of chlorine-containing resin molded products over a long period of time due to their mutual interaction, and can sufficiently suppress discoloration. The organic acids constituting the organic acid salt of zinc used in the present invention are 2-ethylhexanoic acid, octanoic acid, decanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, hydroxy These include stearic acid, benzoic acid, P-t-butylbenzoic acid, toluic acid, naphthenic acid, phenol, cresol nonylphenol, and mercaptoic acid. The amount of these organic acid salts is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the chlorine-containing resin.
It was found that the weight part. Inorganic compounds of zinc related to the present invention include its oxides, hydroxides, phosphites, phosphates, sulfates, and the like. The amount of these compounds is 0.1 to 100 parts by weight of the chlorine-containing resin.
The amount is preferably 10 parts by weight, preferably 0.5 to 5 parts by weight. Inorganic compounds of alkaline earth metals related to the present invention include their oxides, hydroxides, phosphites, phosphates, and sulfates. The amount of these alkaline earth metal inorganic compounds blended is 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the chlorine-containing resin. In addition, the low-temperature anti-aging agent according to the present invention includes ordinary stabilizer components,
It goes without saying that further effects are expected in the coexistence of the stabilizing aid component and the plasticizer component. In addition, various types of antistatic agents, fillers, flame retardants, surfactants, colorants, mold release agents, viscosity modifiers, anti-bacterial agents, and ultraviolet absorbers are added depending on the intended use of the chlorine-containing resin. It does not prevent coexistence with additives. The chlorine-containing resins used in the present invention include polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-styrene, etc. Each of the polymers alone or together with the above resins, acrylonitrile-butadiene-styrene copolymer, ethylene-propylene copolymer, acrylic ester-
One or more blends of butadiene-styrene copolymers, nitrile-butadiene-rubbers may be included. The following examples show that the chlorine-containing resin bonded to the polyurethane foam is more resistant to low-temperature aging when combined with the low-temperature anti-aging agent of the present invention than when the chlorine-containing resin is combined with a regular stabilizer. This shows that it is much more stable. Example 1 The following method was used to adhere polyvinyl chloride to urethane foam. The composition shown below was kneaded for 5 minutes at a roll temperature of 170°C to form a sheet with a thickness of 1 mm. The standard formulation is as follows. Chlorine-containing resin...Polyvinyl chloride 100 parts by weight Plasticizer...Dioctyl phthalate 60 parts by weight Stabilizing agent...Epoxidized soybean oil 3 parts by weight Stabilizer...Barium stearate Calcium stearate 0.7 parts by weight Next, two parts of urethane (EDIFORM AS-
230 and Edyform A-100 (manufactured by Kao Soap Co., Ltd.) were mixed and foamed on a sheet to form a composite of polyvinyl chloride and urethane foam with a thickness of 2 cm. This composite was then exposed to 120° C. in an open gear, and the time until blackening was measured. The results are shown in Table 1. Note) No. 1 in the table is a case where there is no mutual effect due to the combination related to the present invention, and the other cases are cases where a mutual effect appears.

[Table] Example 2 The same conditions as in Example 1 were used. Table 2 shows the results of combining various zinc compounds for low-temperature anti-aging agents.

【table】

[Table] Example 3 The same conditions as in Example 1 were used. The results are shown in Table 3. Combinations were carried out using three combinations: an organic acid salt of zinc, an inorganic compound of zinc, and an inorganic compound of alkaline earth metal.

【table】

Claims (1)

[Scope of Claims] 1. A chlorine-containing resin adhered to or in contact with a polyurethane foam, at least one member from the two groups of organic acid salts of zinc and inorganic compounds of zinc, and a group of inorganic alkaline earth metal compounds. A stabilization method characterized by selecting at least one type from among the following and adding the combination of the two to a chlorine-containing resin as a low-temperature anti-aging agent to prevent deterioration of the properties of the resin in a low-temperature range. 2. Organic acid components listed in Section 1 include 2-ethylhexanoic acid, octanoic acid, decanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, hydroxystearic acid, and benzoic acid. acid, P-t
- A method of stabilization, characterized in that it contains butylbenzoic acid, toluic acid, naphthenic acid, phenol, cresol, nonylphenol, mercaptoic acid. 3. A stabilizing method characterized in that the inorganic zinc compound described in item 1 includes a zinc oxide, hydroxide, phosphite, phosphate, or sulfate. 4. A stabilization method characterized by containing magnesium, calcium, strontium, and barium as the alkaline earth metals described in item 1. 5. A stabilization method characterized in that the inorganic compound of the alkaline earth metal described in Items 1 and 4 includes an oxide, hydroxide, phosphite, phosphate, or sulfate. 6. A stabilizing method according to items 1 and 2, characterized in that 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, of an organic acid salt of zinc is blended with respect to 100 parts by weight of the chlorine-containing resin. 7. A stabilization method characterized in that the inorganic zinc compound described in Items 1 and 3 is blended in 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the chlorine-containing resin. 8. 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight of the alkaline earth metal inorganic compound described in Items 1, 4, and 5, per 100 parts by weight of the chlorine-containing resin. A method of stabilization. 9 As a chlorine-containing resin, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-styrene copolymer each individually or, alternatively, one or more blends of the above resins with acrylonitrile-butadiene-styrene copolymer, ethylene-propylene copolymer, acrylic acid ester-butadiene-styrene copolymer, nitrile-butadiene-rubber. , the method according to item 1, characterized in that low-temperature aging of these is prevented.