JPH07173354A - Vinyl chloride-based resin composition for powder molding - Google Patents

Abstract

PURPOSE:To obtain a resin composition excellent in mold-staining resistance and adhesion to a foamed urethane by adding a plasticizer, barium perchlorate, sodium perchlorate, etc., and white carbon in combination to a vinyl chloride- based resin. CONSTITUTION:This resin composition is composed of (A) a vinyl chloride-based resin, (B) a plasticizer (preferably a trimellitic acid ester-based plasticizer such as trioctyl trimellitate), (C) a compound selected from barium perchlorate, sodium perchlorate and perchloric acid-treated hydrotalcite and (D) white carbon (e.g. anhydrous silicate). The components (B), (C) and (D) are preferably used in a ratio of 50 to 80 pts.wt., 2 to 4 pts.wt. and 0.5 to 5 pts.wt. based on 100 pts.wt. component (A) respectively. In addition, the above-mentioned resin composition can be obtained, e.g. by dry-blending the component (B) with the component (A) under heating, subsequently admixing the components (C) and (D) therewith, uniformly mixing them and then cooling the resultant mixture.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition for powder molding capable of obtaining a molded product having good urethane foam adhesiveness and having little mold contamination during manufacturing of the molded product.

[0002]

2. Description of the Related Art A vinyl chloride resin composition for powder molding is mainly composed of a powdery vinyl chloride resin obtained by suspension polymerization or the like, which is dry-blended with a plasticizer. For example, various additives such as stabilizers, pigments, lubricants and fillers are blended. The main use of the vinyl chloride resin composition for powder molding is automobile interior material moldings, and the interior material is often used as a laminate by injecting and foaming urethane. When urethane is injected and foamed into a vinyl chloride resin molded product, the amine compound in the urethane foam causes an inconvenient phenomenon such as deterioration and deterioration of the molded product, and this phenomenon is particularly accelerated in the presence of heat and light. . Deterioration of molded products due to this amine compound,
For the purpose of preventing deterioration, that is, as an amine resistance measure, in recent years, a method of incorporating barium perchlorate or sodium perchlorate into a vinyl chloride resin composition has been adopted.

For molded articles such as automobile interior materials, however, the resin composition for powder molding is charged into a heated mold, the composition adhering to the mold is melted, and excess unmelted powder is molded. The resin composition for use is discharged, then the composition attached to the mold is reheated, and then the mold is cooled to take out a molded product. When this step is repeated, the mold release agent such as barium perchlorate, stearic acid or its metal salt, or the lubricant and other additives contained in the powder molding composition plate out to contaminate the mold. Cause. Further, if the obtained molded product is stored as it is for a long period of time, barium perchlorate and a lubricant bloom on the surface of the molded product to hinder the adhesion of urethane foam and cause a decrease in the adhesive strength.

[0004]

DISCLOSURE OF THE INVENTION The object of the present invention is to obtain a vinyl chloride resin composition for powder molding, which has good adhesiveness to urethane foam even after the molded article after molding has been left for a long time. As a result of diligent study, it was found that by combining barium perchlorate, sodium perchlorate or perchloric acid-treated hydrotalcite and white carbon together, the above-mentioned object of the present invention can be achieved, and in particular perchlorine. The inventors have found that a combination of acid-treated hydrotalcite and white carbon does not contaminate the mold during molding, and completed the present invention. That is,
An object of the present invention is to provide a vinyl chloride resin composition for powder molding, which has excellent mold stain resistance and good adhesiveness with urethane foam.

[0005]

SUMMARY OF THE INVENTION The gist of the present invention, however, is a resin composition for powder molding obtained by dry blending a vinyl chloride resin with a plasticizer.
At least one selected from barium perchlorate, sodium perchlorate and hydrochlorite treated with perchloric acid, and white carbon are contained in the composition, and a vinyl chloride resin composition for powder molding, characterized in that Exist in.

The present invention will be described in detail. As the vinyl chloride resin of the composition of the present invention, a commercially available vinyl chloride resin can be used as it is. Specifically, a vinyl chloride homopolymer produced by a suspension polymerization method or a copolymer containing a vinyl chloride monomer and a vinyl chloride monomer such as ethylene or vinyl acetate as a main component is used according to the purpose of use. These vinyl chloride resins are porous and are so-called dry blendable resins that absorb the plasticizer when mixed with the plasticizer.

The plasticizer used in the composition of the present invention is not particularly limited as long as it is usually used for vinyl chloride resins, and examples thereof include dibutyl phthalate (DBP) and di-2.
-Phthalate ester-based plasticizers such as ethylhexyl phthalate (DOP), trioctyl trimellitate (TOT
M), trimellitic acid ester-based plasticizers such as tridecyl trimellitate, aliphatic dibasic acid ester-based plasticizers such as dioctyl adipate and diisodecyl adipate, and phosphate ester-based plasticizers such as tricresyl phosphate and trioctyl phosphate Agents, epoxy plasticizers, polyester plasticizers and the like. Among these, it is particularly preferable to use a plasticizer having low volatility during heating, such as a trimellitic acid ester plasticizer and a polyester plasticizer.

The blending amount of the plasticizer is limited to such an amount that the vinyl chloride resin is still present in powder form when the plasticizer is mixed with the vinyl chloride resin. Specifically, for example, vinyl chloride resin 100 It is suitable to be in the range of 20 to 100 parts by weight, preferably 50 to 80 parts by weight with respect to parts by weight. The perchloric acid-treated hydrotalcite, which is an essential component of the composition of the present invention, is added by stirring hydrotalcite in a dilute aqueous solution of perchloric acid, or by adding a concentrated aqueous solution of perchloric acid to hydrotalcite and stirring. And then, if necessary, filtered, dehydrated or dried. Further, as barium perchlorate or sodium perchlorate, commercially available products can be used as they are.

However, the compounding amount of barium perchlorate, sodium perchlorate or perchloric acid-treated hydrotalcite is not particularly limited, but it is usually 0.1% with respect to 100 parts by weight of vinyl chloride resin. A range of 3 to 10 parts by weight, preferably 1 to 5 parts by weight, particularly 2 to 4 parts by weight is suitable. If it is less than 0.3 parts by weight, the effect of improving deterioration and deterioration due to urethane foam is insufficient, and if it is more than 10 parts by weight, the effect of improving urethane foam adhesiveness proportional to the compounding amount is not recognized. It is economically disadvantageous.

The white carbon, which is an essential component of the composition of the present invention, refers to silicic acid anhydride or hydrous calcium silicate, etc., and those which are usually added as a reinforcing agent for synthetic rubbers, plastics, etc. should be used as they are. You can The blending amount of white carbon is not particularly limited, but is usually selected from the range of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of the vinyl chloride resin. If the compounding amount is less than 0.1 part by weight, the effect of preventing plate-out and blooming is small, and the mold stain resistance and the adhesiveness with urethane foam are not sufficient. Although the adhesiveness is improved, it is not economically disadvantageous because it is not necessary to increase the adhesive force more than necessary.

In the composition of the present invention, if necessary, additives such as stabilizers, ultraviolet absorbers, antioxidants, lubricants, fillers and the like usually added to vinyl chloride resins are used for powder molding resin compositions. It can be blended in an appropriate amount within a range that does not deteriorate the physical properties of. The resin composition for powder molding of the present invention is prepared, for example, as follows. First, a vinyl chloride resin is blended with a plasticizer and, if necessary, other additives and dry-blended under heating, and then barium perchlorate, sodium perchlorate or perchloric acid-treated hydrotalcite and white carbon are added. After adding and uniformly mixing, the mixture is cooled and taken out.
Of course, barium perchlorate, sodium perchlorate or perchloric acid-treated hydrotalcite and white carbon may be mixed with other components during dry blending.

In addition, the resin composition for powder molding of the present invention, after being prepared, has an average particle size of 3 produced by an emulsion polymerization method or a fine suspension polymerization method for the purpose of improving the powder fluidity.
A vinyl chloride resin having a particle size of not more than μm, a so-called vinyl chloride paste resin or a fine inorganic filler such as fine calcium carbonate may be added as a powder fluidity improver. The blending amount of the powder fluidity improver is not particularly limited, but is usually 5 to 30 parts by weight, preferably 10 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

The vinyl chloride resin composition for powder molding of the present invention has a desired shape, for example, a crush pad, a door trim, a headrest, mainly by a powder molding method such as an Engel method, a Heisler method, a Hayashi process, and a rotational molding method. It is used to manufacture automobile interior materials such as armrests and console box skins.

[0014]

EXAMPLES Next, the vinyl chloride resin composition for powder molding of the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples without departing from the gist thereof. .

Example 1 and Comparative Example 1 2 kg of a vinyl chloride resin having an average degree of polymerization of 900 produced by the suspension polymerization method was charged into a 20 l supermixer, and 0.02 kg of a pigment was stirred and heated at a constant rotation speed.
Of trioctyl trimellitate containing 1.52 kg of perchloric acid was added, and 70 g of perchloric acid-treated hydrotalcite (ZP68 manufactured by Asahi Denka Co., Ltd.) and 20 g of silicic anhydride (OX50 manufactured by Nippon Aerosil Co., Ltd.) were added. Dry blending was performed to uniformly disperse each component. This was cooled to obtain a resin composition for powder molding. The maximum heating temperature during dry blending was 130 ° C. Next, 240 g of a vinyl chloride paste resin having an average particle size of 3 μm or less and an average polymerization degree of 1000, which was produced by an emulsion polymerization method, was added as a powder fluidity improver to the composition and uniformly dispersed.

A molded article was produced from the composition prepared as described above as follows. The molded product was charged with 200 g of the resin composition in a mold heated to 240 ° C., allowed to stand for 30 seconds, then discharged unmelted surplus composition, and then again heated and melted at 240 ° C. for 150 seconds. . Molding was carried out by peeling the molded product from the mold when the mold temperature reached 50 ° C. Further, for comparison, a composition and a molded product were obtained in the same manner as in the above example except that the hydrochlorite treated with perchloric acid was changed to barium perchlorate and white carbon was not used. With respect to these compositions and molded products after being left for a long period of time, the mold staining property and the urethane foam adhesive property were examined, and the results are shown in Table 1.

The mold contamination and urethane foam adhesiveness were evaluated as follows. Mold contamination: The gloss value of the mold after repeated molding was expressed as a percentage with respect to the gloss value of the mold before molding. The gloss measuring instrument is GP-60 type manufactured by Tokyo Denshoku. Urethane foam adhesion: A vinyl chloride resin molded product was placed in a mold and urethane was injected to obtain a laminate. With respect to the laminate, the vinyl chloride resin molded product and the urethane foam were peeled off by hand and evaluated according to the following criteria.

[Table 1] 5: Material destruction of urethane foam (entire surface) 4: Material destruction of urethane foam (part) 3: Partial interface peeling of about 30% 2: Interface peeling of about 70% 1: Whole surface interface peeling

[0018]

[Table 2]

Examples 2, 3 and Comparative Example 2 The same as Example 1 except that the perchloric acid-treated hydrotalcite was replaced with barium perchlorate (Example 2) and sodium perchlorate (Example 3). To prepare a composition, and a molded article was manufactured. Example 1 shows the urethane foam adhesiveness of the molded product.
The evaluation was performed in the same manner as in Table 2 and shown in Table 2. Further, the urethane foam adhesiveness was evaluated in the same manner as in Example 3 except that white carbon was not used, and the results are shown in Table 2 as Comparative Example 2.

[0020]

[Table 3]

[0021]

The vinyl chloride resin composition for powder molding of the present invention contains perchloric acid-treated hydrotalcite and white carbon, so that there is no plate-out of the components contained in the composition. Since the molded product obtained from the composition has excellent blooming resistance and does not have blooming, the adhesiveness to the urethane foam is maintained even after the molded product is left or stored under severe conditions such as high temperature. It is good and has an effect of preventing deterioration and deterioration due to an amine compound due to urethane foam.

In addition, the combination of barium or sodium perchlorate and white carbon combined with white carbon does not have the effect of improving the mold stain resistance, but does not reach that of the combined use of perchloric acid-treated hydrotalcite. Adhesiveness of urethane foam after long-term storage of the product is equal to or better than that.

Claims (6)

[Claims] 1. A resin composition for powder molding, which is obtained by dry blending a vinyl chloride resin with a plasticizer, wherein barium perchlorate, sodium perchlorate, and perchloric acid are treated. A vinyl chloride-based resin composition for powder molding, comprising at least one selected from hydrotalcite and white carbon. 2. The content of barium perchlorate, sodium perchlorate or hydrotalcite treated with perchloric acid and white carbon is 0.3 to 10 parts by weight and 0.1% by weight per 100 parts by weight of vinyl chloride resin, respectively. The vinyl chloride resin composition for powder molding according to claim 1, which is in the range of 1 to 10 parts by weight. 3. The vinyl chloride resin composition for powder molding according to claim 1 or 2, wherein the plasticizer is a trimellitic acid ester plasticizer or a polyester plasticizer. 4. The vinyl chloride resin composition for powder molding according to claim 1, and 5 to 30 parts by weight of a powder fluidity improver per 100 parts by weight of the vinyl chloride resin. A vinyl chloride resin composition for powder molding, which is uniformly dispersed. 5. The vinyl chloride resin for powder molding according to claim 4, wherein the powder fluidity improver is a vinyl chloride resin having an average particle diameter of 3 μm or less produced by an emulsion polymerization method or a fine suspension polymerization method. Composition. 6. The vinyl chloride resin composition for powder molding according to claim 4, wherein the powder fluidity improver is a fine inorganic filler.