JPH07173353A - Production of vinyl chloride-based resin composition for powder molding - Google Patents

Abstract

PURPOSE:To produce a resin composition remarkably excellent in amine resistance by impregnating barium perchlorate with a plasticizer in advance and subsequently dry-blending it with a vinyl chloride-based resin powder. CONSTITUTION:Barium perchlorate, sodium perchlorate or perchlorate-treated hydrotalcite (hereinafter abbreviated a perchlorate compound) is initially impregnated with a plasticizer (preferably a trimellitic acid ester-based plasticizer such as trioctyl trimellitate). The impregnated perchlorate compound is then blended with a vinyl chloride-based resin powder according to the dry blending method, to produce the objective resin composition containing a perchlorate compound. In addition, the perchlorate compound and the plasticizer are preferably used in an amount of 2 to 5 pts.wt. and 50 to 80 pts.wt. based on 100 pts.wt vinyl chloride-based resin powder respectively. The impregnation of the perchlorate compound with the plasticizer is carried out preferably to a sufficient degree by dispersing the whole amount of the perchlorate compound in the whole amount of the plasticizer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a vinyl chloride resin composition used in powder molding such as rotary molding and powder slush molding having improved amine resistance.

[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 mixed. 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 vinyl chloride resin molded product. Especially, this phenomenon occurs in the presence of heat and light. Remarkably promoted. For the purpose of preventing deterioration and deterioration of molded articles by this amine compound, 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. It has been found that chloric acid treated hydrotalcite can also be used for similar purposes.

However, barium perchlorate, sodium perchlorate or hydrochlorite treated with perchloric acid is separately blended in a high speed stirring mixer such as a super mixer when dry blending a vinyl chloride resin and a plasticizer. Since they are added and mixed, the dispersion state changes only by slight changes in their mixing conditions, etc., so-called uniform dispersibility is poor, and the effect of amine resistance characteristics such as barium perchlorate described above changes and decreases. There was a flaw.

[0004]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The inventors of the present invention have earnestly studied a method for producing a vinyl chloride resin composition for powder molding, which does not affect the amine resistance depending on the production conditions. By impregnating sodium chlorate, perchloric acid-treated hydrotalcite, etc. with a plasticizer in advance and then adding it to vinyl chloride resin powder and dry blending, the amine resistance does not change and a more excellent amine resistance effect is obtained. They have found that they can exert their effects and have completed the present invention. That is, an object of the present invention is to provide a method for producing a vinyl chloride resin composition for powder molding, which is excellent in amine resistance.

[0005]

SUMMARY OF THE INVENTION The gist of the present invention is to produce a vinyl chloride resin composition for powder molding, containing barium perchlorate, sodium perchlorate or hydrotalcite treated with perchloric acid. In the method described above, barium perchlorate, sodium perchlorate or perchloric acid-treated hydrotalcite is impregnated with a plasticizer in advance, and then mixed and dry blended with vinyl chloride resin powder. A method for producing a vinyl chloride resin composition for powder molding.

The present invention will be described in detail. As the vinyl chloride resin powder used in the method for producing 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 method of producing the composition of the present invention is
The vinyl chloride resin is not particularly limited as long as it is usually used in the resin, and for example, dibutyl phthalate (DB
P), phthalate ester-based plasticizers such as di-2-ethylhexyl phthalate (DOP), trimellitate ester-based plasticizers such as trioctyl trimellitate (TOTM) and tridecyl trimellitate, dioctyl adipate,
Examples thereof include aliphatic dibasic acid ester plasticizers such as diisodecyl adipate, phosphoric acid ester plasticizers such as tricresyl phosphate and trioctyl phosphate, epoxy plasticizers and polyester plasticizers. 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 powder. It is suitable to be in the range of 20 to 100 parts by weight, preferably 50 to 80 parts by weight, relative to 100 parts by weight. As barium or sodium perchlorate which is an essential component of the composition of the present invention, commercially available products can be used as they are, and perchloric acid-treated hydrotalcite is hydrotalcite which is a dilute aqueous solution of perchloric acid. Add to the inside and stir, or add a concentrated aqueous solution of perchloric acid to hydrotalcite and stir, then filter if necessary,
It is prepared by dehydration or drying. These may be used in combination of two or more.

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 7 parts by weight, particularly 2 to 5 parts by weight is suitable. If it is less than 0.3 parts by weight, it is difficult to prevent thermal deterioration due to the amine compound, and if it is more than 10 parts by weight, the bleeding phenomenon is likely to occur. If necessary, the composition produced by the method of the present invention may contain stabilizers, ultraviolet absorbers, antioxidants, lubricants, fillers, and other additives usually added to vinyl chloride-based resins. An appropriate amount can be compounded within a range that does not deteriorate the physical properties of the product.

The vinyl chloride resin composition for powder molding of the present invention is produced, for example, as follows. First, the total amount or part of barium perchlorate, sodium perchlorate or perchloric acid-treated hydrotalcite (hereinafter simply referred to as perchloric acid compound) to be mixed with the vinyl chloride resin powder is added to the above plasticizer. Impregnate. The amount of the plasticizer used for impregnation may be the whole amount or a part thereof used in the preparation of the vinyl chloride resin composition for powder molding. The point is that the amount is sufficient to sufficiently impregnate the perchloric acid compound with the plasticizer. In the method of the present invention, it is a desirable embodiment to disperse the entire amount of the perchloric acid compound in the total amount of the plasticizer, and to sufficiently impregnate it.

The method of impregnating the perchloric acid compound with the plasticizer is not particularly limited, but for example, the two are sufficiently mixed with a mixer such as a ribbon blender or a butterfly mixer, and if necessary, with an ink mill or the like. The method of forced impregnation is adopted. Next, the vinyl chloride resin powder is mixed with the plasticizer-impregnated perchloric acid compound prepared as described above and the remaining perchloric acid compound or the plasticizer, and various additives as necessary, and uniformly dry blended. By doing so, a vinyl chloride resin composition for powder molding is produced.

Further, the resin composition for powder molding produced by the method of the present invention has an average particle size produced by an emulsion polymerization method or a fine suspension polymerization method for the purpose of improving the powder flowability after the production. A vinyl chloride resin having a diameter of 3 μm or less, 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 produced by the method 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, console box skins, etc.

[0013]

According to the method of the present invention, barium perchlorate,
By impregnating sodium perchlorate or perchloric acid-treated hydrotalcite with a plasticizer in advance, and then dry blending it with vinyl chloride resin powder, the vinyl chloride resin, plasticizer and perchlorate compound are added separately. Compared with the blended product, even if it is heated at a high temperature for a long time, its physical properties are less deteriorated, and the amine resistance is significantly improved.

[0014]

EXAMPLES Next, the method for producing a 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 unless departing from the gist thereof. Not something.

Examples 1 to 3 and Comparative Examples 1 to 3 60 g of the perchloric acid compound shown in Table 1 was charged into a ribbon blender, and trioctyl trimellitate 1.5 was added thereto.
kg was added and mixed to impregnate the perchloric acid compound with the plasticizer. Separately, a plasticizer containing the perchloric acid compound was added to 2 kg of a vinyl chloride resin having an average degree of polymerization of 900, which was manufactured by the suspension polymerization method, in a 20 l capacity Supermickeys while stirring at a constant rotation speed. Was uniformly dry-blended to prepare a vinyl chloride resin composition for powder molding. After cooling this composition to 60 ° C., 240 g of a vinyl chloride paste resin having an average particle size of 3 μm or less and an average degree of polymerization of 1000 produced by an emulsion polymerization method as a powder fluidity improver was added and uniformly dispersed. .

For comparison, the same procedure as in Example 1 was carried out except that the perchloric acid compound was not impregnated with the plasticizer, and both were separately added to carry out dry blending with the vinyl chloride resin powder. A resin composition was prepared. A molded article was molded from the composition prepared as described above as follows. 200 g of the resin composition was put into a box mold of A3 standard size heated to 240 ° C., left standing for 30 seconds, and then the unmelted surplus composition was discharged.
It was heated and melted for a second. When the mold temperature reached 50 ° C., the molded product was peeled off from the mold. There were no problems in the molding process.

The amine resistance of the molded product was evaluated as follows. 700 mm long and 300 m wide from the above molded product
Cut out a sheet with a thickness of 0.8 mm and cut out this sheet
The sheet was placed in a rectangular urethane mold having an inner size of 800 mm and a depth of 10 mm so that the mold surface of the sheet was in contact with the bottom surface of the aluminum mold. A foaming urethane consisting of 100 parts by weight of polyol and 54 parts by weight of isocyanate was stirred at a high speed for 10 seconds and then injected into the mold to clamp the mold to fix the urethane foam on the back surface of the molded product sheet. Length from this Urenta pasting sheet is 15
A sample cut into a size of 0 mm and a width of 70 mm is put in a gear oven type heating furnace in an atmosphere of 110 ° C for 1000 hours and 2000
Left for hours. The sheet from which the urethane foam was removed from the sample was measured for elongation in accordance with JIS K6301. The results are shown in Table-1.

[0018]

[Table 1]

Claims (6)

[Claims] 1. A method for producing a vinyl chloride resin composition for powder molding, containing barium perchlorate, sodium perchlorate or hydrotalcite treated with perchloric acid, comprising barium perchlorate and sodium perchlorate. Alternatively, a perchloric acid-treated hydrotalcite is impregnated with a plasticizer in advance, and then mixed with a vinyl chloride resin powder, followed by dry blending to produce a vinyl chloride resin composition for powder molding. Method. 2. The vinyl chloride for powder molding according to claim 1, wherein the total amount of barium perchlorate, sodium perchlorate or hydrochlorite treated with perchloric acid to be blended with the vinyl chloride resin powder is impregnated with a plasticizer in advance. Method for producing a resin composition. 3. The method for producing a 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 manufactured by the method according to claim 1, wherein the powder fluidity improver is 5 to 100 parts by weight of the vinyl chloride resin.
A method for producing a vinyl chloride resin composition for powder molding, which comprises uniformly dispersing 30 parts by weight. 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. A method for producing a composition. 6. The method for producing a vinyl chloride resin composition for powder molding according to claim 4, wherein the powder fluidity improver is a fine inorganic filler.