JPH0948896A - Vinyl chloride-based resin composition for powder molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in heat resistance and amine resistance, prevented in discoloration and deterioration and useful as a molding material for automotive interiors by adding a specific perchloric acid metal salt and hydrotalcite to vinyl chloride-based resin composition containing a plasticizer. SOLUTION: This composition is obtained by adding (C) barium perchlorate, sodium perchlorate or magnesium perchlorate, (D) tin perchlorate and (E) hydrotalcite free from water of crystallization to a resin composition obtained by carrying out dry blend of (A) a vinyl chloride-based resin with (B) a trimellitic acid ester based or a polyester-based plasticizer and further, as necessary, adding (F) a powder fluidity improver such as vinyl chloride-based resin having <=10μm average particle diameter and obtained by emulsion polymerization or suspension polymerization thereto and preferably blending the component A with 0.5-10 pts.wt. component C, 0.01-5 pts.wt. component D, 0.5-10 pts.wt. component E and 5-30 pts.wt. component F based on 100 pts.wt. component A.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a vinyl chloride resin composition having improved amine resistance and used for powder molding such as rotary molding and powder slush molding.

[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 a suspension polymerization method or the like, which is dry-blended with a plasticizer.
Depending on the purpose of use, various additives such as stabilizers, pigments, lubricants and fillers are mixed. The main use of the vinyl chloride-based resin composition for powder molding is automobile interior material moldings, and the interior material is usually used as a laminate by injecting and foaming urethane resin. When a urethane resin is injected and foamed into a vinyl chloride resin molded product, the amine compound in the foamed urethane resin causes an inconvenient phenomenon such as deterioration and deterioration of the vinyl chloride resin molded product. In particular, this phenomenon is caused by heat and light. It is significantly promoted in the presence. For the purpose of preventing the deterioration and deterioration of the molded article by this amine compound, that is, as an amine resistance measure, in recent years, a method of blending barium perchlorate and sodium perchlorate with 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, in the interior material as described above, the vinyl chloride resin film deteriorates over time under the climatic conditions of summer when the temperature reaches 70 to 100 ° C., and the flexibility of the film is impaired. There is a problem of discoloration,
The improvement was desired. It has been known that the deterioration is promoted by the transfer of the amine compound existing in the urethane foam resin film to the vinyl chloride resin skin, but an effective means for suppressing such accelerated deterioration by heat has been found. Didn't.

[0004]

DISCLOSURE OF THE INVENTION The inventor has found that the temperature of 10
As a result of intensive studies to develop a vinyl chloride resin composition that does not deteriorate or discolor due to amine even under conditions of around 0 ° C., vinyl chloride resin was found to contain barium perchlorate, sodium perchlorate or perchloric acid. It has been found that the above object can be achieved by combining and blending at least one kind of magnesium, tin perchlorate and hydrotalcite without water of crystallization, and has 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 amine resistance even at high temperatures and has little thermal deterioration and thermal discoloration.

[0005]

The gist of the present invention is to provide a resin composition for powder molding in which a vinyl chloride resin is dry blended with a plasticizer, wherein barium perchlorate is contained in the composition. A vinyl chloride resin composition for powder molding, characterized by containing at least one selected from sodium perchlorate and magnesium perchlorate, tin perchlorate and hydrotalcite without water of crystallization. .

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION To explain the present invention in detail, as the vinyl chloride resin which is the resin component 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-based 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-ethylhexyl phthalate (DOP). Phthalate ester plasticizers, trioctyl trimellitate (TOTM), trimellitate ester plasticizers such as tridecyl trimellitate, tricresyl phosphate,
Examples thereof include phosphate ester-based plasticizers such as trioctyl phosphate, aliphatic dibasic acid ester-based plasticizers such as dioctyl adipate and diisodecyl adipate, epoxy-based plasticizers and polyester-based plasticizers. Among these, especially trimellitic acid ester plasticizers,
It is desirable to use a plasticizer having low volatility upon heating, such as 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. 20 to 100 parts by weight to 100 parts by weight of resin,
It is preferably in the range of 50 to 80 parts by weight. Barium perchlorate which is an essential component of the composition of the present invention,
As sodium perchlorate or magnesium perchlorate, commercially available powder or an aqueous solution thereof is used, and it is necessary to add at least one of them. Although the amount of barium perchlorate, sodium perchlorate or magnesium perchlorate used is not particularly limited, the total amount of these perchloric acid compounds is the vinyl chloride resin 10
A range of 0.5 to 10 parts by weight, preferably a range of 1 to 7 parts by weight, and particularly a range of 2 to 5 parts by weight are suitable per 0 parts by weight.

Tin perchlorate, which acts as a heat stabilizer which is one of the essential components of the composition of the present invention, has a synergistic effect in amine resistance and heat stability when used in combination with the above-mentioned perchloric acid compound. It has extremely excellent amine resistance and thermal stability. When the perchloric acid compound and tin perchlorate are used alone, the initial coloring of the resin composition is inferior and cannot be put to practical use. The amount of tin perchlorate used is in the range of 0.01 to 5 parts by weight, preferably 0.
It is desirable that the content be in the range of 03 to 2 parts by weight, particularly 0.05 to 1 part by weight.

The composition of the present invention can further improve the thermal stability of the composition by containing hydrotalcite without crystal water, that is, by removing the crystal water. The hydrotalcite from which the water of crystallization has been removed can usually be easily prepared by heating commercially available hydrotalcite to 250 ° C. or higher to remove the water of crystallization of hydrotalcite. The hydrotalcite from which water of crystallization is removed is in the range of 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of the vinyl chloride resin.
In particular, it is suitable to contain it in the range of 1.5 to 4 parts by weight.

The composition of the present invention may also contain various well-known additives such as lubricants, antioxidants, fillers, foaming agents, colorants, ultraviolet absorbers, and electrostatic charge as required depending on the purpose of use of the composition. Inhibitors, flame retardants and the like can be added within a range that does not deteriorate the physical properties of the composition. In order to produce the composition of the present invention, a vinyl chloride resin, a plasticizer, barium perchlorate, sodium perchlorate or magnesium perchlorate and tin perchlorate, and hydrotalcite from which water of crystallization is removed are further required. It is prepared by mixing the above-mentioned various additives according to the above and dry blending them under heating so that the vinyl chloride resin completely absorbs the plasticizer. In order to uniformly mix and dry blend these blended components, for example, they may be put into a mixer such as a Henschel mixer, a ribbon blender, a planetary mixer or the like and sufficiently stirred.

The vinyl chloride resin composition of the present invention thus obtained may contain a powder fluidity improver for the purpose of improving its powder fluidity. Examples of the powder fluidity improver include vinyl chloride resins having an average particle size of 10 μm or less, preferably 5 μm or less, which are produced by an emulsion polymerization method or a fine suspension polymerization method, so-called vinyl chloride paste resin and fine calcium carbonate. And the like, and it is preferable to use at least one of them. The blending amount of the powder fluidity improver is not particularly limited, but is based on 100 parts by weight of the vinyl chloride resin.
Usually, the range is 5 to 30 parts by weight, preferably the range is 8 to 15 parts by weight. It is necessary to add the powder fluidity improver to the vinyl chloride resin composition for powder molding obtained by dry blending, and when added during dry blending, the effect of improving the fluidity of the composition is sufficient. Is not demonstrated to

The vinyl chloride resin composition for powder molding of the present invention is obtained by a powder rotational molding method and a powder slush molding method.
Desired shape, e.g. crash pad, door trim,
It has high utility value as a molding material that is compounded with urethane resin such as headrest, armrest, and console box skin, that is, a molding material for automobile interior materials.

[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. . Examples 1 to 3 Vinyl chloride resin 2k having an average degree of polymerization of 900 produced by a suspension polymerization method in a super mixer having a capacity of 20 liters
g of trioctyl trimellitate containing 0.02 kg of pigment while stirring and heating at a constant stirring speed.
Hydrotalcite obtained by adding 52 kg, and further removing barium perchlorate (CPS55R manufactured by Asahi Denka Co., Ltd.) 0.07 kg, tin perchlorate (T47L manufactured by Katsuta Kako Co., Ltd.) 0.002 kg, and crystal water. (Kyowa Chemical Co., Ltd.
Alkamizer 4-2) (0.04 kg, manufactured by Mfg. Co., Ltd.) was added for dry blending. When the temperature of the composition reached 125 ° C., cooling was started, and after cooling to 50 ° C., 0.24 kg of vinyl chloride paste resin having an average degree of polymerization of 1500 and an average particle size of 5 μm or less was uniformly dispersed to obtain a powder. A vinyl chloride resin composition for molding was prepared. 0.2 kg of this resin composition was put into a mold heated to 240 ° C.
After leaving still for 2 seconds, and then discharging the unmelted excess composition,
It was again heated and melted at a temperature of 240 ° C. for 180 seconds. When the mold temperature reached 50 ° C., the molded product was peeled off from the mold (Example 1). Barium perchlorate of Example 1 was replaced with sodium perchlorate (CPL46, Example 2 manufactured by Asahi Denka Co., Ltd.) and magnesium perchlorate (reagent, Example 3).
Molded articles were obtained in the same manner as in Example 1 except that

The amine resistance of each molded article molded as described above was evaluated as follows. A sheet with a length of 700 mm, a width of 300 mm, and a thickness of 0.8 mm is cut out from the molded product, and this sheet is put into a rectangular urethane mold having an inner dimension of 800 mm and a depth of 10 mm, and the mold surface of the sheet is made of aluminum. It was placed so as to contact the bottom of the mold. A foaming urethane composed of 54 parts by weight of isocyanate to 100 parts by weight of polyol was stirred into the mold at a high speed for 10 seconds and then injected and clamped to fix the urethane foam on the back surface of the molded product sheet. Length 150mm, width 70mm from this urethane bonding sheet
The sample cut into the above size was left in a gear oven type heating furnace in an atmosphere of 120 ° C. for 500 hours. The color difference (ΔE) of the sheet from which the urethane foam was removed from the sample was measured by using an integrating sphere type Aucolor VP-1 color difference meter manufactured by Kurashiki Spinning Co., Ltd., and the results are shown in Table 1. Comparative Examples 1 to 3 In Example 1, tin perchlorate and hydrotalcite were not used (Comparative Example 1), hydrotalcite was not used (Comparative Example 2), and tin perchlorate was used. For each of those that were not used (Comparative Example 3), a molded product was manufactured in the same manner as in Example 1, and the color difference was measured and shown in Table 1.

[0016]

[Table 1]

[0017]

The vinyl chloride resin composition for powder molding of the present invention uses barium perchlorate, sodium perchlorate or magnesium perchlorate and tin perchlorate, and hydrotalcite from which water of crystallization has been removed. As a result, it is possible to exhibit extremely excellent heat resistance and amine resistance, and prevent discoloration and deterioration, as compared with the case where each of them is used alone.

Claims (8)

[Claims] 1. A resin composition for powder molding, wherein a vinyl chloride resin is dry blended with a plasticizer, wherein the resin composition is selected from barium perchlorate, sodium perchlorate and magnesium perchlorate. 1. A vinyl chloride resin composition for powder molding, comprising at least one of tin perchlorate and hydrotalcite having no water of crystallization. 2. The vinyl chloride resin composition for powder molding according to claim 1, wherein the plasticizer is a trimellitic acid ester plasticizer or a polyester plasticizer. 3. The content of barium perchlorate, sodium perchlorate or magnesium perchlorate in the range of 0.5 to 10 parts by weight per 100 parts by weight of vinyl chloride resin. A vinyl chloride resin composition for powder molding as described in the above. 4. The powder molding according to claim 1, wherein the content of tin perchlorate is in the range of 0.01 to 5 parts by weight per 100 parts by weight of the vinyl chloride resin. Vinyl chloride resin composition for use. 5. The content of hydrotalcite without water of crystallization is 0.5 to 10 per 100 parts by weight of vinyl chloride resin.
The vinyl chloride resin composition for powder molding according to any one of claims 1 to 4, which is in a range of parts by weight. 6. The vinyl chloride resin composition for powder molding according to claim 1, further comprising a powder fluidity improver of 5 to 100 parts by weight of the vinyl chloride resin.
A vinyl chloride resin composition for powder molding, wherein 30 parts by weight are uniformly dispersed. 7. The vinyl chloride resin for powder molding according to claim 6, wherein the powder fluidity improver is a vinyl chloride resin having an average particle diameter of 10 μm or less produced by an emulsion polymerization method or a fine suspension polymerization method. Resin composition. 8. The vinyl chloride resin composition for powder molding according to claim 6, wherein the powder fluidity improver is a fine inorganic filler.