JPH07102145A - Vinyl chloride-based resin composition - Google Patents

Abstract

PURPOSE:To provide a vinyl chloride-based resin composition composed of a specified vinyl chloride-based resin and MBS resin, excellent in impact resistance, moldability, gelling properties and melt flow properties and useful for a molding, etc. CONSTITUTION:This vinyl chloride-based resin composition is composed of (A) 100 pts.wt. vinyl chloride-based resin prepared by polymerizing monomers composed mainly of vinyl chloride in the presence of a fatty acid ester of pentaerythritol or dipentaerythritol, more preferably a higher fatty acid ester of glycerin and (B) preferably 1 to 50 pts.wt. MBS resin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a vinyl chloride resin composition. More specifically, it has excellent impact resistance and
The present invention relates to a method for producing a vinyl chloride resin having excellent moldability.

[0002]

2. Description of the Related Art Conventionally, in order to improve impact resistance of vinyl chloride resin, it has been proposed and practiced to mix an MBS resin (methyl methacrylate / butadiene / styrene resin). For example, in Japanese Patent Publication No. 34-8136,
85 to 50% by weight of vinyl chloride resin and MBS resin 50
Resin compositions for injection-molding, extrusion-molding, and calendering have been proposed which consist of ~ 15% by weight. Tokusho
42-22541 and Japanese Patent Publication No. 44-453 describe a resin composition comprising an MBS resin in which a rubber component having a fine particle diameter is aggregated and a vinyl chloride resin, which are excellent in impact resistance and transparency. There is.

[0003]

Generally, by mixing the vinyl chloride resin with the MBS resin, the ease of melting (gelling property) and the melt fluidity at the time of melting the resin composition are lowered. To do. Therefore, a vinyl chloride resin composition that is mixed with an MBS resin and has excellent impact resistance, gelling characteristics, and melt flowability is provided.

[0004]

The present invention provides a resin composition comprising a vinyl chloride resin and an MBS resin, wherein the vinyl chloride resin comprises a monomer mainly composed of vinyl chloride,
A vinyl chloride resin composition characterized by being obtained by polymerization in the presence of pentaerythritol or dipentaerythritol fatty acid ester. Further, in a resin composition comprising a vinyl chloride resin and an MBS resin, the vinyl chloride resin contains a monomer mainly containing vinyl chloride, a fatty acid ester of pentaerythritol or dipentaerythritol, and a higher fatty acid of glycerin. A vinyl chloride resin composition characterized by being obtained by polymerization in the presence of an ester.

The vinyl chloride resin in the present invention is a polymer of vinyl chloride alone or a mixture of vinyl chloride as a main component and a mixture with an ethylenically unsaturated monomer copolymerizable therewith.

In particular, in the present invention, the monomer is polymerized in the presence of pentaerythritol or a fatty acid ester of dipentaerythritol.

In another case, the monomer is polymerized in the presence of pentaerythritol or dipentaerythritol fatty acid ester and glycerin higher fatty acid ester.

The fatty acid ester of pentaerythritol or dipentaerythritol is an ester of at least one hydroxyl group in one molecule of pentaerythritol or dipentaerythritol.

As the fatty acid, a monobasic organic acid having about 5 to 22 carbon atoms is suitable. Specifically, for example, hexanoic acid, lauric acid, palmitic acid, stearic acid,
Examples thereof include oleic acid and arachidic acid, and these may be used alone or in combination of two or more. Among them, the fatty acid preferably has 8 to 22 carbon atoms.

The higher fatty acid ester of glycerin is an ester of at least one hydroxyl group in one molecule of glycerin. The fatty acid is the same as above.

As the fatty acid ester of pentaerythritol or dipentaerythritol, so-called mixed ester obtained by esterifying the above fatty acid and a small amount of dibasic organic acid is also suitable. Examples of the mixed ester include those described in JP-A-53-6350.
That is, as the dibasic organic acid that can be used, malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid,
Examples include pimelic acid and phthalic acid. The ratio of the dibasic organic acid to the fatty acid is 1 mol of the former and 3 to 12 of the latter.
It is a mole. Regarding the mixed ester, some of the hydroxyl groups in one molecule of pentaerythritol or dipentaerythritol may remain.

The amount of the fatty acid ester is 100 parts by weight of the monomer.
0.01 to 10 parts by weight with respect to parts by weight, preferably
It is 0.1 to 5 parts by weight. If it is less than 0.01 part by weight, the workability improving effect is not sufficient.

Polymerization methods include suspension polymerization, microsuspension polymerization,
A well-known polymerization method of so-called vinyl chloride or a monomer mainly containing vinyl chloride such as emulsion polymerization and bulk polymerization may be used.
In addition, the type and amount of catalyst used, temperature conditions, equipment used, etc. may be known ones suitable for each of the above-mentioned polymerization methods. The presence of the fatty acid ester does not hinder the polymerization.

Well-known commercially available products can be applied to the MBS resin of the present invention. Among them, those having a butadiene content of 50% or more are preferable because they improve impact resistance.

The amount ratio of the vinyl chloride resin and the MBS resin in the resin composition composed of the vinyl chloride resin and the MBS resin may be within a known range, and it may depend on the impact resistance required depending on the intended use of the resin composition. Can be selected arbitrarily. For example, the latter is 1 to 50 parts by weight with respect to the former 100 parts by weight.

Any method may be used for forming a resin composition from the vinyl chloride resin and the MBS resin as long as they are intimately mixed, and a general thermoplastic resin mixing / kneading method can be applied. That is, the mixture is mixed by a ribbon mixer, a Henschel mixer, or the like and melt-kneaded by a calendar roll, a screw extruder, an injection molding machine, or a Banbury mixer. At this time, well-known stabilizers, plasticizers, colorants, lubricants and the like can be added as in the case of ordinary vinyl chloride resins.

[0017]

INDUSTRIAL APPLICABILITY The vinyl chloride resin composition of the present invention is not only excellent in impact resistance, but also has high fluidity at the time of melting, short gelation time, and low power at the time of gelation. Well balanced. Therefore, it is possible to obtain a precise molding down to a fine portion even if the shape of the molded body is melted and the molding speed is high at the time of molding and the shape is complicated as in the profile extrusion molding.

[0018]

EXAMPLES The present invention will be described in more detail below with reference to examples. Parts and% in the examples and comparative examples are by weight unless otherwise specified. The physical properties were evaluated by the following methods.

Melt fluidity: 100 parts of the resin composition and 3 parts of the lead-based composite stabilizer were kneaded with a roll at 160 ° C. for 5 minutes, and then formed into a sheet. The shredded material of the sheet was measured by a capillary flow characteristics tester (Capillograph-IB type manufactured by Toyo Seiki Co., Ltd.) from a die with a temperature of 160 ° C and a diameter of 2 mmφ to a shear rate of 9.85 sec.
^It was expressed as shear viscosity (poise) when extruded at ^-1 . Gelation property: 100 parts of resin composition and lead-based composite stabilizer 3
Parts and a mixture using a blender while raising the temperature to 130 ° C. for 10 minutes, and measuring the resin with a mixer tester (Labo Plastomill manufactured by Toyo Seiki Co., roller mixer R60 type) at 180 ° C. × 30 rpm, Maximum torque value (Kg
・ M). -Impact strength: 100 parts of the resin composition and 3 parts of the lead-based composite stabilizer were kneaded with a roll at 160 ° C for 5 minutes, and then 90 mm-10
mm and 5 mm test pieces were used. Using this test piece, JIS K7
Based on 111, it was expressed as a Charpy impact value (Kg · cm / cm ² ) at 23 ° C.

Example 1 40 parts of adipic acid and 470 parts of stearic acid were added to 100 parts of pentaerythritol, and 1.5 parts of NaOH as an esterification catalyst was added. After replacing the inside of the reaction system with nitrogen gas, the mixture was heated and stirred at 250 ° C. for 2 hours to carry out an esterification reaction. After the completion of the reaction, the reaction solution was dehydrated to obtain pentaerythritol adipic acid / stearic acid mixed ester.

A polymerization vessel having an internal volume of 100 liter equipped with a stirrer was degassed, and 45 kg of deionized water and vinyl chloride monomer 4 were added.
0 kg, 40 g of partially saponified polyvinyl alcohol, 15 g of tert-butyl peroxypivalate, 200 g of the above mixed ester and 5.5 g of chain transfer agent were charged, and the temperature was 62 ° C.
Polymerization was carried out by raising the temperature up to 9 kg / cm ² G, and when the pressure in the polymerization tank dropped to 9 kg / cm ² G, the unreacted monomer was released under atmospheric pressure to terminate the polymerization. 100 parts by weight of the obtained vinyl chloride resin and MB
A mixture of 5 parts by weight of S resin (Kaneace B-56, manufactured by Kanegafuchi Chemical Industry Co., Ltd.) was evaluated. The evaluation results are shown in Table 1.

Example 2 The procedure of Example 1 was repeated except that the amount of MBS resin was changed to 5 parts by weight instead of 20 parts by weight. The evaluation results are shown in Table 1.

Example 3 Instead of 200 g of mixed ester in Example 1, 200 g of mixed ester and 20 g of glycerine monostearate were used.
The same procedure as in Example 1 was carried out except that 0 g was used for the polymerization.
The evaluation results are shown in Table 1.

Example 4 Example 4 was repeated except that the amount of MBS resin was changed to 5 parts by weight instead of 20 parts by weight. The evaluation results are shown in Table 1.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that the mixed ester was not used. Only the obtained vinyl chloride resin was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 2 Using the vinyl chloride resin obtained in Comparative Example 1, MB
A resin composition containing 5 parts by weight of S resin was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 3 The same procedure as in Comparative Example 2 was repeated except that the amount of the MBS resin was changed to 5 parts by weight instead of 20 parts by weight. The evaluation results are shown in Table 1.

Comparative Example 4 Evaluation was performed in the same manner as in Comparative Example 2 except that 0.5 part by weight of the mixed ester was mixed with the vinyl chloride resin composition obtained in Comparative Example 2. The evaluation results are shown in Table 1.

Comparative Example 5 Evaluation was carried out in the same manner as in Comparative Example 2 except that the vinyl chloride resin composition obtained in Comparative Example 2 was mixed with 0.5 part by weight of the mixed ester and 0.5 part by weight of glycerin monostearate. The evaluation results are shown in Table 1.

Comparative Example 6 Only the vinyl chloride resin obtained in Example 3 was evaluated. The evaluation results are shown in Table 1.

[0031]

[Table 1]

Claims (2)

[Claims] 1. A resin composition comprising a vinyl chloride resin and an MBS resin, wherein the vinyl chloride resin comprises a vinyl chloride-based monomer in the presence of pentaerythritol or dipentaerythritol fatty acid ester. A vinyl chloride resin composition, characterized in that it is obtained by polymerizing into vinyl chloride. 2. A resin composition comprising a vinyl chloride resin and an MBS resin, wherein the vinyl chloride resin contains a monomer mainly containing vinyl chloride, a fatty acid ester of pentaerythritol or dipentaerythritol, and glycerin. The vinyl chloride resin composition obtained by polymerizing in the presence of the higher fatty acid ester.