JP4361746B2 - Vinyl chloride resin composition and molded article thereof - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a vinyl chloride resin composition, and more particularly to a vinyl chloride resin composition capable of improving impact strength and tensile strength by a reaction during molding and a molded product thereof.
[0002]
[Prior art and problems]
For the purpose of improving impact strength, vinyl chloride resin compositions are usually molded by various molding methods by adding core / shell type impact modifiers such as ABS, MBS resin and acrylic rubber to vinyl chloride resin. The
However, although the core / shell type impact modifier is effective in improving the impact strength, it is known that there is a problem that the tensile strength, particularly the tensile strength, is lowered.
When such a core / shell type impact modifier is mixed with a vinyl chloride resin and molded, the impact modifier and polyvinyl chloride do not have a chemical bond. Not expressed.
On the other hand, some core-shell type impact modifiers are copolymerized with polyvinyl chloride in advance, but in that case, there is a problem that industrial production is inferior because the polymerization process of the polyvinyl chloride copolymer is complicated. In addition, in order to improve thermal stability, a technique is known in which hydrazine is added to a dispersion of a chlorinated vinyl chloride resin in a polymerization process while blowing nitrogen gas to perform chemical bonding (for example, Patent Documents). 1).
[0003]
However, when molding vinyl chloride resin, there is no known technique that satisfies specific characteristics of both tensile strength and impact strength by combining specific additives and chemically bonding at the melting temperature. It was.
[0004]
[Patent Document 1]
JP-A-5-239119 [0005]
[Means for Solving the Problems]
The present invention has found a vinyl chloride resin assembly that can solve the above problems, and the gist of the present invention is that
A vinyl chloride characterized in that at least an acrylate copolymer and a reactive compatibilizer are added to a vinyl chloride resin, and the amount of the reactive compatibilizer is less than that of the acrylate copolymer. The resin composition.
[0006]
As the reactive compatibilizing agent, a hydrazine-based compound can be suitably used, and it is preferably added in the range of 0.1 to 2.0 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
As the vinyl chloride resin (hereinafter referred to as “PVC”) in the present invention, an ordinary polyvinyl chloride homopolymer can be used, and a small amount of a copolymerizable monomer such as vinyl acetate, vinylidene chloride or styrene is copolymerized. Copolymers and post-chlorinated products of these resins can also be used. The average degree of polymerization of PVC can be suitably used in the range of about 600 to 1,700, preferably about 820 to 1,450.
[0008]
A normal stabilizer is added to the PVC, and as the stabilizer, an organotin stabilizer having little toxicity, such as a dioctyltin compound, a monobutyltin compound, and a mixture thereof can be preferably used. What is necessary is just to use it as 0.2-3.0 weight part with respect to 100 weight part of PVC as a addition part number of a stabilizer, Preferably it is 0.3-2.5 weight part.
[0009]
In the present invention, it is necessary to use a specific impact modifier for the PVC, and an acrylate copolymer is used. Examples of the acrylate copolymer include acrylic rubber-acrylate copolymer, butadiene rubber-acrylate copolymer, (butadiene-styrene) rubber-acrylate copolymer, (acryl-silicon rubber) -acrylate copolymer, (acrylic) -Butadiene-styrene rubber) -acrylate copolymer.
It is necessary to use the acrylate copolymer in an amount of 4.0 to 15.0 parts by weight, preferably 5.0 to 8.0 parts by weight with respect to 100 parts by weight of PVC. If it is less than 4 parts by weight, the impact strength of the resulting molded product is inferior, and if it exceeds 15 parts by weight, the tensile strength is inferior.
[0010]
In the present invention, it is necessary to add a reactive compatibilizing agent together with the acrylate copolymer, and physical properties can be improved by reacting at the melting temperature at the time of molding. As the reactive compatibilizing agent, a hydrazine-based compound can be preferably used. The following compounds can be used as hydrazine compounds.
(1) hydrazine hydrate, hydrazine salt compound hydrazine hydrochloride, hydrazine hydrochloride, hydrazine hydrobromide, hydrazine sulfate, hydrazine phosphate, hydrazine carbonate, etc. (2) alkyl hydrazine compound benzyl hydrazine, butyl hydrazine hydrochloride, isopropyl hydrazine sulfate , Hydrazinoacetic acid methyl hydrochloride, etc.
(3) Hydrazide Compound Adipic acid dihydrazide, Zebatic acid dihydrazide, Todecandiohydrazide, Isophthalic acid dihydrazide, Propionic acid hydrazide, Salicylic acid hydrazide, Hydroxynaphthoic acid hydrazide, Carbohydrazide, Thiocarbohydrazide, Oxybisbenzenesulfonyl hydrazide, Aminopolyacrylamide, etc. (4) Pyrazole compound (5) Triazole compound (6) Tetrazole compound (7) Thiadiazole compound (8) Pyridazine compound (9) Azo compound
The added amount of the hydrazine-based compound is preferably 0.1 to 5.0 parts by weight, preferably 0.3 to 2.0 parts by weight with respect to 100 parts by weight of PVC. If the amount is less than 0.1 parts by weight, the resulting molded article has poor tensile strength. If the amount exceeds 5 parts by weight, the thermal stability tends to be inferior.
Here, the added part of the hydrazine-based compound needs to be an amount less than the above-mentioned acrylate-based copolymer, and if used exceeding the acrylate-based copolymer, the reaction with the vinyl chloride-based resin proceeds too much, so vinyl chloride There is a problem that the cross-linking of the resin itself is promoted and the molding process becomes difficult due to the increase in viscosity and thermal decomposition.
[0013]
In the composition of the present invention, a metal soap such as calcium stearate, a polyhydric alcohol such as dipentaerythritol, a colorant, a lubricant, an ultraviolet absorber, and the like can be appropriately added.
[0014]
The vinyl chloride resin composition according to the present invention can be prepared by a conventionally known method. For example, a vinyl chloride resin, a hydrazine compound, an acrylate copolymer, and if necessary, other resin additives are weighed in predetermined amounts and mixed in a mixer to form a dry blend. The method of kneading the thing of a form with a kneader is mentioned.
[0015]
There are no particular limitations on the mixer and kneader that can be used, and examples include conventionally known mixers such as a ribbon mixer, a change can mixer, and a super mixer (Henschel mixer). Examples of the kneader include a mixing roll, a Banbury mixer, a Σ blade type kneader, a high-speed biaxial continuous mixer, and an extruder type kneader.
[0016]
The vinyl chloride resin composition according to the present invention can produce products and parts having excellent target transparency by a conventionally known molding method such as extrusion molding, injection molding, compression molding and the like. As products and parts, extrusion molded products such as corrugated sheets, flat plates, and pipes can be suitably manufactured.
[0017]
【Example】
Examples of the present invention will be described below, but the present invention is not limited thereto.
Common formulation Vinyl chloride resin (degree of polymerization 1300) ... 100 parts by weight tin stabilizer (dioctyltin mercapto) ... 1 part by weight lubricant (polyethylene wax / dipentaerythritol stearate =
1/1 mixed lubricant one pack) ...... 1 part by weight chlorinated polyethylene ...... 1.5 parts by weight colorant ............ 0.3 parts by weight [0018]
[Example 1]
5 parts by weight of an acrylic impact modifier (silicon acrylic: “Metbrene S2001” manufactured by Mitsubishi Rayon Co., Ltd.) and 0.5 part of a hydrazine compound (adipic acid dihydrazide: “ADH” manufactured by Nippon Hydrazine Co., Ltd.) A part by weight was blended.
1 kg of the above blend was mixed with a Henschel mixer, and then kneaded for 5 minutes at 190 ° C. using two rolls to obtain a 0.5 mm thick sheet. The obtained sheet was heated and pressurized at 195 ° C. for 15 minutes at 100 Kg / cm ² with a heating press to obtain 1 mm and 5 mm thick samples. Impact strength and tensile strength were measured using the obtained samples.
As a result, the impact strength was 97 cm, and the tensile strength was 46.0 MPa.
Usually, an impact strength of 85 cm or more and a tensile strength of 44 MPa or more can be said to be good as an impact-resistant hard vinyl chloride resin molded product.
[0019]
In addition, the measuring method of impact strength and tensile strength is as follows.
-Impact strength Measured according to JIS7211. Using a sample with a thickness of 1 mm, a falling weight test was performed in a 2 kg weight tip R = 5 mm and −10 ° C. atmosphere, and a 50% fracture height was measured.
-Tensile strength Measured according to JIS K 6745. Sample thickness 5 mm, measurement temperature 23 ° C.
[0020]
[Example 2]
A sample was obtained in the same manner as in Example 1 except that acetone thiosemicarbazone (“ATS” manufactured by Nippon Hydrazine Co., Ltd.) was used instead of the hydrazine compound used in Example 1. Impact strength and tensile strength were measured using the obtained samples.
As a result, the impact strength was 87 cm and the tensile strength was 46.5 MPa.
[0021]
[Comparative Example 1]
A sample was obtained with the same composition as in Example 1 except that the hydrazine compound was not used in the composition of Example 1. Impact strength and tensile strength were measured using the obtained samples.
As a result, the impact strength was as low as 80 cm and the tensile strength was 45.9 MPa.
[0022]
[Comparative Example 2]
The same composition as in Example 1 except that the composition of Example 1 was changed to 7 parts by weight of the acrylic impact modifier (silicon acrylic type: “Metbrene S2001” manufactured by Mitsubishi Rayon Co., Ltd.) and no hydrazine compound was used. A sample was obtained. Impact strength and tensile strength were measured using the obtained samples.
As a result, the impact strength was 85 cm, the tensile strength was 41.0 MPa, the impact strength was good, but the tensile strength was low.
[0023]
【The invention's effect】
As described above, according to the resin composition of the present invention, it is excellent in moldability, appearance, strength, and the like of the obtained molded product, and can be used for manufacturing various molded products such as flat plates, pipes, and profile extrusion products. Is big.

Claims (4)

A vinyl chloride resin, at least acrylate copolymer made by adding the hydrazine compound as a reactive compatibilizing agent, the addition amount of the addition amount is less acrylate copolymer of the reactive compatibilizer A vinyl chloride-based resin composition ( excluding those containing a hydrazine-based compound as a foaming agent ). The vinyl chloride resin composition according to claim 1, wherein the hydrazine compound is a compound that reacts with the vinyl chloride resin and the acrylate copolymer depending on a melting temperature at the time of molding.   The vinyl chloride resin composition according to claim 1 or 2, wherein 0.1 to 5.0 parts by weight of a reactive compatibilizer is added to 100 parts by weight of the vinyl chloride resin. A molded article obtained by molding the vinyl chloride resin composition according to any one of claims 1 to 3 , wherein the hydrazine compound is reacted with a vinyl chloride resin and an acrylate copolymer. Molded articles characterized by being ( except those containing foamed hydrazine compounds) .