JPH0632957A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition which gives a molding excellent in flame retardancy, weatherability, rigidity, impact strength, high-temperature mechanical strength, heat distortion resistance, etc., by compounding specified vinyl chloride resin, a specified styrene copolymer, and an AES resin each in a specified amount. CONSTITUTION:This resin composition consists of 40-70wt.% vinyl chloride resin having an average Cl, content of 59-70wt.% (e.g. chlorinated vinyl chloride resin), 15-40wt.% styrene copolymer (e.g. styrene/acrylonitrile copolymer) formed by copolymerizing a styrenic compound with a vinyl cyanide compound, and 5-40wt.% AES resin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to a vinyl chloride resin composition.

[0002]

2. Description of the Related Art Vinyl chloride resin has excellent properties such as flame retardancy, rigidity, weather resistance, and chemical resistance, but since it has low impact strength and poor thermal deformation resistance, It was unsuitable for use in equipment housings (called OA) and internal parts of automobiles that become hot.

In order to improve the heat distortion resistance of the vinyl chloride resin, it has been practiced to mix the vinyl chloride resin and the chlorinated vinyl chloride resin to increase the average chlorine content of the vinyl chloride resin. However, as the average chlorine content of the vinyl chloride resin increases, there is a problem in that the impact strength of the molded product is reduced, and the heat fluidity is reduced, resulting in reduced molding performance.

In order to improve the heat fluidity of the vinyl chloride resin composition, a styrene copolymer obtained by copolymerizing a styrene compound and a vinyl cyanide compound is added, and the impact of the molded product is In order to increase strength, acrylonitrile-butadiene-styrene copolymer (hereinafter ABS
Resin) is added. It has also been proposed to use the styrene-based copolymer in combination with an ABS resin (for example, JP-A-63-191851).

However, in order to obtain high heat distortion resistance and high impact strength with the above composition, the styrene copolymer and the ABS resin must be added in a large amount, and as a result, flame retardancy is reduced. It had the drawback of falling. Also, A
The addition of the BS resin has a drawback that the weather resistance such as a significant discoloration in the outdoors is remarkably lowered and the rigidity is lowered so that it is easily deformed.

Chlorinated polyethylene is also used as an impact strength improver. For example, Japanese Patent Laid-Open No. 3-1340
Japanese Patent Laid-Open No. 44-44 proposes a vinyl chloride resin composition comprising a vinyl chloride resin, the styrene copolymer, and chlorinated polyethylene. However, the molded product obtained from this composition has a problem that the tensile elongation upon heating is small and the high temperature mechanical strength is lowered such as cracking when stress is applied.

[0007]

SUMMARY OF THE INVENTION In view of the above-mentioned drawbacks, the present invention has good heat fluidity, can easily mold a molded body, and has flame retardancy, weather resistance and rigidity of the obtained molded body. It is an object of the present invention to provide a vinyl chloride resin composition which is excellent in impact strength, mechanical strength at high temperature, thermal deformation resistance, etc. and can be suitably used for housings of OA equipment, internal parts of automobiles and the like.

[0008]

As the vinyl chloride resin used in the present invention, a homopolymer of vinyl chloride, and another monomer or two or more monomers containing vinyl chloride as a main component and copolymerizable therewith And copolymers of these polymers, and chlorinated products of these polymers or mixtures of these polymers.

As the monomer copolymerizable with the above-mentioned vinyl chloride, α-such as ethylene, propylene and 1-butene can be used.
Olefin, vinyl acetate, vinyl propionate, vinyl stearate and other vinyl esters, styrene, α
-Styrenes such as methyl styrene, vinyl ethers such as isobutyl vinyl ether, cetyl vinyl ether and phenyl vinyl ether, alkyl (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate, vinylidene chloride, halogen such as vinyl fluoride Vinyl chlorides, cyclohexylmaleimide,
Examples include N-substituted maleimides such as phenylmaleimide.

The average degree of polymerization of the vinyl chloride resin is not particularly limited, but when it is small, the impact strength of the obtained molded article is lowered, and when it is large, the heat fluidity is lowered and the molding performance is lowered. It is preferably 300 to 800, and more preferably 300 to 800.

If the average chlorine content of the vinyl chloride resin decreases, the heat distortion resistance decreases, and if it increases, the impact strength decreases, the heat fluidity decreases, and the molding performance decreases. Limited. Therefore, the vinyl chloride resin, so that the average chlorine content is within the above range,
Used alone or in combination of two or more kinds of resins, preferably a homopolymer of vinyl chloride or a copolymer of vinyl chloride as a main component and another one or two or more kinds of monomers copolymerizable therewith. , A mixture of these polymers with a chlorinated product.

The styrene copolymer used in the present invention is a copolymer of a styrene compound and a vinyl cyanide compound.

Examples of the styrene compound include
Examples thereof include styrene and α-methylstyrene, and styrene is preferable because it has excellent heat fluidity and good molding performance.

Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile, and acrylonitrile is preferable because it has excellent compatibility with vinyl chloride resins.

Acrylonitrile-styrene resin can be preferably used for the above styrene copolymer.

From the viewpoint of impact strength and thermal fluidity, the styrene-based copolymer is preferably a copolymer of a styrene-based compound and a vinyl cyanide compound in a weight ratio of 60:40 to 80:20. The weight average molecular weight is preferably 30,000 to 150,000, because when the weight average molecular weight decreases, the impact strength of the obtained molded article decreases, and when the weight average molecular weight increases, the heat fluidity decreases and the molding performance decreases.

The AES resin used in the first invention is a resin obtained by graft-polymerizing acrylonitrile, EPM or EPDM, and styrene. Where EPM
Is a copolymer of ethylene and propylene, and EPD
M is a terpolymer containing ethylene, propylene and a non-conjugated diene as a third component, and examples of the non-conjugated diene include dicyclopentadiene and methyltetrahydroindene (formally named 4-methyl-bicyclo [4.3.0. ] Nona-3,7-diene), ethylidene norbornene (formal name 5-ethylidene-bicyclo [2.2.1] hept-
2-ene), 1,4-hexadiene and the like.

When the weight average molecular weight of the AES resin is small, the impact strength of the obtained molded article is low, and when it is large, the heat fluidity is low and the molding performance is low.
10,000 is preferable.

Examples of the above-mentioned AES resin include, for example, the product name Rovel manufactured by Uniroyal Co., the product name Unibright manufactured by Sumitomo Nogatac Co., Ltd., and the product name JSR manufactured by Japan Synthetic Rubber Co., Ltd.
AES etc. are on the market.

The vinyl chloride resin composition of the first invention is
The above vinyl chloride resin, styrene copolymer, and AE
Although it is a composition comprising S resin, when the amount of vinyl chloride resin used is reduced, the flame retardancy is reduced, and when the amount of styrene copolymer used is reduced, the heat fluidity is reduced, and when it is increased, the impact strength and If the amount of AES resin used is low, the impact strength is low, and if it is high, the heat distortion resistance and heat fluidity are low.
~ 70 wt%, 15-40 wt% styrene copolymer
%, AES resin is 5 to 40 wt%.

When the residual crystallinity of the chlorinated polyethylene used in the second invention is small, the tensile elongation at high temperature is low, the high temperature mechanical strength is low such as cracking when stress is applied, and when it is high, the impact is high. Since the improvement in strength becomes small, it is 5 to 30%, preferably 10 to 2
It is 0%. The degree of chlorination of chlorinated polyethylene is not particularly limited, but impact strength is reduced regardless of whether it is small or large, so that it is preferably 25 to 40 wt%. Further, the weight average molecular weight of chlorinated polyethylene is preferably 100,000 to 150,000, because when the weight average molecular weight becomes small, the impact strength of the obtained molded article decreases, and when it becomes large, the heat fluidity decreases and the molding performance decreases.

The vinyl chloride resin composition of the second invention is
A composition comprising the vinyl chloride resin, a styrene copolymer, and the chlorinated polyethylene, but the flame retardance decreases when the amount of the vinyl chloride resin used decreases, and the amount of the styrene copolymer used. When the amount of chlorinated polyethylene decreases, the heat fluidity decreases, and when the amount of chlorinated polyethylene decreases, the impact strength decreases, and when the amount of chlorinated polyethylene decreases, the heat deformation resistance and heat fluidity decrease. 30 ~ 70wt% vinyl chloride resin, 20 ~ 55wt% styrene copolymer, 5 ~ 35 chlorinated polyethylene
wt%.

To the vinyl chloride resin composition of the first invention, chlorinated polyethylene may be further added in order to further improve flame retardancy and heat fluidity. Is preferably 5 to 30% chlorinated polyethylene.

An AES resin may be further added to the vinyl chloride resin composition of the second invention in order to further improve impact strength.

An acrylic rubber resin may be further added to the vinyl chloride resin composition of the first invention and the second invention in order to further improve impact strength.

The above-mentioned acrylic rubber-based resin means methyl acrylate, ethyl acrylate, butyl acrylate,
It is a copolymer mainly composed of acrylate such as octyl acrylate and the like with 2-chloroethyl vinyl ether, methyl vinyl ketone, acrylic acid, acrylonitrile, butadiene and the like.

Examples of the acrylic rubber-based resin include Kane-Ace FM (trade name, manufactured by Kanegafuchi Chemical Co., Ltd.) and Kureha KM-334 (trade name, manufactured by Kureha Chemical Co., Ltd.).

When two or more kinds of AES resin, chlorinated polyethylene and acrylic rubber resin are used in combination with the vinyl chloride resin composition of the first invention and the second invention, the total amount of use and vinyl chloride are used. The ratio of the total amount of the styrene-based copolymer to the resin-based resin is preferably 10:90 to 30:70.

The vinyl chloride resin composition of the present invention comprises:
Further conventionally used, lubricants such as polymethylmethacrylate-based processing aids, dibutyltin malate, dibutyltin mercapto, metal soap, heat stabilizers such as lead compounds, antioxidants, ultraviolet absorbers, calcium carbonate,
Fillers such as glass fibers, pigments such as titanium oxide, dyes and the like may be appropriately added.

As a method of molding a molded product from the vinyl chloride resin composition of the present invention, a conventionally known method can be adopted, and examples thereof include extrusion molding, calender molding, roll press molding and injection molding. It is particularly suitable for injection molding.

For injection-molding the vinyl chloride resin composition of the present invention, for example, the composition is uniformly mixed with a supermixer, and the mixture or this mixture is supplied to an extruder and then pelletized. The pellets obtained by cutting may be supplied to an injection molding machine, heated and melted, injected and filled in a mold, solidified, and then demolded. The injection conditions are generally a barrel temperature of 160 to 190 ° C. and an injection pressure of 100. ~ 1
It is 50 kgf / cm ² .

[0032]

Embodiments of the present invention will be described below. In addition,
"Parts" means "parts by weight".

In the following examples, the residual crystallinity of chlorinated polyethylene and the flame retardancy, impact strength, rigidity, high temperature mechanical strength, weather resistance, and heat distortion resistance of the obtained sample,
The thermal fluidity of the composition was evaluated as follows. (1) Residual crystallinity: The area ratio of the absorption peaks of the melting points before and after chlorination of crystalline polyethylene into chlorinated polyethylene was evaluated by DSC. (2) Flame retardancy: UL-94 for 1/16 inch thick samples
It evaluated based on the V method. (3) Impact strength: A notched Izod strength of a 0.125-inch sample was measured at 23 ° C. according to ASTM D-256. (4) Rigidity: The flexural modulus was measured at 23 ° C. according to ASTM D-790, and the presence or absence of cracks in the test piece after the measurement was observed. (5) High temperature mechanical strength: in accordance with ASTM D-790,
The flexural modulus was measured at 60 ° C. and the presence or absence of cracks in the test piece after the measurement was observed. (6) Weather resistance: ΔE (CIE 1976) of a sample tested for 1000 hours with a sunshine weather o-meter.
L ^* a ^* b ^* color system) was measured. (7) Thermal deformation resistance: in accordance with ASTM D-643, without annealing a 0.25 inch thick sample,
The heat distortion temperature was measured under a load of 18.6 kgf / cm ² . (8) Thermal fluidity: A Koka type flow tester was used to measure the discharge rate at a nozzle size of 1φ × 10 mm, a load of 100 kgf / cm ² , and a temperature of 205 ° C.

Examples 1 to 7 and Comparative Examples 1 to 4 Predetermined amounts of vinyl chloride resin, chlorinated vinyl chloride resin and styrene-based copolymer (styrene; 76 wt%, shown in Table 1)
Acrylonitrile; 24 wt%, molecular weight 65000),
AES resin (Sumitomo Nogatak Co., Ltd., trade name Unibright PSN-627, weight average molecular weight 150,000), acrylic rubber resin (Kureha Chemical Co., Ltd., trade name Kureha KM-33)
4), ABS resin, and total amount of chlorinated polyethylene 1
00 parts of dibutyltin malate (manufactured by Sankyo Machine Gosei Co.,
Trade name BM (N)) 3 parts, dibutyltin mercapto (Sankoki Gosei Co., Ltd., trade name JF-9B) 0.5 part, calcium stearate 1 part, and ester lubricant (Henkel Hakusui Co., trade name Roxyol) G70S) together with 1 part was supplied to a super mixer (manufactured by Kawata Manufacturing Co., Ltd.), mixed well until it reached 100 ° C by spontaneous heat generation, cooled to 40 ° C with a cooling mixer, and then kneaded with a roll mill at 180 ° C for 3 minutes. I got a thing. 190 the obtained kneaded product
A sample for measurement was obtained by pressing for 10 minutes at a temperature of 150 kgf / cm ² . The physical properties of the obtained sample were measured, and the results are shown in Table 1.

[0035]

[Table 1]

Examples 8 to 14, Comparative Examples 5 to 7 Vinyl chloride resin, chlorinated vinyl chloride resin, styrene copolymer, AES resin, acrylic rubber resin, ABS resin, and chlorinated polyethylene are shown in Table 2. The same procedure as in Example 1 was carried out except that the amount was changed to that shown in. The physical properties of the obtained sample were measured, and the results are shown in Table 2.

[0037]

[Table 2]

[0038]

The vinyl chloride resin composition of the present invention comprises
The heat fluidity is good, and the molded body can be easily molded. The obtained molded article is excellent in flame retardancy, weather resistance, rigidity, impact strength, high temperature mechanical strength, heat deformation resistance, etc.
It is suitable for use in the housing of equipment A, internal parts of automobiles, etc., and also applicable to outdoor applications.

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Claims (2)

[Claims] 1. A vinyl chloride resin having an average chlorine content of 59 to 70 wt%, 40 to 70 wt%, and a styrene copolymer 15 to 40 wt%, which is obtained by copolymerizing a styrene compound and a vinyl cyanide compound. AES resin 5-40w
A vinyl chloride resin composition comprising t%. 2. A vinyl chloride resin having an average chlorine content of 59 to 70 wt%, 30 to 70 wt%, and a styrene copolymer 20 to 55 wt%, which is obtained by copolymerizing a styrene compound and a vinyl cyanide compound. Residual crystallinity is 5 to 3
A vinyl chloride resin composition comprising 0% chlorinated polyethylene 5-35 wt%.