JPH0525346A - Vinyl chloride resin composition - Google Patents

Abstract

(57) [Summary] [Structure] (A) A copolymer of vinyl chloride and diallyl esters or a copolymer of vinyl chloride and a monomer copolymerizable with vinyl chloride and diallyl esters, which comprises tetrahydrofuran A 100% soluble vinyl chloride resin, (B) a copolymer of vinyl chloride and a diallyl ester, or a copolymer of vinyl chloride, a monomer copolymerizable with vinyl chloride, and a diallyl ester, which comprises tetrahydrofuran A vinyl chloride resin having an insoluble gel content of 10 to 80% by weight and a balance of tetrahydrofuran-soluble content,
(C) contains a plasticizer, and uses the vinyl chloride resin as the component (A) and the vinyl chloride resin as the component (B) in a weight ratio of 99: 1 to 90:10. ,
A vinyl chloride resin composition comprising 30 to 200 parts by weight of a plasticizer as the component (C) and 100 parts by weight of the vinyl chloride resin as the components (A) and (B). provide. [Effect] The vinyl chloride resin composition of the present invention has excellent processability, rubber elasticity, particularly compression set, and has a matting effect. Therefore, it is suitable for automobiles and building materials such as window frame packings. Can be used for.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition which is excellent in processability, rubber elasticity, particularly compression set, and matting effect.

[0002]

2. Prior Art and Problems to be Solved by the Invention
Vinyl chloride resin is classified into hard and soft depending on the application, but especially in soft applications, for automobiles,
It has a wide range of uses such as packing for window frame building materials and agricultural vinyl sheets. Among them, there is particularly high demand for applications such as automobiles and building material window frame packings, but when used for these applications, a plasticizer is added to vinyl chloride resin so that it has a soft and rubber-like feel. Need to be softened.

However, the general soft vinyl chloride resin has poor creep resistance and the restoring force (compression set) after applying stress is smaller than that of rubber, so that such rubber elasticity is required. Its intended use was limited.

[0004] Therefore, for these applications, a rubber having a characteristic of being superior in compression set to a soft vinyl chloride resin is generally used. However, when a rubber is used, a vulcanization step is required, so that a working step is required. There is a drawback that the number of materials increases and the material cannot be recycled.

Therefore, it is possible to improve the compression set of the soft vinyl chloride resin composition so as to be suitable for applications such as automobiles and building material window frame packings, and to improve the matting property in terms of appearance. Is requested.

In response to such demands, various proposals have hitherto been made, for example, in Japanese Patent Publication No. Sho 64-3899, a vinyl chloride-based resin containing 10 to 80% by weight of a gel content insoluble in tetrahydrofuran and the balance a soluble content in tetrahydrofuran. A vinyl chloride resin composition has been proposed which comprises 100 parts by weight of a resin, 5 to 50 parts by weight of a crosslinked rubber-like substance having a dissolved content in tetrahydrofuran of 70% by weight or less, and 30 to 200 parts by weight of a plasticizer.

However, this type of vinyl chloride resin composition has a problem that the cost is very high because a large amount of rubber is used. Further, a composition obtained by not blending a rubber component with a vinyl chloride resin containing a tetrahydrofuran-insoluble gel component of this kind, but merely blending a plasticizer is inferior in processability, and has gelation property in the case of extrusion molding. Poor, it is impossible to obtain a good molded product.

The present invention has been made in view of the above circumstances,
An object of the present invention is to provide a vinyl chloride resin composition which is excellent in processability, rubber elasticity, particularly compression set, and is excellent in matting effect.

[0009]

Means and Actions for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has found that (A) a copolymer of vinyl chloride and diallyl esters or vinyl chloride and vinyl chloride. A copolymer of a copolymerizable monomer and a diallyl ester, which is a 100% soluble vinyl chloride resin in tetrahydrofuran, (B) a copolymer of vinyl chloride and a diallyl ester, or vinyl chloride and vinyl chloride. A copolymer of a copolymerizable monomer and a diallyl ester, which contains 10 to 80% by weight of a gel content insoluble in tetrahydrofuran and the balance a tetrahydrofuran soluble resin, and (C) a plasticizer. In addition, the weight ratio of the vinyl chloride resin as the component (A) to the vinyl chloride resin as the component (B) is 99: 1 to 1: 1.
When it is used in a ratio of 90:10 and 30 to 200 parts by weight of the plasticizer as the component (C) is blended with 100 parts by weight of the vinyl chloride resin as the component (A) and the vinyl chloride resin as the component (B).
The vinyl chloride resin composition obtained has good compression set, excellent processability, and matteness which are not possible with general soft vinyl chloride resins, and is cost effective because it does not use rubber. It was discovered that

That is, in a general soft vinyl chloride resin,
50 to 200 parts by weight of a plasticizer is added to a vinyl chloride resin having an average degree of polymerization of 2000 to 4000.
Such a composition is inferior in various physical properties such as compression set, and in order to obtain high physical properties, a vinyl chloride resin having a high average degree of polymerization must be used.

However, when a vinyl chloride resin having a high degree of polymerization, particularly 3500 or more is used, there is a problem that the plasticizing efficiency is lowered and the amount of the plasticizer needs to be increased, and further, the gelation is caused by the increase of the melt viscosity. There are problems such as poor workability and poor workability. For this reason, the processing temperature must be raised to make the workability appropriate,
As a result, the matteness of the surface becomes poor.

On the other hand, the present inventors have focused on vinyl chloride or a copolymer of vinyl chloride and a monomer copolymerizable therewith and a diallyl ester, and as such a copolymer completely dissolved in tetrahydrofuran. And a partially soluble one are used together, and a completely dissolved one and a partially dissolved one are used together in a weight ratio of 99: 1 to 90:10. It has been found that a synergistic effect can provide excellent compression set, workability, and matting effect.

In this case, when a copolymer which is partially soluble in tetrahydrofuran, that is, a copolymer containing vinyl chloride or vinyl chloride, a monomer copolymerizable therewith and a diallyl ester and containing a tetrahydrofuran insoluble component is used alone, Has excellent surface mattability, but has poor gelation property and poor processability.

Therefore, the present invention provides the above-mentioned component (A) vinyl chloride resin, component (B) vinyl chloride resin, and (C).
Component (A) component vinyl chloride resin and component (B) component vinyl chloride resin are used in a weight ratio of 99: 1 to 90:10, and
A vinyl chloride resin composition comprising 30 to 200 parts by weight of a plasticizer as the component (C) and 100 parts by weight of the vinyl chloride resin as the components (A) and (B). provide.

In the present invention, the "tetrahydrofuran-insoluble gel component" means an extraction residue extracted with hot tetrahydrofuran for 22 hours using a Soxhlet extractor and separated with a 350 mesh filter.

The present invention will be described in more detail below. The vinyl chloride resin composition of the present invention comprises a vinyl chloride resin which is 100% soluble in tetrahydrofuran (A) and tetrahydrofuran (B) as described above. With a vinyl chloride resin that partially dissolves in
It comprises a plasticizer as component (C).

In the present invention, both the components (A) and (B) are copolymers of vinyl chloride and diallyl esters or copolymers of vinyl chloride and vinyl chloride copolymerizable monomers and diallyl esters. Use coalescing.

Examples of diallyl esters include diallyl phthalate, diallyl isophthalate, diallyl terephthalate, and other phthalic acid diallyl esters, diallyl malate, diallyl fumarate, diallyl adipate, diallyl azelate, diallyl sebacate, and the like. Examples thereof include diallyl esters of saturated dibasic acid.

Examples of monomers copolymerizable with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate; acrylic acid esters or methacrylic acid esters such as methyl acrylate and ethyl acrylate; ethylene and propylene. Olefins; maleic anhydride; acrylonitrile; styrene; vinylidene chloride and the like.

The component (A) of the composition of the present invention comprises 1% of tetrahydrofuran in the above-mentioned vinyl chloride copolymer.
Use one that dissolves 00%. In order to obtain such a vinyl chloride-based copolymer completely soluble in tetrahydrofuran, 0.01 to 2% by weight of diallyl ester is added to 100% by weight of vinyl chloride monomer in the polymerization system, particularly 0.05 to It is preferable to add 0.12% by weight.
If the amount added is less than 0.01% by weight, the degree of polymerization of the obtained vinyl chloride-based copolymer may be low and the physical properties may be deteriorated. If the amount added is more than 2% by weight, a gel component may be formed.
Further, among the above-mentioned diallyl esters, diallyl phthalate is preferable because it does not affect the processability more than other diallyl esters. The polymerization method is not particularly limited, but the suspension polymerization method is preferable.

On the other hand, the component (B) of the composition of the present invention is a vinyl chloride copolymer having a gel content insoluble in tetrahydrofuran of 10 to 80% by weight, preferably 15 to 30% by weight, and the balance being a tetrahydrofuran soluble content. use. If the gel content insoluble in tetrahydrofuran is less than 10%, a good matting effect cannot be obtained, and if it exceeds 80% by weight, workability becomes poor.

In order to obtain such a vinyl chloride copolymer partially soluble in tetrahydrofuran, 0.05 to 5% by weight of diallyl ester is added to 100% by weight of vinyl chloride monomer in the polymerization system. Is preferred.
Among the above-mentioned diallyl esters, diallyl malate is preferably used because it is superior in matting property to those of other diallyl esters.

In the composition of the present invention, the vinyl chloride resin as the component (A) and the vinyl chloride resin as the component (B) are contained in a weight ratio of 99: 1 to 90:10, preferably 9%.
It is necessary to set the ratio to 7: 3 to 94: 6. If the proportion of the component (B) is lower than this range, the matte surface property is unfavorable and the surface becomes glossy. On the other hand, if the proportion of the component (B) is higher than the above range, the gel component is produced more than necessary. Processability, especially gelling property, is not preferable.

The type of the plasticizer as the component (C) is not particularly limited, and examples thereof include alkyl esters of aromatic polybasic acids such as dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate, dioctyl adipate, dioctyl azelate, dioctyl sebac. Examples thereof include alkyl esters of aliphatic polybasic acids such as cate.

In the composition of the present invention, the compounding amount of the plasticizer as the component (C) is 30 to 200 parts by weight based on 100 parts by weight of the total of the vinyl chloride resin as the above components (A) and (B). And preferably 40 to 150 parts by weight. If the blending amount is less than 30 parts by weight, the compression set becomes large, and if the blending amount exceeds 200 parts by weight, the productivity and processability become poor.

In the composition of the present invention, in addition to the above-mentioned components, a necessary amount of a thermoplastic resin, a heat stabilizer, a filler, a pigment, a processing aid and the like can be blended.

Here, examples of the thermoplastic resin include general polyvinyl chloride resin, ethylene-vinyl acetate copolymer, chlorinated polyethylene, ABS resin, AS resin, urethane, acrylic resin and the like.

Examples of the heat stabilizers include lead stabilizers such as tribasic lead sulfate, tin stabilizers such as dibutyltin malate, and metallic soaps such as zinc stearate and calcium stearate.

Examples of the filler include calcium carbonate, titanium oxide, talc, asbestos, aluminum hydroxide, magnesium hydroxide and the like.

Further, as the pigment, for example, carbon black, chrome yellow, titanium oxide and the like can be mentioned, and as a processing aid, it is used in a usual vinyl chloride resin composition such as low molecular weight polyethylene and higher fatty acid ester. One can be used.

The vinyl chloride resin composition of the present invention can be manufactured by the same steps as the conventional vinyl chloride resin composition. For example, the above components (A), (B) and (C) are mixed with a thermoplastic resin, a heat stabilizer, etc., if necessary, with a mixer such as a super mixer or a blender, and then a Banbury mixer, a mixing roll, an extruder, etc. It can be kneaded and manufactured.

The processability of the vinyl chloride resin composition of the present invention produced as described above is as good as that of a general soft vinyl chloride resin, and therefore, it is the same as that of a general soft vinyl chloride resin. Injection molding, extrusion molding, press molding,
It can be molded by blow molding, calender molding, or the like.

[0033]

EXAMPLES Hereinafter, the present invention will be specifically shown by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Examples and Comparative Examples] The vinyl chloride resin as the component (A) was produced by charging a vinyl chloride monomer, a suspending agent and a polymerization initiator in a 2 m ³ autoclave, and adding 0.05% by weight of diallyl phthalate. Or 0.1
Suspension polymerization was carried out at a polymerization temperature of 40 ° C. in the presence of 2% by weight to obtain the following two kinds of resins (hereinafter referred to as resin A). Resin number Tetrahydrofuran insoluble content Addition amount of diallyl phthalate Average degree of polymerization A-10 10% by weight 0.05% by weight 2700 A-20% by weight 0.12% by weight 3400 (B) Component vinyl chloride resin production Kaisho 59-
According to the method described in Japanese Patent Publication No. 43045, the following tetrahydrofuran-insoluble matter is 10% by weight and 80
Two kinds of resins (hereinafter, referred to as resin B) having a weight% were obtained. Resin number Tetrahydrofuran insoluble content Amount of diallymalate added B-1 10% by weight 0.7% by weight B-2 70% by weight 1.0% by weight

These resins A and B were used in the proportions shown in Table 1, and 100 parts by weight of the total amount of these resins were blended according to the following formulation, using a 100 liter hot mixer. A compound was prepared by using the compound, and kneaded into pellets using a Banbury mixer having a capacity of 50 liters. Compounding formula Tin stabilizer 0.5 parts by weight Epoxy stabilizer 2.0 〃 Polyethylene lubricant 1.0 〃 Calcium carbonate 20 〃 Black carbon 1.0 〃 Plasticizer (dioctyl phthalate) 80 〃

The pellets were formed into a sheet by a 6-inch roll having a temperature of 170 ° C., subjected to press working, and JIS-
The compression set was measured according to K-6301. A sheet was extruded from the pellets using an extruder having an inner diameter of 50 mm, and the mattness of the surface was visually evaluated according to the following criteria. Good: Delustrated very well Poor: Almost delustered

Regarding workability, a plastograph manufactured by Brabender was used for the kneaded pellets, and in the plastograph test, those having a required gelation time shorter than that of the straight vinyl chloride resin were evaluated as good, and those having a longer gelation time were evaluated as poor.

For comparison, a general-purpose vinyl chloride resin having a tetrahydrofuran insoluble content of 0% and an average degree of polymerization of 3000 obtained without adding diallyl ester was similarly tested. The results are also shown in Table 1.

[0039]

[Table 1]

From the results shown in Table 1, the general-purpose vinyl chloride resin is
Although the compression set and the matteness are inferior, the matteness is inferior when the resin A (100% dissolved in tetrahydrofuran) is used alone, and the processability is inferior when the resin B (partially dissolved in tetrahydrofuran) is used, the resin A It is recognized that the combination of the resin and the resin B has good compression set, processability, and matteness.

[0041]

The vinyl chloride resin composition of the present invention is excellent in workability and rubber elasticity, particularly in compression set.
Moreover, it has an excellent matte effect, and therefore can be suitably used for automobiles, building material window frame packings and the like.

Claims (1)

1. A copolymer of vinyl chloride and diallyl esters or a copolymer of vinyl chloride and a monomer copolymerizable with vinyl chloride, and diallyl esters, comprising: A vinyl chloride resin which is 100% soluble in tetrahydrofuran, (B) a copolymer of vinyl chloride and a diallyl ester, or a copolymer of vinyl chloride, a monomer copolymerizable with vinyl chloride and a diallyl ester, 10% to 80% by weight of a gel component insoluble in tetrahydrofuran and the balance comprising a tetrahydrofuran soluble component, (C) a plasticizer, and a vinyl chloride resin of the above component (A) and (B) The vinyl chloride resin as the component is used in a weight ratio of 99: 1 to 90:10, and the plasticizer as the component (C) is a salt of the components (A) and (B). 100 parts by weight of the total of the vinyl resin from 30 to 200
A vinyl chloride resin composition characterized by being mixed in parts by weight.