JPH05295205A - Vinyl chloride-based resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition excellent in heat resistance and thermal stability. CONSTITUTION:The objective composition can be obtained by blending 100 pts.wt. of a vinyl chloride-based resin with 5-100 pts.wt. of an A-B type block copolymer made up of the A-component consisting of at least one kind of structural unit selected from (meth) acrylic esters and vinyl esters and the B- component consisting of structural unit (s) derived from at least one kind of radical-polymerizable monomer different from the A-component.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a vinyl chloride resin composition having excellent heat stability.

[0002]

2. Description of the Related Art Vinyl chloride resin has mechanical strength, weather resistance,
It has excellent physical properties such as chemical resistance and self-extinguishing property, and is widely used for pipes, plates, films, sheets, containers, etc., but it has a low softening temperature and poor thermal deformation resistance. Hard vinyl chloride resin generally causes thermal deformation at 70 to 80 ° C., and therefore cannot be used at temperatures higher than that.

Various methods have been proposed in order to improve the heat distortion resistance, for example, vinyl chloride-N-allyl maleimide copolymer and the like. Although this copolymer has improved heat resistance and excellent fluidity, it has the drawback of being poor in thermal stability and being easily dehydrochlorinated during heat molding.

Further, in order to improve the thermal stability, it has been proposed to add an organic tin stabilizer, a lead stabilizer, a violite compound, etc., but the thermal stability is still insufficient. .

Further, in JP-A-2-276847, a vinyl chloride resin, a methyl methacrylate component, N
Selected from the group consisting of alkyl acrylates, methacrylic acid alkyl esters, aromatic vinyl compounds and vinyl cyanide compounds in the presence of a copolymer of a substituted maleimide component and an aromatic vinyl component or an elastomer containing a conjugated diene component. Although a method of blending a copolymer obtained by graft-polymerizing one or more monomers has been proposed, impact resistance is improved but thermal stability is still insufficient.

[0006]

In view of the above drawbacks, an object of the present invention is to provide a vinyl chloride resin composition having excellent heat resistance and heat stability.

[0007]

Means for Solving the Problems As a result of intensive studies for achieving the above object, the present inventors have found that the component (A) is (meth) acrylic acid ester and vinyl per 100 parts by weight of vinyl chloride resin. From a structural unit derived from one or more structural units derived from one or more kinds selected from esters, and the component B being derived from one or two or more radical-polymerizable monomers different from the component A. The present invention has been completed by finding out a vinyl chloride resin composition characterized by containing 5 to 100 parts by weight of the following AB type block copolymer.

The AB block copolymer used in the present invention comprises a structural unit in which the component A is derived from one or more selected from (meth) acrylic esters and vinyl esters, and B The component is an AB block copolymer composed of structural units derived from one or more radical-polymerizable monomers different from the component A, and the component B is preferably a vinyl ester or a maleimide compound. , A block copolymer composed of structural units derived from one or more monomers selected from aromatic vinyl.

Of the above-mentioned monomers, the (meth) acrylic acid ester is preferably one in which the alkyl group usually has 1 to 22 carbon atoms, and specifically, methyl (meth) acrylate, (meth ) Ethyl acrylate, butyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, amyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid Examples include decyl, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and benzyl (meth) acrylate.

Examples of vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl palmitate, vinyl stearate and olein. Examples thereof include vinyl acetate and vinyl pivalate.

Examples of the aromatic vinyl include styrene, α-methylstyrene, o-chlorostyrene, p-chlorostyrene and vinyltoluene.

As the maleimide compound, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-tert-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, Examples thereof include N-hydroxyphenyl maleimide and N-lauroyl maleimide.

Monomers other than the above are (meth) acrylic acid, (meth) acrylic acid amide, vinyl ether,
Aromatic vinyl, maleimide compound, unsaturated dicarboxylic acid (anhydride), vinyl cyanide, vinylpyrrolidone, α-
Various things such as olefill are possible.

As the unsaturated dicarboxylic acid anhydride, maleic anhydride, chloromaleic acid anhydride, dichloromaleic acid anhydride, citraconic acid anhydride, itaconic acid anhydride,
Examples thereof include phenyl maleic anhydride and aconitic anhydride.

Examples of vinyl cyanide include acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, and acrylonitrile is particularly preferable.

In the AB type block copolymer used in the present invention, it is sufficient that the A component and the B component are linearly bonded and both form a main chain, and the other A component and the B component.
Both or one of the components may be grafted.

In the vinyl chloride resin composition of the present invention, various rubber components may be added, if necessary, in addition to the vinyl chloride resin and the AB block copolymer. Examples of the rubber component used here include polybutadiene, styrene-butadiene block polymer, nitrile rubber, maleated rubber, polyisoprene rubber, butadiene-acrylonitrile rubber, and ethylene-propylene-diene terpolymer.

The degree of polymerization of the components A and B of the AB block copolymer used in the present invention is not particularly limited, but both components have an average degree of polymerization (Pn) of 5000 or less. preferable.

The AB type block copolymer used in the present invention has a structure represented by the following formula (1) AB-(1) where A: a structural unit derived from a (meth) acrylic acid ester. The polymer B is represented by a polymer composed of structural units derived from a radically polymerizable monomer different from the component A. The production method is not particularly limited, but when radically polymerizing the monomer of the component A or the component B, thiolcarboxylic acid or 2-acetylthioethylthiol, 10-acetylthiodecanethiol, etc. Polymerization in the presence of a compound containing a thioester and a thiol group, the resulting polymer is treated with an alkali such as sodium hydroxide or ammonia to give a polymer having a thiol group at one end, The method of obtaining the block copolymer by the radical polymerization of the monomer of one component is the most preferable as the method of obtaining the block copolymer simply and highly efficiently. In this case, a block copolymer in which the A component and the B component are bonded via a sulfur atom is obtained. This manufacturing method is described in detail in JP-A-59-189111.

The constitution of the vinyl chloride resin composition of the present invention is as described above, and calcium stearate, zinc stearate, barium stearate, cadmium stearate, which are used as stabilizers for vinyl chloride resins, Metallic soaps such as lead stearate, dibasic sulfates, dibasic lead stearate, calcium hydroxide, inorganic stabilizers such as calcium silicate, lubricants, pigments, fillers, impact modifiers, processing aids, An ultraviolet absorber or the like may be added.

[0021]

EXAMPLES Next, the present invention will be described with reference to Examples and Comparative Examples.
This will be described more specifically. In the following, parts and% mean parts by weight and% by weight, respectively. Examples 1 to 9: A vinyl chloride resin was blended with the AB block copolymer shown in Table 1 and the various additives shown below, and each was mixed with a mixer to obtain 19
A sheet was obtained by kneading with a roll at 0 ° C. for 3 minutes. The obtained sheet was supplied to a gear oven at 190 ° C., and the time until blackening (aging blackening time) was measured. Also, the obtained sheet is supplied to a press molding machine, and the temperature is 190 ° C and 75 kg.
Press molding was performed for 5 minutes under the condition of / cm ² to obtain a molded plate. The Vicat softening temperature of the obtained molded plate was measured.
The results are shown in Table 2. Comparative Examples 1 to 5: In the composition of the above-mentioned examples, the composition in which the homopolymer or the random copolymer shown in Table 1 was mixed instead of the AB block copolymer was prepared under the same conditions as in the above-mentioned example. A sheet is obtained, the blackening time of the sheet is measured, and a press-molded plate of the sheet is molded,
The Vicat softening temperature was measured. The results are shown in Table 2 together with the results of the examples. << Compound and its compound composition >> Addition amount Vinyl chloride resin (degree of polymerization: 1050) 100 parts Block copolymer (see Table 1) Described in Table 1 Lubricant (Hoechst-Wax OP) 0.5 part Lead stearate 0.8 parts Barium stearate 0.6 parts Tribasic lead sulfate 1.8 parts

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

As is apparent from the above examples, the vinyl chloride resin composition of the present invention has excellent heat resistance and thermal stability. Therefore, the plate, pipe, and
It can be suitably used as a material for forming sheets, containers and the like.

Claims (1)

[Claims] 1. To 100 parts by weight of vinyl chloride resin,
Among the radically polymerizable monomers in which the component A is composed of structural units derived from one or more selected from (meth) acrylic acid esters and vinyl esters, and the component B is different from the component A AB type block copolymers 5 to 10 composed of structural units derived from one kind or two or more kinds
A vinyl chloride resin composition comprising 0 parts by weight.