JPS6198760A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:A composition having improved flame retardance, heat resistance, and impact resistance in a good balance, obtained by blending a styrenic copolymer with Cl-PVC and CPE, where the components are blended in good compatibility. CONSTITUTION:(A) A compolymer of a vinyl aromatic compound and an ethylenic unsaturated dicarboxylic acid compound is blended with (B) an after- chlorinated polyvinyl chloride resin (Cl-PVC), and (C) a chlorinated polyethylene resin (CPE). A copolymer using p-methyl-styrene is preferable as the component A, and 1-40 wt.% acid monomer is used. 7-88 wt.% component A is blended with 10-58 wt.% component B, and 2-35 wt.% component C.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a thermoplastic resin composition, and more particularly to a thermoplastic resin composition comprising a styrenic copolymer and a chlorinated resin.

BACKGROUND OF THE INVENTION Styrenic resins are widely used as molding materials in many fields, but are required to be flame retardant for applications such as building materials, insulation materials, and household electrical appliances.

In order to make styrenic resin flame retardant, it has been attempted to add, for example, -rogen flame retardants or metal oxides such as antimony oxide to the resin, but the impact resistance of the resin If the temperature decreases significantly, the thermal stability and weather resistance will decrease.

Recently, a composition containing chlorinated polyvinyl chloride resin has been proposed in order to make the copolymer of styrene and maleic anhydride, which is known as a heat-resistant styrenic resin, flame retardant (Unexamined Japanese Patent Publication No. Although the flame retardance is improved, the impact resistance is poor.

Further, in US Pat. No. 4.13 to 155, a halogen-containing rubber such as chlorinated polyethylene, a halogen-based flame retardant, antimony oxide, and a smoke suppressant are blended into a copolymer of styrene and maleic anhydride. A composition is disclosed. However, since chlorinated polyethylene is not easily compatible with the copolymer, it is difficult to form a uniform composition, and this composition also has the disadvantage of poor heat resistance.

Furthermore, since it contains flame retardants and metal oxides, it has poor impact resistance.

Problems to be Solved by the Invention The object of the present invention is to provide a styrenic resin composition having well-balanced flame retardancy, heat resistance, and impact resistance.

As a result of extensive research, the present inventors have discovered that a composition consisting of a copolymer of a vinyl aromatic compound and an ethylenically unsaturated dicarboxylic acid compound, a post-chlorinated polyvinyl chloride resin, and a chlorinated polyethylene resin has been developed. The present invention was achieved by discovering that the object of the invention can be achieved.

That is, the gist of the present invention is to provide a copolymer of (a) a vinyl aromatic compound and an ethylenically unsaturated dicarboxylic acid compound, (b) a post-chlorinated polyvinyl chloride resin, and (C) a chlorinated polyethylene resin. It is a thermoplastic resin composition.

Composition component (1) Copolymer of a vinyl aromatic compound and an ethylenically unsaturated dicarboxylic acid compound A vinyl aromatic compound (hereinafter referred to as vinyl monomer) and an ethylenically unsaturated dicarboxylic acid compound (hereinafter referred to as a (hereinafter referred to as the copolymer)
) The monomers used in producing Y are styrene and its derivatives. Specific examples include styrene, α-methylstyrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene,
, chlorstyrene, dichlorostyrene, chloromethylstyrene, etc., as well as mixtures thereof.

In addition, acid monomers (°C) mean ethylenically unsaturated dicarboxylic acids, their anhydrides, half esters of the dicarboxylic acids, and mixtures thereof. Specific examples of these acid monomers include maleic acid, Fumaric acid, itaconic acid, citraconic acid, mesaconic acid, methylmaleic acid, ethylitaconic acid, chloromaleic acid, dichloromaleic acid and their acid anhydrides, and their combinations with alcohols such as methanol, ethanol, butanol, hexanol, dichloromaleic acid, Examples include tono half esters such as chlorpropatol, benzyl alcohol, and cyclohexenol.

The copolymer can be obtained by reacting the above-mentioned vinyl monomer and the above-mentioned acid monomer under heating, but it can also be obtained by solution polymerization of both in the presence or absence of a radical polymerization initiator. A copolymer that is homogeneous and exhibits biophilic properties is desirable.

When using the copolymer prepared using styrene, especially p-methylstyrene, as the vinyl monomer, the composition of the present invention exhibits excellent performance. The amount is 1 to 40% by weight, preferably 5 to 20% by weight, and the weight average molecular weight (Mw) is usually about 100,000 to about 400,000, and the molecular weight distribution (M
w/Mn) is 2.0 to 3.5.

(2) Post-chlorinated polyvinyl chloride resin Post-chlorinated polyvinyl chloride resin (hereinafter referred to as C't-PV
C) means a resin having a chlorine content of 58 to 70% by weight, obtained by chlorinating a polyvinyl chloride resin having a degree of polymerization of 200 to t500.

This ct-pvc can usually be produced by blowing chlorine into a solution of polyvinyl chloride resin dissolved in a solvent such as chloroform while heating. Alternatively, it can be produced by suspending polyvinyl chloride resin powder in water and blowing chlorine gas at 80 to 120°C in the presence of a surfactant.

(3) Chlorinated polyethylene resin Chlorinated polyethylene resin (hereinafter referred to as CPE) is a polymer obtained by chlorinating polyethylene resin,
The chlorine content is 30 to 50% by weight. Konoyo 5
CPE usually uses polyethylene resin with carbon tetrachloride, etc.
- Obtained by forming a solution or suspension of logenated hydrocarbon and chlorinating it at 60°C or lower. In addition, polyethylene resin powder was suspended in water, and in the presence of a surfactant, 8
It can also be produced by blowing chlorine gas at 0 to 120°C.

Composition The composition of the present invention comprises the copolymers, at-pvc and cp.
The proportions of these three components in the composition are 7 to 88% by weight of the copolymer, preferably 15 to 75% by weight, 10 to 58% by weight of C4-PVC, and preferably 10 to 58% by weight of C4-PVC. CPE is 20 to 55% by weight, CPE is 2 to 65% by weight, preferably 5 to 30% by weight.

The composition of the present invention may further have a degree of polymerization of 200 to 200, if necessary.
1.500 polyvinyl chloride resin (hereinafter referred to as PVC) can be blended.

The amount incorporated is usually up to 50% by weight in the above composition,
It is preferably 10 to 30% by weight.

pvcy< By blending, each component in the composition,
In the meantime, the compatibility between ct-pvc and CPE can be further improved.

The composition of the present invention comprises the copolymer, ct-pvc and CP.
E. Further, the optional component PVCkz can be obtained by mixing in the above blending ratio, but each component is evenly dispersed,
To make a composition with palatable properties, melt kneading in a bath using a mixer such as a Prabender, an extruder, a Banbury mixer, or a mixing roll, or a bath liquid in which each component is dissolved and mixed using a suitable medium. A mixing method by kneading is preferred.

The composition of the present invention having the above-mentioned structure has sufficient flame retardancy, but if necessary, known flame retardants such as hexabromobenzene, pentabromotoluene, pentabromophenol, decabromodiphenyl ether, etc. may be added. Halogenated aromatic compounds, phosphate esters such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, tris(dibromoglopyru) phosphate, and antimony compounds such as antimony oxide, triphenylantimony, tris(dibroheptaphenyl) ) Antimony etc! There is no restriction on blending.

Effects of the Invention The composition of the present invention is a styrenic resin composition that is excellent in flame retardancy, heat resistance, and impact resistance in a well-balanced manner. Moreover, each component in the composition is uniformly compatible with each other, and therefore the appearance is good.

The composition of the present invention having the above note '+/J can be used as a molding material before industrial parts such as housings of electrical products, parts, wiring devices (e.g. sockets, connectors), disaster prevention equipment, measuring instruments, etc. These molded products can be easily molded by ordinary plastic molding methods.Examples The present invention will be explained in detail with reference to examples below. 0 Example 1 Copolymer of styrene and maleic anhydride (trade name manufactured by Sekisui Co., Ltd., Dylark 332, maleic anhydride content 15
%, Mw250,000) (hereinafter referred to as SMA), 40 parts, C1-PVC (manufactured by Tokuyama Katsusui Kogyo Co., Ltd., trade name, Sekisui P)
VCHA-12 parts 8% average degree of polymerization 510, chlorine content 6
4%) and 20 parts of CPE (trade name manufactured by Showa Denko K.K., Elasrene 404B, chlorine content 40%) and 2 parts of diptyltin malate as heat stabilizer and calcium stearate 11JYs in a single screw extruder of 65 tmφ.
A composition was obtained by mixing wires under the conditions of 200°C and 60 r, p, m.0 A test piece was made from the obtained composition using an injection molding machine (200°C), and its physical properties were evaluated using the following test method. The results are shown in Table 1.

Izotsu impact strength: JIS K7110 (with non-stop) heat distortion temperature: JIS K7207 (1 & 6 to 9
7cm" load) Flame retardance: UL-94 method (thickness: 1716 inches) Compatibility: Visual inspection of test pieces Composition !# was prepared in the same manner as in Example 1 except for the following.The physical properties of the obtained composition were measured and the results are shown in Table 1.

Examples 7 and 8 In addition to SMA, CL-PVC and CPE, pvc (
Manufactured by Sekisui Kogyo Co., Ltd. Product name: Sekisui pvcT, S-40
A composition was prepared in the same manner as in Example 1, except that the four components were mixed in the proportions shown in Table 1. The physical properties of the obtained braided material were measured and the results are shown in Table 1 of ya1'.

Comparison 11-4 A composition was prepared in the same manner as in Example 1 or Example 7, except that Ct-PVC and/or CPGG were not used and the proportions of each component were as shown in Table 1. The physical properties of the obtained composition were measured and are shown in Table 1.

As is clear from Table 1, the composition of the present invention has excellent impact resistance, heat resistance, and flame retardancy in a well-balanced manner.

Example 9 In place of the SMA used in Example 1 at ℃, 78q6 SMA containing anhydrous maleic acid (trade name, manufactured by Sekisui Co., Ltd., Dailarc 232, Mw 222,000) was used.
A composition was prepared in the same manner as in Example 1. The physical properties of the obtained composition were measured and the results are shown in Table 1.

Example 10 Synthesis of copolymer of p-methylstyrene and maleic anhydride 1 oosv of p-methylstyrene with a purity of 910% (the remainder being m-methylstyrene) was placed in a polymerization vessel equipped with a stirrer and heated to 100°C. To this, 10 parts of anhydrous malein powder,
0.2 parts of azobisisobutyronitrile and 20 parts of methyl ethyl ketone were added continuously over 8 hours with stirring, and copolymerization was carried out while maintaining the temperature at 100°C. After adding the anhydrous maleic acid, stir at the same temperature for an additional 2 hours.
Continued. Next, 200 parts of methyl ethyl ketone was added and cooled, and the entire solution was poured into 20 times the volume of methanol to separate the polymer.

The polymer was dried to give 15% maleic anhydride moieties, Qw
210,000, Mw/Mn2.4 copolymer of p-methylstyrene and anhydrous maleic (hereinafter referred to as PMSM)
was synthesized.

Preparation of Composition SMA % used in Example 1: , PMSM obtained above was replaced with PMSM, CL-PVC
A composition was prepared in the same manner as in Example 1, except that the blending proportions of C'PE and C'PE were as shown in Table 2.

The physical properties of the obtained composition were measured and the results are shown in Table 2.

Examples 11 to 15 Compositions were prepared in the same manner as in Example 10, except that the blending ratios of PMSM, Ct-PVC, and CPH were as shown in Table 2. The physical properties of the obtained composition were measured and the results are shown in Table 2.

Example 16.17 Besides PM8M, Ct-PVC and CPE,
A composition was prepared in the same manner as in Example 10, except that the pvcy used in Example 7 was used and the proportions of the four components were as shown in Table 2. The physical properties of the obtained composition were measured and the results are shown in Table 2.

Comparative Examples 5 to 8 CL-P'l/C and/or CPF, ff: Same as Example 10 or Example 16 except that the blending ratio of each component was changed as shown in Table 2 without using it. Composition begging prepared.

The physical properties of the obtained composition were measured and the results are shown in Table 2.

Example 18 The same procedure as in Example 10 was carried out at °C, the anhydride maleic content was 8 cm,
Mvr224,000, Mvr/Mn ”1.29 P
MSM'1 was synthesized. A composition was prepared in the same manner as in Example 10 except that this PMSMg was used. The physical properties of the obtained composition were measured and the results are shown in Table 2.

As is clear from Tables 1 and 2, it can be seen that the effects of the composition prepared using 1, especially PMSM, are remarkable.

Claims (1)

[Claims] A thermoplastic resin composition comprising (a) a copolymer of a vinyl aromatic compound and an ethylenically unsaturated dicarboxylic acid compound, (b) a post-chlorinated polyvinyl chloride resin, and (c) a chlorinated polyethylene resin.