JPS60248758A - Heat-resistant, flame-retardant and impact-resistant resin composition - Google Patents

Abstract

PURPOSE:To provide a composition having excellent heat-resistance, flame-retardance, and impact resistance, and composed of a rubber-containing resin, a chlorine-containing resin and a copolymer composed of methacrylic acid, and styrene, methacrylic acid ester, acrylonitrile, etc. CONSTITUTION:The objective resin can be produced by compounding (A) 35- 70(wt)% copolymer composed of (i) 5-40pts.(wt.) of methacrylic acid, (ii) 95- 60pts. of one or more monomers selected from styrene (e.g. p-methylstyrene), methacrylic acid ester and acrylonitrile, and (iii) 0-20pts. of a monomer copolymerizable therewith, with (B) 5-40% rubber-containing resin such as MBS resin, ABS resin, etc. and (C) 20-60% chlorine-containing resin such as (chlorinated) polyvinyl chloride resin, etc. Preferably, the resin is a heat-resistant graft copolymer prepared by the bulk or suspension polymerization of the monomers A or by the polymerization of the monomers A in the presence of the resin B, or a chlorine-containing graft copolymer prepared by the suspension polymerization of a vinyl chloride monomer in the presence of the resin B.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a resin composition having excellent heat resistance, flame retardancy, and impact resistance. More specifically, 5 to 40 parts by weight of methacrylic acid, 95 to 60 parts by weight of at least one monomer selected from styrene, methacrylic acid ester, and acrylonitrile.
35 to 70 parts by weight of a copolymer consisting of 0 to 20 parts by weight of other monomers copolymerizable with these (based on a total of 100 parts by weight of monomers) 5 to 40 parts by weight of a resin
and 20 to 600 to 60 parts by weight of chlorine-containing resin.The present invention relates to a resin composition having excellent heat resistance, flame retardancy, and impact resistance.

(Prior Art) Recently, the demand for heat-resistant, flame-retardant, and impact-resistant resins has been increasing in the fields of automobile parts, electrical parts, and OA equipment parts. Conventionally, engineering plastics such as polycarbonate and polyarylate, and mixtures of ABC resin and flame retardants have been used, but the former have drawbacks such as being expensive and the latter having insufficient heat resistance.

(Problems to be Solved by the Invention) An object of the present invention is to provide an industrially advantageous resin composition that improves the above-mentioned drawbacks and has excellent heat resistance, flame retardancy, and impact resistance.

(Means for Solving the Problems) The present invention will be explained in detail below. The present invention includes 5 to 40 parts by weight of methacrylic acid, preferably 10 to 30 parts by weight, and 95 to 60 parts by weight, preferably 90 to 60 parts by weight of at least one monomer selected from styrene, methacrylic acid ester, and acrylonitrile. 70 parts by weight, and 85 to 85 parts by weight of other monomers copolymerizable with these.
70% by weight, preferably 40-600-60 parts by weight of resin 5-40 parts by weight, preferably 10-300-30 parts by weight Resin 20-600-60 parts by weight or 30-500 parts by weight
50 parts by weight of a heat-resistant, flame-retardant, impact-resistant resin composition.

If the methacrylic acid content in the copolymer is less than 5 parts by weight, the effect of improving heat resistance will be small, and if it exceeds 40 parts by weight, processing and moldability will become difficult, which is not preferable.

The proportions of styrene, methyl methacrylate, and acrylonitrile used may be arbitrary.

The styrene referred to in the present invention includes styrene and styrene derivatives such as 1-butylstyrene, p-methylstyrene, and p-halogenated styrene, which may be used alone or in combination. Acrylonitrile refers to acrylonitrile and methacrylonitrile, which may be used alone or in combination. The methacrylic ester refers to methacrylic esters such as methyl methacrylate and ethyl methacrylate, which may be used alone or in combination.

In the present invention, monomers copolymerizable with these include maleic anhydride, maleimide compounds such as N-phenylmaleimide and N-methylmaleimide, acrylic acid and its esters, and known monomers such as σ-methylstyrene. refers to a monomer.

These may also be used alone or in combination.

The rubber-based resin referred to in the present invention refers to MBS-based resin, ABEi
resin, polybutadiene resin, SBS resin, SBR
It refers to known rubber-based resins such as chloroprene-based resins, isoprene-based resins, chlorinated ethylene-based resins, NBR-based resins, and ethylene-vinyl acetate copolymer-based resins.

The chlorine-containing resin in the present invention refers to polyvinyl chloride resin,
And/or vinyl chloride copolymers made of vinyl chloride and known monomers such as ethylene, butene-1, allyl chloride, vinyl acetate, propylene, etc., and polyvinyl chloride resins. chlorinated polyvinyl chloride resin.

The copolymer of the present invention can be obtained by a known emulsion polymerization method, suspension polymerization method, bulk polymerization method, etc. using the above-mentioned monomers. Copolymers obtained by emulsion polymerization are difficult to handle due to their small particle size, and require a coagulation process.
Furthermore, the transparency of the molded product is reduced due to the emulsifier remaining in the copolymer particles. Therefore, it is preferable to produce the copolymer by a suspension polymerization method or a bulk polymerization method. In the emulsion polymerization method or suspension polymerization method, known emulsifiers and dispersants are used.

As the polymerization initiator, a known water-soluble initiator or redox initiator is used in the emulsion polymerization method.

Furthermore, in suspension and bulk polymerization methods, known oil-soluble initiators are used.

However, since methacrylic acid is water-soluble, it is advantageous to use a bulk polymerization method or a bulk/suspension polymerization method in which suspension polymerization is carried out from the middle of the bulk polymerization in terms of polymerization wastewater and the polymerizability of methacrylic acid.

The copolymer used in the present invention has a specific viscosity [η8P) of 0.
．． 01-0.7, preferably 0.03-0.5 (0,3
Dimethylformamide solution) can be suitably used.

In this Ashimei, it may be a blend system of a copolymer, a rubber resin, and a chlorine-containing resin, and a heat-resistant graft copolymer and a chlorine-containing resin obtained by producing a copolymer in the coexistence of a rubber resin. Alternatively, it may be a blend system of a chlorine-containing graft copolymer obtained by producing a chlorine-containing resin in the coexistence of a copolymer and a rubber resin.

It is better to use heat-resistant graft copolymers or chlorine-containing graft copolymers for copolymers, rubber resins, chlorine-containing resins,
It is superior to each blend system in terms of transparency, heat resistance, and impact strength.

Heat-resistant graft copolymers, like copolymers, can be produced by methods such as emulsion polymerization, suspension polymerization, bulk polymerization, or bulk/suspension polymerization.

Further, when the rubber resin is obtained by emulsion polymerization, monomers and a dispersant constituting the copolymer are added to the rubber resin latex, and suspension polymerization is carried out. That is, a heat-resistant graph H copolymer can also be obtained by emulsion/suspension polymerization.

A chlorine-containing graft copolymer can be obtained by polymerizing a vinyl chloride monomer in the coexistence of a rubber resin.

In this case, known polymerization initiators, emulsifiers, dispersants, etc. used in the polymerization of vinyl chloride monomers are used. Further, as the polymerization method, emulsion polymerization method, bulk polymerization method, suspension polymerization method, bulk/suspension polymerization method, emulsion/suspension polymerization method, etc. are employed, and in this case, suspension polymerization method is preferable.

In the present invention, a copolymer, a rubber resin, a chlorine-containing resin, a heat-resistant graft copolymer, and a chlorine-containing graft copolymer may be arbitrarily mixed. However, these composition ratios are: 35 to 70 parts by weight of copolymer, 5 to 40 parts by weight of resin,
The amount of chlorine-containing resin should be 20-60% by weight.

In the present invention, in order to adjust the molecular weight of copolymers, heat-resistant graft copolymers, and chlorine-containing graft copolymers, known chain transfer agents such as t-dodecyl mercaptan, 2-mercaptoethanol, and thiophenol, and diallyl phthalate are used. , diethyl glycol diacrylate, diethylene glycol dimethacrylate, and other known polyfunctional compounds may be used in the production of these copolymers.

Known lubricants such as behenic acid, ethylene bisstearylamide, stearic acid, and liquid paraffin may be added during the production of the copolymer, heat-resistant graft copolymer, or chlorine-containing graft copolymer.

The heat-resistant, flame-retardant, impact-resistant resin composition of the present invention can be used by blending it with the above-mentioned lubricants, known pigments, colorants, antioxidants, flame retardants, thermal stabilizers, and various other polymers. It's okay. As various polymers, there are known ones such as As-based resin, MMA-based resin, and engineering plastics.

The resin composition of the present invention can be easily processed and molded using an injection molding machine, a roll molding machine, an extrusion molding machine, or the like.

(Examples and Effects of the Invention) Examples of the present invention are shown below, but these do not limit the present invention in any way.

Production of copolymer and heat-resistant graft copolymer: 1,1'-azobiscyclohexane carbonitrite (abbreviated as ACN), 1.
1-dibutylperoxy-3゜5.5-1-limethylcyclohexane (abbreviated as B'll'C), methacrylic acid,
100 parts (the same parts by weight and below) of a mixed monomer (Table 1) consisting of styrene, methyl methacrylate, and acrylonitrile were charged and polymerized at -95°C for 3 hours. Next, 200 ml of ion-exchanged water in which 0.5 part of methylcellulose was dissolved
9'5°C for 6 hours. Then, heat treatment was performed at 115°C for 4 hours. After dehydration, 1
It was dried at 50°C for 1 hour, and the polymerization conversion rates of the copolymer and heat-resistant graft copolymer were determined. The results are shown in Table-1.

Table-1 Rice 1 Kane Ace B-28 (Kanebuchi Chemical Co., Ltd.) Rice 2 Styrene-butadiene block polymer with butadiene content of 70 *-3 Kane Ace FM (Kanebuchi Chemical Co., Ltd.) Production of chlorine-containing graft copolymer: Stirring blade In a polymerization vessel with an internal volume of 161 mm, di-butyl neodecanate (abbreviated as t, ND), azobisisobutyronitrile (abbreviated as AIBN), 2-mercaptoethanol (abbreviated as 2-ME), and partially saponified polyacetic acid were added. Vinyl (abbreviation P
VA), rubber resin, and ion-exchanged water, and after degassing,
PVC was added. Polymerization was carried out at 70°C for 8 hours, unreacted vinyl chloride was recovered, and after dehydration, a vinyl chloride-based graft copolymer was obtained. The polymerization conversion rate is shown in Table-2.

Rice 1: Same as used in Table-1.

Examples 1-11. Comparative Examples 1 to 4 3.0 parts by weight of dibutyltin maleate and 10 parts by weight of ester lubricant were added to 100 parts by weight of the mixture of the various copolymers obtained in Tables 1 and 2, polyvinyl chloride, and rubber resin. The parts were blended and pellets were made using an extruder. Then,
A test piece was produced by applying this pellet to an injection molding machine.

From this test piece, as a measure of heat resistance, 5 kg
/cA load Vicat softening temperature (°C) and impact strength were measured by notched Izot impact value according to JI'S-7110. In addition, to measure flame retardancy, the length x width x thickness is 16 z x 1 cm x 0.5
A test piece of Cn1 was ignited with a gas burner, and judgment was made based on the time from when the gas burner was released until the flame disappeared and the size of the flame. The evaluation criteria are as follows.

○: The flame goes out immediately.

△: The flame is small and continues to burn.

×: The flame continues to burn without becoming smaller.

The results are shown in Table 3.

The following can be seen from Table 3. That is, from the comparison of Examples 1, 2゜3, 4, 5.6, and 7.8.9, it is found that using a chlorine-containing graft copolymer has better heat resistance than using a copolymer. It is superior in terms of durability, impact strength, and flammability. Furthermore, from a comparison between Example 10 and Comparative Examples 1 to 4, it was found that impact strength was not achieved when the rubber content was low (Comparative Example 1,
4) If too much, heat resistance will not be achieved (Comparative Example 2). Also,
If the amount of copolymer used is too small, heat resistance will not be achieved (Comparative Example 3), and if it is too large, the amount of rubber-based resin and chlorine-containing resin will decrease, resulting in poor impact strength and flame retardance (Comparative Example 4) . It is also found that heat resistance is improved by using a copolymer with a high acrylic acid content (comparison of Examples 10 and 11).

Patent applicant Kanebuchi Chemical Industry Co., Ltd. Agent: Patent attorney Asa Noma

Claims (4)

[Claims] (1) 5 to 40 parts by weight of methacrylic acid, 95 to 60 parts by weight of at least one monomer selected from styrene, methacrylic acid ester, and acrylonitrile, and 0 to 20 parts by weight of other monomers copolymerizable with these. Parts by weight (monomer total 1
00 parts by weight) copolymer consisting of 35 to 70
% by weight, 5 to 40 parts by weight of rubber-based resin, and 20 to 600 to 60 parts by weight of chlorine-containing resin. (2) The heat-resistant, flame-retardant, impact-resistant resin composition according to claim 1, which uses a heat-resistant kraft copolymer obtained by polymerizing a monomer mixture in the coexistence of a rubber-based resin. (3) The heat-resistant, flame-retardant, impact-resistant resin composition according to claim 1, which uses a chlorine-containing graft copolymer obtained by producing a chlorine-containing resin in the coexistence of a rubber-based resin. (4) During polymerization, switching from bulk polymerization to suspension polymerization
Claim 1 or 2 uses a copolymer or a heat-resistant graft copolymer obtained by a suspension polymerization method.
The heat-resistant, flame-retardant, impact-resistant resin composition described in 1.