JPH064748B2 - Impact resistant resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to an impact resistant resin composition having excellent impact resistance and good flame retardancy. More in detail, (A) impact-resistant resin group, (B) crystalline chlorinated polyethylene, (C) antimony oxide and a flame retardant consisting of a bromine-containing organic compound,
(D) Dehydrochlorination inhibitor and (E) Phenol-based antioxidant, impact-resistant resin is butadiene-containing rubber, ethylene-propylene-diene-based multi-component copolymer rubber mainly composed of ethylene and propylene, and acrylic acid. A graft copolymer obtained by graft-copolymerizing at least one rubber selected from the group consisting of ester rubbers with styrene and at least one vinyl compound selected from the group consisting of acrylonitrile and methyl methacrylate, Moreover, crystalline chlorinated polyethylene exhibits an amorphous peak at a black angle 2θ of 12 to 13 ° by the X-ray wide angle diffraction method.
Shows crystalline peaks depending on crystalline polyethylene at 21 ° and 24 °, respectively, and polyethylene crystals are 3
-50% by weight and chlorine content of 15-50% by weight relates to an impact resistant resin composition, which not only has excellent impact resistance but also good flame retardancy. The purpose of the present invention is to provide a resin composition.

2. Description of the Related Art Presently, acrylonitrile-is used as a casing for electric and electronic devices such as television receivers, word processors, various computers, fax machines, and audio equipment.
Impact-resistant resins such as butadiene-styrene terpolymer resin are widely used. Compositions obtained by blending various flame retardants for imparting flame retardancy to these impact resistant resins are generally used. When the blending amount of the flame retardant is relatively small, the flame retardance is not sufficient, and when the flame retardant is blended in a considerably large amount, the cost becomes high, and the impact resistance of the composition decreases, The flame retardant may bleed on the surface of the molded product, and there is a problem in flame retardance such as fire sag. For this reason, it is considered to blend an amorphous chlorinated polyethylene rubber often used as a flame retardant. However, even though this amorphous chlorinated polyethylene is rubber, there is a problem that the impact resistance of the resulting composition is not satisfactory.

Problems to be Solved by the Invention From the above, the present invention does not have these drawbacks (problems), that is, not only good impact strength and workability but also good flame retardancy, The object is to obtain an optimal composition when manufacturing a housing for equipment and electronic equipment.

Means and Actions for Solving Problems According to the present invention, these problems consist of (A) impact resistant resin, (B) crystalline chlorinated polyethylene (C) antimony oxide and bromine-containing organic compound. The flame-retardant agent, (D) dehydrochlorination inhibitor, and (E) phenolic antioxidant, and the composition ratio of the impact-resistant resin in the total amount of the impact-resistant resin and crystalline chlorinated polyethylene is 75 ~
It is 99% by weight, and the composition ratio of the antimony oxide and bromine-containing organic compound is 100% by weight based on the total amount of the impact resistant resin and the crystalline chlorinated polyethylene.
0.5 to 40 parts by weight, the composition ratio of the dehydrochlorination inhibitor is 0.1 to 10 parts by weight, the composition ratio of the phenolic antioxidant is 0.1 to 7.0 parts by weight, and the impact resistance resin is butadiene. From rubber containing (hereinafter referred to as "butadiene-containing rubber"), ethylene-propylene-diene multi-component copolymer rubber containing ethylene and propylene as main components (hereinafter referred to as "ethylene-propylene rubber") and acrylic ester rubber A graft copolymer obtained by graft-copolymerizing styrene and at least one vinyl compound selected from the group consisting of acrylonitrile and methyl methacrylate onto at least one rubber selected from the group consisting of crystalline chlorine and Of polyethylene with a black angle of 2θ by the X-ray wide angle diffraction method
Shows an amorphous peak at 12 to 13 degrees, and shows a crystalline peak depending on crystalline polyethylene at a black angle 2θ of 21 degrees and 24 degrees, respectively, and polyethylene crystals remain 3 to 50% by weight. And has a chlorine content of 15 to 5
The impact resistant resin composition is 0% by weight.

Can be solved by. Hereinafter, the present invention will be specifically described.

(A) Impact-resistant resin The impact-resistant resin used in the present invention comprises acrylonitrile and methyl methacrylate in at least one rubber selected from the group consisting of butadiene-containing rubber, ethylene-propylene rubber and acrylate rubber. It is obtained by graft-copolymerizing at least one vinyl compound selected from the group.

(1) Butadiene-based rubber The butadiene-based rubber contains butadiene as a main component (60% by weight).
Above), and is a butadiene homopolymer rubber or a copolymer rubber (SBR, NBR) of butadiene and a small amount of styrene or acrylonitrile. The copolymer rubber of butadiene and styrene may be a block copolymer rubber or a random copolymer rubber.

(2) Ethylene-propylene rubber Further, the ethylene-propylene rubber is mainly composed of ethylene and propylene, and has two double bonds such as 1.4-pentadiene, 1.5-hexadiene and 3.3-dimethyl-1.5-hexadiene. A linear or branched diolefin having only one double bond at the end, such as 1.4-hexadiene and 6-methyl-1.5-heptadiene, or a bicyclo [2.2. It is a multi-component copolymer rubber obtained by copolymerizing a small amount (generally 10% by weight or less) of a monomer such as a cyclic diene hydrocarbon such as 1] -heptene-2 and its derivatives. Of these copolymer rubbers and multicomponent copolymer rubbers, those having a weight ratio of ethylene monomer units to propylene monomer units of 30/70 to 70/30 are preferable.

(3) Acrylate ester-based rubber An acrylate ester-based rubber means an acrylate ester (eg, butyl acrylate) and a small amount (generally 10% by weight or less) of another monomer (eg, acrylonitrile). Is obtained by emulsion polymerization of and in the presence of a catalyst such as persulfate, and is usually called acrylic rubber.

In producing the impact resistant resin of the present invention, among these rubber-like materials, those having a Mooney viscosity of 20 to 140 are preferable, and those having a Mooney viscosity of 30 to 120 are particularly preferable, depending on the kind of the rubber-like material. Is. Further, these rubber-like materials are industrially widely produced and widely used. Their manufacturing methods, properties, and uses are widely known [for example, Shu Kanbara, "Synthetic Rubber Handbook" (Showa 42,
Published by Asakura Shoten)].

(4) Production of impact-resistant resin The impact-resistant resin used in the present invention is styrene and another vinyl compound (acrylonitrile,
It is produced by graft-polymerizing at least one of (methyl methacrylate). Examples of the graft polymerization method include a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, an aqueous suspension polymerization method, and a method of combining these graft polymerization methods (for example, a method of performing bulk polymerization and then aqueous suspension polymerization). Generally, the amount of the rubber-like material used to produce 100 parts by weight of the impact resistant resin is 3 to 40 parts by weight, preferably 5 to 35 parts by weight, and particularly
5 to 30 parts by weight is preferable (a relatively large amount of a rubber-like material is used to produce a rubber-rich graft polymer, and the graft polymer is mixed with the above-mentioned styrene, acrylonitrile, or methyl methacrylate. A homopolymer resin or a copolymer resin may be mixed, but the amount of the rubber-like material used in this case is calculated as a mixture.) Further, the monomer (styrene, acrylonitrile, The molecular weight of (methyl methacrylate) is usually 1000 to 300,000, preferably 2000 to 200,000. In general, it is rare for a monomer to be completely bonded to a rubber-like material, and there are a graft material and a homopolymer or copolymer of a monomer which is not bonded to the rubber-like material. These homopolymers and copolymers are used as they are without separation.

(5) Representative examples of impact resistant resins Representative examples of impact resistant resins produced as described above include butadiene homopolymer rubber, styrene and butadiene block or random copolymer rubber (SBR), or acrylonitrile and butadiene copolymer. Acrylonitrile-butadiene-styrene terpolymer resin (ABS resin) obtained by graft copolymerizing styrene and acrylonitrile onto polymer rubber (NBR), butadiene homopolymer rubber or SBR with styrene and methyl methacrylate graft copolymerization Methyl methacrylate-butadiene-styrene terpolymer resin (MBS resin) obtained by the above, acrylonitrile-acrylic ester-styrene terpolymer obtained by graft-copolymerizing acrylonitrile and styrene onto acrylic ester rubber Examples thereof include a resin (AAS resin) and a graft copolymer resin (AES resin) obtained by graft-copolymerizing acrylonitrile and styrene on an ethylene-propylene rubber.

These impact-resistant resins are industrially produced and used in various fields, and the production method is well known.

(B) Crystalline chlorinated polyethylene The crystalline chlorinated polyethylene used in the present invention is obtained by chlorinating polyethylene powder or particles in an aqueous suspension or chlorinating polyethylene dissolved in an organic solvent. (Obtainable by chlorination in an aqueous suspension). It is a crystalline chlorinated polyethylene having a chlorine content of 15 to 50% by weight, and particularly preferably a crystalline chlorinated polyethylene having a chlorine content of 20 to 45% by weight.

The polyethylene is obtained by homopolymerizing ethylene or by copolymerizing ethylene with at most 10% by weight of α-olefin (generally having at most 12 carbon atoms). Its density is generally from 0.900 to 0.980 g / cm ³ . Further, its molecular weight is 50,000 to 800,000.

The crystalline chlorinated polyethylene of the present invention has a polyethylene content of 3 to 50% by weight, and its typical characteristic is a specific gravity of 1.00 to 1.30, and a tensile breaking strength in a tensile test measurement according to JIS K-6301. Is 50 to 150 kg / cm ² and the tensile elongation at break is 500 to 800%. The hardness (Shore A) is 70 to 98, and the volume resistivity (measured by ASTM D-254) is 1.0 × 10 ^{13 to} 1.0 × 10 ¹⁵ Ω · cm. The X-ray wide-angle diffraction pattern of the crystalline chlorinated polyethylene used in the examples was measured by Cu-Kα ray using an X-ray wide-angle diffractometer (Rigaku Denki Co., Ltd., trade name Geiger Flex 2028). The X-ray wide-angle diffraction pattern of the amorphous chlorinated polyethylene used in FIG. 1 and in the examples and comparative examples is shown by the dotted line (a) in FIG. The X-ray wide-angle diffractogram of the butene-1 copolymer is shown as the solid line (b) in FIG. From the X-ray wide angle diffraction pattern, ethylene-butene-1
Bragg Copolymer (Crystalline Polyethylene)
Angle 2θ = 21 degrees (110) plane, Bragg angle 2θ = 24 degrees (2
It can be seen that the crystallinity peak of 00) is exhibited. Also,
Amorphous chlorinated polyethylene has a Bragg angle of 2θ = 12 degrees
Although the amorphous peak is clearly visible at 13 degrees, the crystalline peak of the crystalline polyethylene is completely disappeared. Furthermore, crystalline chlorinated polyethylene shows a peak similar to that of amorphous chlorinated polyethylene at Bragg angles 2θ = 12 to 13 °, and crystalline properties depending on crystalline polyethylene at Bragg angles 2θ = 21 ° and 24 °, respectively. It is clear that it shows a peak. In FIG. 1, the amount of crystalline polyethylene in the whole is 10 to 15%, and this amount can be arbitrarily changed depending on the production conditions of chlorinated polyethylene.

(C) Antimony Oxide Furthermore, the antimony oxide used in the present invention is generally used as a flame retardant aid for the bromine-containing organic compound. Representative examples include antimony trioxide and antimony pentoxide.

These bromine-containing organic compounds and antimony oxide are well known in the following "Handbook, rubber / plastic compounding chemicals" and the like. The antimony oxide also has an average particle size of 1 to 150 microns.

(D) Bromine-containing organic compound The bromine-containing organic compound used in the present invention is widely known as a flame retardant. Typical examples are tris (2,3-dibromopropyl) phosphate, bis (2,3-dibromopropyl) -dichloropropyl phosphate, brominated bisphenol S, tris (bromocresyl) phosphate, brominated diphenyl, brominated Phosphate ester-based tetra-bromozotane, hexabromo-benzene and tris (dibromobutyl)
Phosphate is included.

(E) Dehydrochlorination Inhibitor Further, the dehydrochlorination inhibitor used in the present invention is generally a dehydrochlorination polymer such as a vinyl chloride polymer, which is produced by heat or the like containing a halogen atom (mainly chlorine atom). It is widely used to prevent hydrogen chloride. The dehydrochlorination inhibitor is roughly classified into metallic soap, a mixture of inorganic acid salt metals, metal oxides, organotin compounds and pure organic compounds. Typical examples of these are Japanese Patent Application No. 59-1.
No. 36526. These dehydrochlorination inhibitors are described on pages 268 to 319 of "Handbook, Rubber / Plastic Blended Chemicals" (published by Rubber Digest, 1974) edited by Rubber Digest. Among these dehydrochlorination inhibitors, inorganic acid salts, metal oxides and organic tin compounds are preferable, and inorganic acid salts and metal oxides are particularly preferable. Especially, dibasic lead phthalate, dibasic lead stearate, tribasic lead sulfate, basic lead silicate, magnesium oxide and lead oxide are preferable.

(F) Phenolic Antioxidant The phenolic antioxidant used in the present invention is generally used as an antioxidant for organic substances such as synthetic resins. Among the phenolic antioxidants, the general formulas of typical ones are represented by the following formulas (formula (I) to formula (IV)).

[Hereinafter referred to as "phenolic compound (1)"] [Hereinafter referred to as "phenolic compound (2)"] [Hereinafter referred to as "phenolic compound (3)"] and [Hereinafter, referred to as "phenolic compound (4)"] However, R ₁ , R ₂ and R ₃ may be the same or different, and a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and 4 to 4 carbon atoms.
Selected from the group consisting of 20 cycloalkyl groups, 1-alkylcycloalkyl groups having 1 to 20 carbon atoms and 1-alkylbenzyl groups having 1 to 20 carbon atoms. It is a hydrocarbon group,
At least two of R ₁ , R ₂ and R ₃ are the hydrocarbon groups, R ₄ is an alkyl group having 1 to 6 carbon atoms, R ₅ and R ₆ may be the same or different, A hydrogen atom, the above hydrocarbon group or an aralkyl group having 7 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, at least one of R ₅ and R ₆ is the hydrocarbon group or the above. An aralkyl group, R ₇ and R ₈ may be the same and different,
Hydrogen atom or alkyl group having 1 to 12 carbon atoms, cycloalkyl group having 4 to 12 carbon atoms, allyl group having 6 to 12 carbon atoms or alkyl group having 1 to 12 carbon atoms Is a 1-alkylcycloalkyl group or 1-alkylbenzyl group, R ₉ is an alkylidene group having 1 to 12 carbon atoms or an alkylene group, x is an integer of 1 to 6, y is 1, 2 or 3.

Representative examples of the phenolic compound (1) are described in JP-A-49-45051. This phenolic compound
Among formulas (1), it is preferable that in formula (I) above, R ₁ , R ₂ and R ₃ each have at most 3 carbon atoms.

A representative example of the phenolic compound (2) is JP-A-49-7646.
No. 8 and No. 49-137692. Among the phenolic compounds, in the above formula (II), R ₄
It preferably has 3 or 4 carbon atoms.

Further, a representative example of the phenolic compound (3) is disclosed in JP-A-49-13
0502 and 49-137692. Among the phenolic anti-compounds, those having ₅ or less carbon atoms in R ₅ and R _{6 in} the above formula (III) are preferable, and those having 4 or more carbon atoms are particularly preferable.

Moreover, a representative example of the phenolic compound (4) is disclosed in JP-A-49-13.
1159 and 49-137692. Among the phenolic anti-compounds, in the above formula (IV), R ₇ and R ₈ preferably have at most 18 carbon atoms, and particularly preferably 4 or less. Further, R ₉ preferably has at most 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms.

Furthermore, the heat resistance (workability at high temperature) of the composition obtained by blending the thiopropionate-based antioxidant and / or the organic phosphorus-based antioxidant can be improved, and deterioration and coloring can occur. It is possible to produce a molded product without any damage.

(G) Thiopropionate-based antioxidant The thiopropionate-based antioxidant is used as an antioxidant for organic substances such as synthetic resins like the above-mentioned phenol-based antioxidant, It is often used in combination with the phenolic antioxidant. Among the thiopropionate antioxidants, the general formulas of typical ones are shown by the following formulas [formula (V) to (VI)].

(However, R ₁₀ , R ₁₁ and R ₁₂ may be the same or different,
A hydrocarbon group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an aryl group and an aralkyl group, and n is an integer of 1 to 20) The thiopropionate antioxidant A typical example of the agent is "Handbook / Rubber / Plastic compounded chemicals" edited by Rubber Digest.
(Rubber Digest, 1974), pages 105-111, and Yamada et al., "Plastic compounding agents (basics and applications)" (Taisei, 1969), pages 111-130. It is described in detail. Among the thiopropionate type antioxidants, the above-mentioned formulas (V) and (VI)
In the formula, R ₁₀ , R ₁₁ and R ₁₂ each preferably have at most 20 carbon atoms, and particularly preferably 12 or more carbon atoms. Representative examples of suitable thiopropionate antioxidants include dilauryl thiopropionate and pentaerythritol tetrakis (β-lauryl thiopropionate).

(H) Organophosphorus Antioxidant In addition, the organophosphorus antioxidant is used as an antioxidant for organic substances such as synthetic resins like the above-mentioned phenolic antioxidant and thiopropionate antioxidant. And is often used in combination with the phenolic antioxidant and the thiopropionate antioxidant.

Among the organophosphorus antioxidants, a general formula of a typical one is represented by the following formula (VII).

(However, R ₁₃ , R ₁₄ and R ₁₅ may be the same or different,
Hydrogen groups and hydrocarbon groups selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, allyl groups, aralkyl groups, alkaryl groups and alkenyl groups, at least one of which is a hydrocarbon group. is there.

Typical examples of the organophosphorus antioxidants are pp. 297 to 299 of "Handbook / Rubber / Plastic Blended Chemicals" edited by Rubber Digest Co. (Rubber Digest Co., 1974).
Page and "Additives for Plastics and Rubber Practical Handbook" (Chemical Industry Co., Ltd., published in 1970), pages 183 to 185.

In the formula (VII) among the organophosphorus antioxidants,
It is preferable that each of R ₁₃ , R ₁₄ and R ₁₅ has 9 to 20 carbon atoms. Representative examples of suitable organophosphorus antioxidants include triphenyl phosphite, trioctadecyl phosphite and trinolyl phenyl phosphite.

(J) composition ratio In the impact resistant resin composition of the present invention, the composition ratio of the impact resistant resin in the total amount of the impact resistant resin and the crystalline chlorinated polyethylene is 75 to 99% by weight, 75 ~ 98
% By weight is preferred, especially 80 to 98% by weight. When the composition ratio of the impact resistant resin in the total amount of the impact resistant resin and the crystalline chlorinated polyethylene is less than 75% by weight,
The composition obtained has good flame retardancy, but is unfavorable because it lowers rigidity and impact resistance. On the other hand, 99% by weight
If it exceeds the range, the rigidity and impact resistance are excellent, but drip and glowing occur in flame retardancy, and the flame retardancy is insufficient.

Total amount of impact resistant resin and crystalline chlorinated polyethylene
The composition ratio of the other composition components to 100 parts by weight is as follows.

The total amount of antimony oxide and bromine-containing organic compounds is 5.0 to 40 parts by weight, preferably 5.0 to 35 parts by weight, and more preferably 10 to 35 parts by weight. When the composition ratio of the antimony oxide and the bromine-containing organic compound is less than 5.0 parts by weight as the total amount thereof, a composition having sufficient flame retardancy cannot be obtained. On the other hand, if it exceeds 40 parts by weight,
Not only the moldability of the composition decreases, but also the thermal stability during molding deteriorates. The composition ratio of the bromine-containing organic compound in the total amount of antimony oxide and the bromine-containing organic compound is usually 5 to 95% by weight (that is, the composition ratio of antimony oxide is 95 to 5% by weight), and 10 to 90% by weight. % By weight is preferred and 20-80% by weight is particularly preferred.

Further, the dehydrochlorination inhibitor is 0.1 to 10 parts by weight, preferably 0.1 to 7.0 parts by weight, and 0.1 to 6.0 parts by weight is suitable. The phenolic antioxidant is 0.1 to 7.0 parts by weight, preferably 0.1 to 6.0 parts by weight, particularly 0.1 to 5.0 parts by weight.
Weight parts are preferred. When a thiopropionate-based antioxidant and / or an organic phosphorus-based antioxidant is used in combination with the phenol-based antioxidant, the composition ratio of these compounds is the total amount of the impact-resistant resin and the crystalline chlorinated compound. Generally at most for 100 parts by weight of total polyethylene
It is 0.7 parts by weight, especially 6.0 parts by weight is desirable. Further, the composition ratio of the thiopropionate-based antioxidant and the organic phosphorus-based antioxidant in the total amount of the phenol-based antioxidant, the thiopropionate-based antioxidant and the organic phosphorus-based antioxidant is those The total amount is at most 80% by weight, preferably 75% by weight or less. When the composition ratio of the dehydrochlorination inhibitor and the phenolic antioxidant is less than the lower limit, dehydrochlorination and deterioration due to oxygen and heat cannot be sufficiently prevented. On the other hand, if the content exceeds the upper limit, not only the effect obtained by the addition cannot be exhibited, but also the mold may be contaminated during molding and bleeding may occur on the surface of the obtained molded product.

(K) Production of the composition, molding method, etc. To produce the composition of the present invention, the above-described impact-resistant resin, crystalline chlorinated polyethylene, flame retardant consisting of antimony oxide and bromine-containing organic compound, dechlorination Although the purpose can be achieved by uniformly blending a hydrogen antioxidant and a phenolic antioxidant, and further a thiopropionate antioxidant and / or an organophosphorus antioxidant, the thermoplastic resin ( Among them, additives such as heat and light stabilizers, fillers, colorants, lubricants, plasticizers and antistatic agents, which are widely used in the field of impact-resistant resins, are added depending on the purpose of use of the composition. You may add the characteristic of the composition of this invention in the range which does not impair essentially.

As a mixing method, a method of dry blending using a mixer such as a Henschel mixer, which is generally used in the field of synthetic resins, and mixing while melting using a mixer such as an open roll, an extrusion mixer, a kneader and a bumper. There is a way to do it. Among these mixing methods, two or more kinds of these mixing methods may be used together in order to obtain a more uniform composition (for example, after dry blending in advance, the mixture is melt mixed). Among them, when using a dry blend together, even when using one or two or more melt kneading method in combination, in producing a molded product by the molding method described below, it is manufactured into pellets by using a pelletizer and used. It is preferable.

Among the above mixing methods, it is necessary to carry out at a temperature at which the impact-resistant resin, crystalline chlorinated polyethylene and halogen-containing organic compound used are melted, regardless of whether they are melt-kneaded or molded by the molding method described below. . However, if they are carried out at elevated temperatures, they can cause thermal decomposition or dehydrohalogenation reactions, it is
It is necessary to carry out at a temperature below ℃.

The composition of the present invention may be molded into a desired shape by applying a molding method such as an injection molding method, an extrusion molding method, a compression molding method and a hollow molding method which are generally used in the field of synthetic resins. Further, after being formed into a sheet using an extrusion molding machine, this sheet may be formed into a desired shape by a secondary processing method such as a vacuum forming method or a pressure forming method.

Examples and Comparative Examples Hereinafter, the present invention will be described in more detail with reference to Examples.

In Examples and Comparative Examples, the tensile test (referred to as the "E _B") Tensile (called hereinafter "T _B") strength and elongation were measured using a Tensilon tester according JIS K6911. In addition, the melt flow index (hereinafter `` M.
I.) is measured according to JIS K6730 at a temperature of 210 ° C and a load of 2.16Kg, and the impact resistance test is according to ASTM D256.
The temperature was measured at 23 ° C and -20 ° C. Furthermore, the flame retardancy test was measured according to the UL-94 method, and the presence or absence of trip was visually observed.

The impact-resistant resins, crystalline chlorinated polyethylene, non-crystalline chlorinated polyethylene, antimony oxide, bromine-containing organic compounds, dehydrochlorination inhibitors, phenolic antioxidants, thiopropoxides used in Examples and Comparative Examples. The production methods, types, and physical properties of the pionate-based antioxidant and the organic phosphorus-based antioxidant are shown below.

[(A) Impact resistant resin]

As impact resistant resin, acrylonitrile-butadiene-
Styrene terpolymer resin (hereinafter referred to as "ABS"), methyl methacrylate-butadiene-styrene terpolymer resin (hereinafter referred to as "MBS"), acrylonitrile-acrylic ester rubber-styrene terpolymer resin ( Hereinafter referred to as "AAS"), acrylonitrile-olefin rubber-styrene multi-component copolymer resin (hereinafter referred to as "AES")
Was used in the same manner as the ABS resin, MBS resin, AAS resin and AES resin used in the examples and comparative examples of JP-A-58-134144.

[(B) Crystalline chlorinated polyethylene]

As crystalline chlorinated polyethylene, ethylene-butene-1 copolymer containing 3.0% by weight of butene-1 (density 0.94
Chlorination of 0 g / cm ³ and average molecular weight of about 150,000 in an aqueous suspension to give crystalline chlorinated polyethylene [chlorine content 30.2% by weight, residual crystal amount of polyethylene 7.15% by weight, Mooney viscosity (ML _{1+ 4} ) 110, hereinafter referred to as "BCPE"] was manufactured.

[(C) Amorphous chlorinated polyethylene]

As amorphous chlorinated polyethylene, the density is 0.950 g / cm ³ ,
Polyethylene (average molecular weight about 200,000) is chlorinated in an aqueous suspension by chlorination polyethylene [chlorine content 40.2% by weight, amorphous, Mooney viscosity (MS _{1 + 4} ) 80,
Hereinafter referred to as "CPE").

[(D) Antimony oxide and bromine-containing organic compound]

As antimony oxide, antimony trioxide having a density of 5.25 g / cm ³ (hereinafter referred to as “Sb ₂ O ₃ ”) is used, and as the bromine-containing organic compound, tetrabromobisphenol having a bromine content of 61% by weight or more. A derivative (melting point: 50 ° C., hereinafter referred to as “TBA”) was used.

[(E) Dehydrochlorination inhibitor]

As the dehydrochlorination inhibitor, magnesium oxide (100 mesh pass, hereinafter referred to as “MgO”) and calcium stearate (hereinafter referred to as “Ca-St”) having a specific surface area of 150 m ² / g were used.

[(F) Phenolic antioxidant, etc.]

As a phenolic antioxidant, n-octadecyl-
3- [4'-hydroxy-3 ', 5'-di-tertiarybutyl-phenyl) propionate (hereinafter referred to as "AO-1") was used as a thiopropionate antioxidant and dilaurylthiodipropionate. Onate (hereinafter referred to as "AO-2") was used, and trioctadecyl phosphite (hereinafter referred to as "AO-3") was used as an organic phosphorus antioxidant.

Examples 1-10, Comparative Examples 1-14 Impact-resistant resins and crystalline chlorinated polyethylene whose amounts and types are shown in Table 1 in advance are dry blended using a Henschel mixer, and each mixture obtained is further blended. Antimony oxide, a dehydrochlorination inhibitor, a phenolic antioxidant, etc., the amounts and types of which are shown in Table 1 were added, and dry blending was performed for 4 minutes. The temperature of each mixture thus obtained is
160 ℃, 180 ℃ for cylinder 2, 180 for cylinder 3
The composition (pellets) was manufactured while kneading using a vent type twin-screw extruder (diameter 30 mm) set to ℃, adapter 180 ° C., and die 170 ° C.

Each pellet thus obtained is hot-pressed under the conditions of temperature of 210 ° C. and pressure of 200 kg / cm ² for 3 minutes of preheating time and 2 minutes of pressing time to make a sheet with a thickness of 2 mm. did.

Comparative Example 15 Pellets were produced by performing dry blending and melt kneading under the same conditions as in Example 6 except that CPE (the compounding amount was the same as in Example 16) was used instead of BCPE used in Example 6. . The obtained pellets were hot pressed in the same manner as in Example 6 to prepare a sheet.

Comparative Example 16 Pellets were produced by dry blending and melt-kneading under the same conditions as in Example 6, except that the blending amount of BCPE used in Example 6 was changed to 30 parts by weight. The obtained pellets were hot pressed in the same manner as in Example 6 to prepare a sheet.

The tensile strength (T _B ) of each sheet obtained as described above,
Elongation measurements (E _B), impact resistance test (23 ° C. and -20 ° C.),
A flame retardancy test was conducted. Further, the melt flow index (MI) of the pellet obtained by the extruder was measured. The results are shown in Table 2.

In Comparative Example 14, deterioration occurred during melt-kneading and sheet formation.

From the results of the above Examples and Comparative Examples, the impact-resistant resin composition obtained by the present invention, 23 ° C. in impact test
It is clear that the impact resistance is excellent not only at low temperature but also at low temperature, and the flame retardancy is also good.

Furthermore, the composition obtained by the present invention is not only good in tensile strength, but also promising for housings and the like because it is a well-balanced composition in combination with melt flow index and flame retardancy. it is obvious.

EFFECTS OF THE INVENTION The impact resistant resin composition obtained by the present invention is a composition which not only has good impact resistance but also exhibits the following effects (features).

(1) Excellent weather resistance.

(2) Good flame retardancy can be obtained despite the addition of a small amount of flame retardant.

(3) Excellent heat resistance.

The impact-resistant resin composition obtained by the present invention not only has the excellent effects as described above,
Due to its good flame retardancy, it can be used in the following fields.

(1) Television receivers (2) Word processors, various computers (3) Electric and electronic devices such as facsimiles and audio equipment (4) Housings for home appliances (5) Automotive instrument panels

[Brief description of drawings]

FIG. 1 is an X-ray wide-angle diffraction pattern of the crystalline chlorinated polyethylene (BCPE) used in the examples. Also, in FIG.
(a) (dotted line) is an X-ray wide-angle diffraction pattern of the amorphous chlorinated polyethylene (CPE) used in Examples and Comparative Examples, and (b) (solid line) in FIG. 2 is the chlorinated polyethylene. FIG. 3 is an X-ray wide-angle diffraction pattern of the ethylene-butene-1 copolymer used in the production of

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Claims (1)

[Claims] 1. A flame-retardant comprising (A) an impact resistant resin, (B) a crystalline chlorinated polyethylene, (C) an antimony oxide and a bromine-containing organic compound, (D) a dehydrochlorination inhibitor, and (E) ) The composition ratio of the impact-resistant resin in the total amount of the impact-resistant resin and the crystalline chlorinated polyethylene is 75-
99% by weight, the composition ratio of the antimony oxide and the bromine-containing organic compound is 0.5 to 40 parts by weight based on 100 parts by weight of the total amount of the impact-resistant resin and the crystalline chlorinated polyethylene, and the total amount thereof is 0.5 to 40 parts by weight. The composition ratio of the hydrogen chloride inhibitor is 0.1 to 10 parts by weight, and the composition ratio of the phenolic antioxidant is 0.1 to 7.0 parts by weight, and the impact-resistant resin contains butadiene-containing rubber, ethylene and propylene as main components. Grafting styrene and at least one vinyl compound selected from the group consisting of acrylonitrile and methyl methacrylate onto at least one rubber selected from the group consisting of ethylene-propylene-diene multi-component copolymer rubber and acrylic ester rubber. It is a graft copolymer obtained by copolymerization, and is a crystalline chlorinated polymer. Ethylene exhibits an amorphous peak at a black angle 2θ of 12 ° to 13 ° by X-ray wide angle diffraction method, and exhibits crystalline peaks at 21 ° and 24 ° of black angle 2θ depending on crystalline polyethylene, and Impact-resistant resin composition in which 3 to 50% by weight of polyethylene crystals remain and the chlorine content is 15 to 50% by weight.